CN103740404A - High-nitrogen high-aromatic hydrocarbon hydrogenation modification method - Google Patents

Abstract

The invention provides a high-nitrogen high-aromatic hydrocarbon hydrogenation modification method, and hydrogenation depth is reasonably arranged according molecule sizes of raw material components with concise flow, and the method is good for catalysts in each zone to perform functions, thereby realizing hydrogenation conversion of all fractions. A first zone reaction effluent 1RP is obtained from coal tar 1F in a first hydrogenation reaction zone 1R, and the first zone reaction effluent 1RP is separated into a first zone hot high-pressure separated oil 1L and a first zone hot high-pressure separated gas 1V by a first zone high-pressure separation part 1HHPS, and the first zone hot high-pressure separated oil 1L is separated into a hydrogenation raw material 1LL and heavy oil 1LH mainly composed of macro-molecules which are difficult to be converted by hydrogenation in a separation part 1 FRAC, and the hydrogenation raw material 1LL and the first zone hot high-pressure separated gas 1V are sent into a second hydrogenation reaction zone 2R. On the basis of realization of all light hydrogenation modification of coal tar 1F by using wide aperture hydrogenation modified catalyst in 1R, and dry point of 2R raw material hydrocarbon is controlled, thereby guarantying operation period of 2R and quality of oil produced by hydrogenation.

Description

The high aromatic hydrogenation method for modifying of a kind of high nitrogen

Technical field

The present invention relates to the high aromatic hydrogenation method for modifying of a kind of high nitrogen, thermal high separating step and hot high score oil fractionating step are set between two hydroconversion reaction zones of series connection, hot high score oil content heats up in a steamer for hydrogenating materials 1LL and the main heavy oil 1LH being comprised of the macromole that is difficult to hydrocracking, hydrogenating materials 1LLHe mono-district hot high score gas 1V removes the second hydroconversion reaction zone 2R, thereby control doing of 2R raw material hydrocarbon, guarantee operational cycle and the hydrogenated oil quality of 2R; Say especially and the present invention relates to a kind of hydrogenating conversion process that conventional boiling point is greater than the coal tar of the coal tar component that the coal tar component of 530 ℃ and conventional boiling point be less than 530 ℃ that simultaneously comprises; More particularly the present invention relates to coalite tar hydrogenating conversion process in a kind of poor quality.

Background technology

In poor quality, the full cut of coalite tar is wide fraction oil product, comprise the cut (containing 2～6 Polycyclic aromatic hydrocarbons) that conventional boiling point that molecular dimension is little is 200～530 ℃ lower than the cut (contained aromatic hydrocarbons is monocycle) of 200 ℃ and the medium conventional boiling point of molecular dimension, conventionally also comprise conventional boiling point that molecular dimension is large and (contain 7 rings and above aromatic hydrocarbons thereof higher than the cut of 530 ℃, colloid, bituminous matter) be coal-tar pitch component, according to the difference of the hot procedure operational condition of coalite tar in coal and generation, quantity and the nature difference of the contained coal-tar pitch of middle coalite tar are larger, comprise the hydroconversion process that hydroconversion process that conventional boiling point is greater than the coal tar of the coal tar component that the coal tar component of 530 ℃ and conventional boiling point be less than 530 ℃ produces diesel component such as coalite tar in full cut simultaneously and substantially can be divided into preposition shallow degree hydro-upgrading process and rearmounted deep hydrogenation upgrading process, there is following features:

1. in preposition shallow degree hydro-upgrading process, while being 2～13% such as the carbon residue content of middle coalite tar in certain scope, the hydrogenation catalyst of similar processing petroleum residual oil is such as hydrodemetallation (HDM), hydrogenating desulfurization, hydrogenation deoxidation, hydrodenitrification, hydrogenation aromatic hydrocarbon saturation catalyst can be processed the above-mentioned middle coalite tar that contains coal-tar pitch, the general character of these catalyzer is to have larger inner duct, activity a little less than, can adapt to the colloid that carbon residue content is high, bitum shallow degree hydro-upgrading, so obtain the shallow degree hydro-upgrading product LQHO of coal-tar pitch, and in the shallow degree hydro-upgrading of this coal-tar pitch process, in middle coalite tar, conventional boiling point is lower than the existence of cut LY or its shallow degree hydro-upgrading product LYHO of 530 ℃, can reduce catalyzer surfaces externally and internally liquid viscosity, the shallow degree hydrogenation that the improves coal-tar pitch molecular diffusion in journey catalyzer duct of correcting one's mistakes, in short be beneficial to the shallow degree hydro-upgrading of coal-tar pitch process,

2. in rearmounted deep hydrogenation upgrading process, the deep hydrogenation upgrading reaction process that conventional boiling point is converted into diesel component lower than the cut LY of 530 ℃ or its shallow degree hydro-upgrading product LYHO in middle coalite tar, the general character of the catalyzer using is that inner duct is moderate, activity is stronger, be difficult to adapt to and maybe can not adapt to the colloid that carbon residue content is high, macromole in bitum shallow degree hydro-upgrading product LQHO such as conventional boiling point higher than the cut LQHO-H of 530 ℃ hybrid process, if combine processing LQHO-H, when consequently LQHO-H content is low, need improve temperature of reaction, LQHO-H content reduces the quality of final hydrogenated products diesel oil or the deactivation rate reduction of erection time of quickening catalyzer of LY or LYHO when high.

Above analytic explanation, in full cut during coalite tar hydrotreatment, shallow degree hydro-upgrading process, degree of depth upgrading process, the mutual relationship existing between lighting end, coal-tar pitch cut, hydrogenation catalyst three is different.Indicated on the one hand the improvement direction of degree of depth upgrading section catalyzer, indicated on the one hand the improvement direction of operating procedure, the present invention proposes improving one's methods of a kind of operating procedure.

The conception of a kind of coal tar hydro-conversion method of the present invention is that thermal high separating step and hot high score oil fractionating step are set between two hydroconversion reaction zones of series connection, coal tar 1F is separated into a district hot high score oil 1LHe mono-district hot high score gas 1V through the first hydroconversion reaction zone 1R gained one district reaction effluent 1RPJing mono-district thermal high separate part 1HHPS, the heavy oil 1LH that one district hot high score oil 1L is separated into hydrogenating materials 1LL and is mainly comprised of the macromole that is difficult to hydrocracking at separate part 1FRAC, hydrogenating materials 1LLHe mono-district hot high score gas 1V removes the second hydroconversion reaction zone 2R.This conception, according to the feed composition molecular size reasonable arrangement hydrogenation degree of depth, give full play to the function of each district's catalyzer, centering coalite tar can be realized hydrogenation of total effluent and transform, advantage is: 1. at 1R, utilize wide aperture catalyst for hydro-upgrading coal tar 1F to be realized on the basis of whole shallow degree hydro-upgradings, control doing of 2R raw material hydrocarbon, guarantee operational cycle and the hydrogenated oil quality of 2R; 2. can process inferior raw material; 3. accidental state one district hot high score oil 1L all discharges hydrogenation reaction system in time.

The method of the invention has no report.

The high aromatic hydrocarbons of high nitrogen of the present invention, it can be any suitable raw material hydrocarbon, refer specifically to and comprise the oil product that conventional boiling point is greater than the coal tar component that the coal tar component of 530 ℃ and conventional boiling point be less than 530 ℃ simultaneously, now raw material hydrocarbon is selected from the full cut of coal-tar middle oil or the full cut of coalite tar or coal-tar middle oil part cut or coalite tar part cut; Raw material hydrocarbon can be also the coal tar that removes specific components, is selected from and removes the coal tar of phenol component or remove the coal tar of naphthalene component or remove the coal tar of anthracene component.

Therefore, the first object of the present invention is to propose a kind of middle coalite tar hydrogenation and produces improving one's methods of diesel component, thermal high separating step and hot high score oil fractionating step are set between two hydroconversion reaction zones of series connection, hot high score oil content heats up in a steamer for hydrogenating materials 1LL and the main heavy oil 1LH being comprised of the macromole that is difficult to hydrocracking, hydrogenating materials 1LLHe mono-district hot high score gas 1V removes the second hydroconversion reaction zone 2R, thereby control doing of 2R raw material hydrocarbon, guarantee operational cycle and the hydrogenated oil quality of 2R; The second object of the present invention is to propose the high aromatic hydrogenation method for modifying of a kind of high nitrogen.

Summary of the invention

The high aromatic hydrogenation method for modifying of a kind of high nitrogen of the present invention, is characterized in that comprising following steps:

1. at the first hydroconversion reaction zone 1R, under hydrogen He Yi district hydrogenation catalyst 1RC existence condition, high aromatic hydrocarbons the first raw material hydrocarbon 1F of high nitrogen completes district hydro-upgrading reaction, generates one and forms Yi district reaction effluent 1RP by hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon;

② mono-district thermal high separate part 1HHPS, a district reaction effluent 1RP is separated into contain low boiling hydrocarbon and foreign gas Yi district hot high score gas gas 1V and who is mainly comprised of hydrogen on volume and mainly by conventional liq hydrocarbon, forms Yi district hot high score fluid body 1L;

The separating of oil part 1FRAC of the ③ mono-hot high score in district, a district hot high score oil 1L is separated into hydrogenating materials 1LL and main by the heavy oil 1LH that is difficult to be formed by the macromole of the second hydroconversion reaction zone 2R hydrocracking;

4. at the second hydroconversion reaction zone 2R, under Er district hydrogenation catalyst 2RC existence condition, one district hot high score gas gas 1VYu bis-district hydrogenation catalyst 2RC contacts, hydrogenating materials 1LLYu bis-district hydrogenation catalyst 2RC contacts, carry out the hydro-upgrading reaction of 2nd district, generate one and form Er district reaction effluent 2RP by hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon; Separated two district reaction effluent 2RP obtain hydrogen-rich gas 2VHe bis-district hydrogenated oil 2RPO, and hydroconversion reaction zone is returned at least a portion hydrogen-rich gas 2V circulation.

One district hot high score oil 1L, conventionally first reducing pressure deviates from gas and then enters separating step, it is characterized in that: the separating of oil part 1FRAC of the ③ mono-hot high score in district, after one district hot high score oil 1L step-down, enter low pressure separate part 1HLPS and be separated into low minute gas 1HLPSV and low minute oily 1HLPSL, low minute oily 1HLPSL through the fractionating step that comprising separation column be separated into mainly the hydrogenating materials 1LL that formed lower than the hydrocarbon component of 500 ℃ by conventional boiling point and main by conventional boiling point, higher than the hydrocarbon component of 500 ℃, formed comprise conventional boiling point higher than the heavy oil 1LH of the hydrocarbon component of 530 ℃.

The present invention is particularly suitable for the situation that the first raw material hydrocarbon is middle coalite tar.

The present invention, the separating of oil part 1FRAC of the hot high score in Yi district, at least a portion heavy oil 1LH can be circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC contact.

The present invention, the separating of oil part 1FRAC of the hot high score in Yi district, at least a portion heavy oil 1LH can obtain pyrogenic reaction effluent through coking, separated pyrogenic reaction effluent obtains mainly the hydrogenating materials 1LHL being comprised of lower than the hydrocarbon component of 530 ℃ conventional boiling point, and hydrogenating materials 1LHL is circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC contact or is circulated to the second hydroconversion reaction zone 2RYu bis-district hydrogenation catalyst 2RC and contacts.

Each step operational condition of the present invention is generally:

1. the first hydroconversion reaction zone 1R operational condition is: temperature is that 180～440 ℃, pressure are that 6.0～30.0MPa, district's Hydrobon catalyst volume space velocity are 0.05～15hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 250～400 ℃, pressure are 6.0～30.0MPa;

4. the second hydroconversion reaction zone 2R operational condition is: temperature is that 280～460 ℃, pressure are that 6.0～30.0MPa, two district's Hydrobon catalyst volume space velocities are 0.05～15hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1.

Each step operational condition of the present invention is generally:

1. the first hydroconversion reaction zone operational condition is: temperature is that 180～360 ℃, pressure are that 12.0～25.0MPa, district's Hydrobon catalyst volume space velocity are 0.15～2.0hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 280～350 ℃, pressure are 12.0～25.0MPa;

4. the second hydroconversion reaction zone operational condition is: temperature is that 320～440 ℃, pressure are that 12.0～25.0MPa, two district's Hydrobon catalyst volume space velocities are 0.15～2.0hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1.

The Action Target of hydro-upgrading reactive moieties of the present invention is generally:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is 2～13%, hydrogen consumption at the first hydroconversion reaction zone 1R accounts for 25～65% of the first raw material hydrocarbon total hydrogen consumption, the olefin saturated rate of coal tar is greater than 90%, the oxygen extrusion rate of coal tar is greater than 90%, in one district reaction effluent 1RP, amount of metal is with the ratio of hydrocarbon group component lower than 4/1000000ths, and the carbon residue decreasing ratio of coal tar is greater than 35%;

The cetane value of the full cut of diesel oil in ④Er district reaction effluent 2RP is higher than 28.

The Action Target of hydro-upgrading reactive moieties of the present invention is generally:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is 2～10%, hydrogen consumption at the first hydroconversion reaction zone 1R accounts for 35～55% of the first raw material hydrocarbon total hydrogen consumption, the olefin saturated rate of coal tar is greater than 95%, the oxygen extrusion rate of coal tar is greater than 95%, in one district reaction effluent 1RP, amount of metal is with the ratio of hydrocarbon group component lower than 2/1000000ths, and the carbon residue decreasing ratio of coal tar is greater than 45%;

The cetane value of the full cut of diesel oil in ④Er district reaction effluent 2RP is higher than 32.

The separate mode of the present invention two district reaction effluent 2RP is generally: ④ bis-district cold anticyclone separate part 2LHPS, water filling Hou Er district reaction effluent 2RPW be separated into one on volume mainly by hydrogen forms Er district cold high score gas gas 2LHPSV, one mainly by conventional liq hydrocarbon form Er district cold high score fluid body 2LHPSL and one main by water, formed contain ammonia components Er district cold high score water liquid 2LHPSW; At least a portion two district cold high score gas gas 2LHPSV enter hydro-upgrading reactive moieties as hydrogen-rich gas 2V; Two district's heat separate part 2LHPS service temperature of colding pressing is 20～70 ℃.

When the separate mode of the present invention two district reaction effluent 2RP comprises two district thermal high separate part 2HHPS, it is characterized in that: ④ bis-district thermal high separate part 2HHPS, two district reaction effluent 2RP are separated into one and on volume, mainly by hydrogen, form Er district hot high score gas gas 2HHPSV and one and mainly by conventional liq hydrocarbon, form Er district hot high score fluid body 2HHPSL, and at least a portion two district hot high score gas gas 2HHPSV enter two district cold anticyclone separate part 2LHPS; Two district's thermal high separate part 2HHPS service temperatures are generally 200～380 ℃, are generally is 280～350 ℃.

The present invention, separated two district hydrogenated oil 2RPO obtain two district's narrow fraction oil products, and at least a portion two district's narrow fraction oil products are circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC contact or are circulated to the second hydroconversion reaction zone 2RYu bis-district hydrogenation catalyst 2RC contacts.

The present invention, separated two district hydrogenated oil 2RPO obtain two district's narrow fraction oil products, and at least a portion is mainly greater than the component of 350 ℃ by conventional boiling point and forms Er district narrow fraction oil product and be circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC and contact or be circulated to the second hydroconversion reaction zone 2RYu bis-district hydrogenation catalyst 2RC and contact.

In high aromatic hydrocarbons the first raw material hydrocarbon 1F of high nitrogen of the present invention, aromaticity content is greater than 40 % by weight, and conventional boiling point is greater than 20 % by weight higher than the aromaticity content of 350 ℃, and Conradson carbon residue is 2～13%.

A kind of a particular job mode of the present invention is that the second hydroconversion reaction zone 2R carries out hydrocracking reaction, it is characterized in that:

1. the first raw material hydrocarbon completes deep hydrofinishing reaction at the first hydroconversion reaction zone 1R, and the cetane value of the full cut of diesel oil in a district reaction effluent 1RP is higher than 24;

4. the second hydroconversion reaction zone 2R is used hydrocracking catalyst to carry out hydrocracking reaction to the raw material hydrocarbon of the second hydroconversion reaction zone 2R; The cetane value of the full cut of diesel oil in two district reaction effluent 2RP is higher than 32.

A kind of a particular job mode of the present invention is that the second hydroconversion reaction zone 2R carries out hydrocracking reaction, and its operational condition is generally:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is that the 2～13%, first hydroconversion reaction zone 1R operational condition is: temperature is that 180～440 ℃, pressure are that 10.0～25.0MPa, district's Hydrobon catalyst volume space velocity are 0.05～1.25hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1, the cetane value of the full cut of diesel oil in a district reaction effluent 1RP is higher than 26;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 250～400 ℃, pressure are 10.0～25.0MPa;

4. the second hydroconversion reaction zone 2R operational condition is: temperature is that 300～460 ℃, pressure are that 6.0～30.0MPa, two district's hydrocracking catalyst volume space velocities are 0.15～3.0hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1; The cetane value of the full cut of diesel oil in two district reaction effluent 2RP is higher than 38.

A kind of a particular job mode of the present invention is that the second hydroconversion reaction zone 2R carries out hydrocracking reaction, and its operational condition is generally:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is that the 2～10%, first hydroconversion reaction zone 1R operational condition is: temperature is that 180～440 ℃, pressure are that 12.0～18.0MPa, district's Hydrobon catalyst volume space velocity are 0.15～0.65hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1, the cetane value of the full cut of diesel oil in a district reaction effluent 1RP is higher than 32;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 280～350 ℃, pressure are 12.0～18.0MPa;

4. the second hydroconversion reaction zone 2R operational condition is: temperature is that 330～420 ℃, pressure are that 12.0～18.0MPa, two district's hydrocracking catalyst volume space velocities are 0.25～2.0hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1; The cetane value of the full cut of diesel oil in two district reaction effluent 2RP is higher than 42.

The present invention, be applicable to any the first suitable raw material hydrocarbon, be particularly suitable for comprising the oil product that conventional boiling point is greater than the coal tar component that the coal tar component of 530 ℃ and conventional boiling point be less than 530 ℃, now the first raw material hydrocarbon is selected from the full cut of coal-tar middle oil or the full cut of coalite tar or coal-tar middle oil part cut or coalite tar part cut simultaneously; The first raw material hydrocarbon can be the coal tar that removes specific components, is selected from and removes the coal tar of phenol component or remove the coal tar of naphthalene component or remove the coal tar of anthracene component.

Accompanying drawing explanation

Accompanying drawing is principle process schematic diagram of the present invention.As shown in drawings, high aromatic hydrocarbons the first raw material hydrocarbon 1F of high nitrogen enters the first hydroconversion reaction zone 1R, under hydrogen He Yi district hydrogenation catalyst 1RC existence condition, high aromatic hydrocarbons the first raw material hydrocarbon 1F of high nitrogen completes district hydro-upgrading reaction, generates one and forms Yi district reaction effluent 1RP by hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon; Yi district thermal high separate part 1HHPS, a district reaction effluent 1RP is separated into contain low boiling hydrocarbon and foreign gas Yi district hot high score gas gas 1V and who is mainly comprised of hydrogen on volume and mainly by conventional liq hydrocarbon, forms Yi district hot high score fluid body 1L; The separating of oil part 1FRAC of the hot high score in Yi district, a district hot high score oil 1L is separated into hydrogenating materials 1LL and main by the heavy oil 1LH that is difficult to be formed by the macromole of the second hydroconversion reaction zone 2R hydrocracking; At the second hydroconversion reaction zone 2R, under Er district hydrogenation catalyst 2RC existence condition, one district hot high score gas gas 1VYu bis-district hydrogenation catalyst 2RC contacts, hydrogenating materials 1LLYu bis-district hydrogenation catalyst 2RC contacts, carry out the hydro-upgrading reaction of 2nd district, generate one and form Er district reaction effluent 2RP by hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon.

embodiment

Below describe the present invention in detail.

Pressure of the present invention is absolute pressure.

Conventional boiling point of the present invention refers to the vapor-liquid equilibrium temperature of material under a barometric point.

Impurity composition of the present invention refers to the hydride of non-hydrocarbon component in stock oil as water, ammonia, hydrogen sulfide, hydrogenchloride etc.

Conventional gas hydrocarbon of the present invention refers to the hydro carbons that is gaseous state under normal condition, comprises methane, ethane, propane, butane.

Conventional liq hydrocarbon of the present invention refers to the hydro carbons being in a liquid state under normal condition, comprises the hydro carbons that pentane and boiling point thereof are higher.

Proportion of the present invention, unless stated otherwise, refers to the ratio of fluid density and normal pressure under normal pressure, 15.6 ℃ of conditions, 15.6 ℃ of Water Under density.

Petroleum naphtha component of the present invention refers to conventional boiling point lower than the conventional liq hydrocarbon of 200 ℃.

It is the hydro carbons of 200～375 ℃ that diesel component of the present invention refers to conventional boiling point.

The composition of component of the present invention or concentration or content or yield value, unless stated otherwise, be weight basis value.

The first raw material hydrocarbon of the present invention is the high aromatic hydrocarbons of high nitrogen, can be the coal tar from pyrolysis of coal or coal generating gas process.Coal tar of the present invention can be coalite tar, coal-tar middle oil, coal-tar heavy oil cut and mixing oil thereof.All variations within the specific limits of processing condition due to raw coal character, pyrolysis of coal or coal generating gas process, coal tar oil properties also changes within the specific limits, the processing condition of coal-tar heavy oil primary distillation process and product requirement also change within the specific limits, therefore the character of coal-tar heavy oil cut also changes within the specific limits.Hydrogenating materials coal tar oil properties of the present invention, conventional boiling point is generally 50～650 ℃ and is generally 60～550 ℃, proportion is generally 0.91～1.22, water-content is generally 0.2～5.0%, and conventionally metal content is that 2～80PPm, sulphur content are 0.4～0.8%, nitrogen content is 0.4～1.8%, oxygen level is 0.4～8.0%.

The high aromatic hydrogenation method for modifying of a kind of high nitrogen of the present invention, is characterized in that comprising following steps:

The high aromatic hydrogenation method for modifying of a kind of high nitrogen of the present invention, is characterized in that comprising following steps:

1. at the first hydroconversion reaction zone 1R, under hydrogen He Yi district hydrogenation catalyst 1RC existence condition, high aromatic hydrocarbons the first raw material hydrocarbon 1F of high nitrogen completes district hydro-upgrading reaction, generates one and forms Yi district reaction effluent 1RP by hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon;

② mono-district thermal high separate part 1HHPS, a district reaction effluent 1RP is separated into contain low boiling hydrocarbon and foreign gas Yi district hot high score gas gas 1V and who is mainly comprised of hydrogen on volume and mainly by conventional liq hydrocarbon, forms Yi district hot high score fluid body 1L;

The separating of oil part 1FRAC of the ③ mono-hot high score in district, a district hot high score oil 1L is separated into hydrogenating materials 1LL and main by the heavy oil 1LH that is difficult to be formed by the macromole of the second hydroconversion reaction zone 2R hydrocracking;

4. at the second hydroconversion reaction zone 2R, under Er district hydrogenation catalyst 2RC existence condition, one district hot high score gas gas 1VYu bis-district hydrogenation catalyst 2RC contacts, hydrogenating materials 1LLYu bis-district hydrogenation catalyst 2RC contacts, carry out the hydro-upgrading reaction of 2nd district, generate one and form Er district reaction effluent 2RP by hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon; Separated two district reaction effluent 2RP obtain hydrogen-rich gas 2VHe bis-district hydrogenated oil 2RPO, and hydroconversion reaction zone is returned at least a portion hydrogen-rich gas 2V circulation.

One district hot high score oil 1L, conventionally first reducing pressure deviates from gas and then enters separating step, it is characterized in that: the separating of oil part 1FRAC of the ③ mono-hot high score in district, after one district hot high score oil 1L step-down, enter low pressure separate part 1HLPS and be separated into low minute gas 1HLPSV and low minute oily 1HLPSL, low minute oily 1HLPSL through the fractionating step that comprising separation column be separated into mainly the hydrogenating materials 1LL that formed lower than the hydrocarbon component of 500 ℃ by conventional boiling point and main by conventional boiling point, higher than the hydrocarbon component of 500 ℃, formed comprise conventional boiling point higher than the heavy oil 1LH of the hydrocarbon component of 530 ℃.

The present invention is particularly suitable for the situation that the first raw material hydrocarbon is middle coalite tar.

The present invention, the separating of oil part 1FRAC of the hot high score in Yi district, at least a portion heavy oil 1LH can be circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC contact.

The present invention, the separating of oil part 1FRAC of the hot high score in Yi district, at least a portion heavy oil 1LH can obtain pyrogenic reaction effluent through coking, separated pyrogenic reaction effluent obtains mainly the hydrogenating materials 1LHL being comprised of lower than the hydrocarbon component of 530 ℃ conventional boiling point, and hydrogenating materials 1LHL is circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC contact or is circulated to the second hydroconversion reaction zone 2RYu bis-district hydrogenation catalyst 2RC and contacts.

Each step operational condition of the present invention is generally:

1. the first hydroconversion reaction zone 1R operational condition is: temperature is that 180～440 ℃, pressure are that 6.0～30.0MPa, district's Hydrobon catalyst volume space velocity are 0.05～15hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 250～400 ℃, pressure are 6.0～30.0MPa;

4. the second hydroconversion reaction zone 2R operational condition is: temperature is that 280～460 ℃, pressure are that 6.0～30.0MPa, two district's Hydrobon catalyst volume space velocities are 0.05～15hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1.

Each step operational condition of the present invention is generally:

1. the first hydroconversion reaction zone operational condition is: temperature is that 180～360 ℃, pressure are that 12.0～25.0MPa, district's Hydrobon catalyst volume space velocity are 0.15～2.0hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 280～350 ℃, pressure are 12.0～25.0MPa;

4. the second hydroconversion reaction zone operational condition is: temperature is that 320～440 ℃, pressure are that 12.0～25.0MPa, two district's Hydrobon catalyst volume space velocities are 0.15～2.0hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1.

The Action Target of hydro-upgrading reactive moieties of the present invention is generally:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is 2～13%, hydrogen consumption at the first hydroconversion reaction zone 1R accounts for 25～65% of the first raw material hydrocarbon total hydrogen consumption, the olefin saturated rate of coal tar is greater than 90%, the oxygen extrusion rate of coal tar is greater than 90%, in one district reaction effluent 1RP, amount of metal is with the ratio of hydrocarbon group component lower than 4/1000000ths, and the carbon residue decreasing ratio of coal tar is greater than 35%;

The cetane value of the full cut of diesel oil in ④Er district reaction effluent 2RP is higher than 28.

The Action Target of hydro-upgrading reactive moieties of the present invention is generally:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is 2～10%, hydrogen consumption at the first hydroconversion reaction zone 1R accounts for 35～55% of the first raw material hydrocarbon total hydrogen consumption, the olefin saturated rate of coal tar is greater than 95%, the oxygen extrusion rate of coal tar is greater than 95%, in one district reaction effluent 1RP, amount of metal is with the ratio of hydrocarbon group component lower than 2/1000000ths, and the carbon residue decreasing ratio of coal tar is greater than 45%;

The cetane value of the full cut of diesel oil in ④Er district reaction effluent 2RP is higher than 32.

The separate mode of the present invention two district reaction effluent 2RP is generally: ④ bis-district cold anticyclone separate part 2LHPS, water filling Hou Er district reaction effluent 2RPW be separated into one on volume mainly by hydrogen forms Er district cold high score gas gas 2LHPSV, one mainly by conventional liq hydrocarbon form Er district cold high score fluid body 2LHPSL and one main by water, formed contain ammonia components Er district cold high score water liquid 2LHPSW; At least a portion two district cold high score gas gas 2LHPSV enter hydro-upgrading reactive moieties as hydrogen-rich gas 2V; Two district's heat separate part 2LHPS service temperature of colding pressing is 20～70 ℃.

When the separate mode of the present invention two district reaction effluent 2RP comprises two district thermal high separate part 2HHPS, it is characterized in that: ④ bis-district thermal high separate part 2HHPS, two district reaction effluent 2RP are separated into one and on volume, mainly by hydrogen, form Er district hot high score gas gas 2HHPSV and one and mainly by conventional liq hydrocarbon, form Er district hot high score fluid body 2HHPSL, and at least a portion two district hot high score gas gas 2HHPSV enter two district cold anticyclone separate part 2LHPS; Two district's thermal high separate part 2HHPS service temperatures are generally 200～380 ℃, are generally is 280～350 ℃.

The present invention, separated two district hydrogenated oil 2RPO obtain two district's narrow fraction oil products, and at least a portion two district's narrow fraction oil products are circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC contact or are circulated to the second hydroconversion reaction zone 2RYu bis-district hydrogenation catalyst 2RC contacts.

The present invention, separated two district hydrogenated oil 2RPO obtain two district's narrow fraction oil products, and at least a portion is mainly greater than the component of 350 ℃ by conventional boiling point and forms Er district narrow fraction oil product and be circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC and contact or be circulated to the second hydroconversion reaction zone 2RYu bis-district hydrogenation catalyst 2RC and contact.

In high aromatic hydrocarbons the first raw material hydrocarbon 1F of high nitrogen of the present invention, aromaticity content is greater than 40 % by weight, and conventional boiling point is greater than 20 % by weight higher than the aromaticity content of 350 ℃, and Conradson carbon residue is 2～13%.

A kind of a particular job mode of the present invention is that the second hydroconversion reaction zone 2R carries out hydrocracking reaction, it is characterized in that:

1. the first raw material hydrocarbon completes deep hydrofinishing reaction at the first hydroconversion reaction zone 1R, and the cetane value of the full cut of diesel oil in a district reaction effluent 1RP is higher than 24;

4. the second hydroconversion reaction zone 2R is used hydrocracking catalyst to carry out hydrocracking reaction to the raw material hydrocarbon of the second hydroconversion reaction zone 2R; The cetane value of the full cut of diesel oil in two district reaction effluent 2RP is higher than 32.

A kind of a particular job mode of the present invention is that the second hydroconversion reaction zone 2R carries out hydrocracking reaction, and its operational condition is generally:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is that the 2～13%, first hydroconversion reaction zone 1R operational condition is: temperature is that 180～440 ℃, pressure are that 10.0～25.0MPa, district's Hydrobon catalyst volume space velocity are 0.05～1.25hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1, the cetane value of the full cut of diesel oil in a district reaction effluent 1RP is higher than 26;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 250～400 ℃, pressure are 10.0～25.0MPa;

4. the second hydroconversion reaction zone 2R operational condition is: temperature is that 300～460 ℃, pressure are that 6.0～30.0MPa, two district's hydrocracking catalyst volume space velocities are 0.15～3.0hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1; The cetane value of the full cut of diesel oil in two district reaction effluent 2RP is higher than 38.

A kind of a particular job mode of the present invention is that the second hydroconversion reaction zone 2R carries out hydrocracking reaction, and its operational condition is generally:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is that the 2～10%, first hydroconversion reaction zone 1R operational condition is: temperature is that 180～440 ℃, pressure are that 12.0～18.0MPa, district's Hydrobon catalyst volume space velocity are 0.15～0.65hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1, the cetane value of the full cut of diesel oil in a district reaction effluent 1RP is higher than 32;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 280～350 ℃, pressure are 12.0～18.0MPa;

4. the second hydroconversion reaction zone 2R operational condition is: temperature is that 330～420 ℃, pressure are that 12.0～18.0MPa, two district's hydrocracking catalyst volume space velocities are 0.25～2.0hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1; The cetane value of the full cut of diesel oil in two district reaction effluent 2RP is higher than 42.

The present invention, be applicable to any the first suitable raw material hydrocarbon, be particularly suitable for comprising the oil product that conventional boiling point is greater than the coal tar component that the coal tar component of 530 ℃ and conventional boiling point be less than 530 ℃, now the first raw material hydrocarbon is selected from the full cut of coal-tar middle oil or the full cut of coalite tar or coal-tar middle oil part cut or coalite tar part cut simultaneously; The first raw material hydrocarbon can be the coal tar that removes specific components, is selected from and removes the coal tar of phenol component or remove the coal tar of naphthalene component or remove the coal tar of anthracene component.

In the hydro-upgrading process of coal tar, water is disadvantageous component, on the one hand, in heat temperature raising process before coal tar enters the hydrogenator of the first hydroconversion reaction zone 1R, the existence of water can aggravate the corrosion of acids to pipeline, equipment etc. in coal tar, the metal ions such as iron that corrosion produces enter hydrogenator, for guaranteeing the operational cycle of expection, must use more Hydrodemetalation catalyst (protective material) to increase hydrogen consumption simultaneously; On the other hand, the increase of raw water content will improve reaction process steam partial pressure, unfavorable to catalyst performance stabilised and long-term operation.Therefore, before coal tar enters the first hydroconversion reaction zone 1R, conventionally carry out processed to reduce as much as possible water-content, the method for coal tar dehydration is unrestricted, such as the dehydration of pressurized, heated liquid, distillation dehydration, electric field desalting and dewatering and be used in combination.

The coal tar conventional method of dewatering is decompression dehydration after heat temperature raising: first by coal tar, under certain pressure, (such as pressure-controlling is at 0.5～1.0MPa) is heated to 80～200 ℃ preferably 100～160 ℃, then enter the water trap (flash tank or dehydration tower) in the lower operation of negative pressure (if pressure-controlling is in 0.025～0.05MPa (absolute pressure)), the water vapor of oily is discharged water trap top, after condensing cooling, enter liquid collecting tank and then discharge system, liquid collecting tank is connected with vacuum system.Dehydrated coal tar is discharged from water trap bottom.

Industry coal tar also contains harmful solid particulate (solid particulate that is greater than 10～20 microns such as diameter) conventionally; in order to prevent that harmful solid particulate from damaging coal tar high-pressure delivery pump and being deposited on beds, carries out coal tar filtration under the proper temperature condition of conventionally dewatering forward and backward at coal tar.

The present invention advises that industrial coal tar dewaters and filtration treatment before entering hydrogenation reaction part.

District's hydro-upgrading of the present invention reacts a word, refer to the hydrofining reaction process that the first raw material hydrocarbon 1F occurs under hydrogen and suitable Yi district hydrogenation catalyst 1RC existence condition, its minimum reaction depth should possess MIN industrial significance: be the second hydroconversion reaction zone 2R suitable hydro-upgrading raw material hydrocarbon is provided, should determine according to the requirement of feed coal tar 1F character He Er district hydrogenation catalyst 2RCDui bis-district's feedstock properties: generally this process completes olefins hydrogenation, hydrodemetallation (HDM), appropriateness removal of ccr by hydrotreating, shallow appropriate hydrogenating desulfurization, appropriateness hydrodenitrification, appropriateness aromatic saturation, the first raw material hydrocarbon, in the hydrogen consumption of the first hydroconversion reaction zone 1R, accounts for the first raw material hydrocarbon total hydrogen consumption: be generally 10～65%, be generally 35～55%, the olefin saturated rate of this process coal tar: be generally greater than 75%, be conventionally greater than 95%, more preferably greater than 98%, the oxygen extrusion rate of this process coal tar: be generally greater than 70%, be conventionally greater than 90%, more preferably greater than 95%, the metal extrusion rate of this process coal tar: be generally greater than 80%, be conventionally greater than 95%, more preferably greater than 99%, this process to the carbon residue decreasing ratio of feed coal tar be greater than 25%, be conventionally greater than 40%, more preferably greater than 65%, to delay coking speed, the prolong operation cycle of two district's catalyst for hydro-upgrading, under these conditions, complete certain desulfurization, denitrification percent simultaneously, conventionally wish that the hydrocarbon ils in a district reaction effluent 1RP preferably possesses certain light transmission.

The first raw material hydrocarbon total hydrogen consumption refers to the first raw material hydrocarbon of unit weight in the gross weight of the hydrogen of the first hydroconversion reaction zone 1R and the second hydroconversion reaction zone 2R consumption.

The first described hydroconversion reaction zone 1R carries out coal tar one district hydro-upgrading reaction, difference because of the difference of coal tar raw material character (olefin(e) centent, metal content, oxygen level, sulphur content, nitrogen content, aromaticity content, boiling range, proportion, carbon residue content) and the hydrofining degree of depth (olefins hydrogenation, hydrodemetallation (HDM), hydrogenation deoxidation, removal of ccr by hydrotreating, hydrogenating desulfurization, hydrodenitrification, aromatic hydrogenation be saturated, hydrofining " cracking ") to a certain degree, the variation range of its operational condition is very wide, should determine according to concrete coal tar hydrogenation modification reaction target.

Described the first hydroconversion reaction zone 1R that carries out coal tar one district hydro-upgrading reaction, use Yi district hydrogenation catalyst 1RC can be the series combination of one or two or more catalyzer and load in mixture.One district hydrogenation catalyst 1RC can be Hydrobon catalyst and combination or its function combinations such as olefins hydrogenation catalyzer, Hydrodemetalation catalyst, hydrogenation deoxidation catalyst, removal of ccr by hydrotreating catalyzer, Hydrobon catalyst, hydrodenitrogenation catalyst, hydrocatalyst for saturating arylhydrocarbon.Because coal tar contains alkene, metal, therefore make spent hydroprocessing catalyst before Hydrobon catalyst, carry out hydrogenation olefin saturated, hydrodemetallation (HDM).

The first described hydroconversion reaction zone 1R, any supplementary sulphur can be added to reactive moieties as required, to guarantee the necessary minimum concentration of hydrogen sulfide of reactive moieties, guarantee that the necessary hydrogen sulfide sectional pressure of catalyzer of reaction process is not less than minimum must value: such as 500PPm or 1000PPm.Described supplementary sulphur can be the material without undesirable action to coal tar hydrogenation modification process that sulfide hydrogen maybe can be converted into hydrogen sulfide, such as hydrogen sulfide containing gas or oil product, or after contacting with high-temperature hydrogen, be converted into the dithiocarbonic anhydride of hydrogen sulfide or Methyl disulfide etc.

According to the present invention, setting steps object is 2. in order to obtain a district hot high score fluid body 1L, then the separation of the hot high score fluid in implementation step ③Yi district body 1L, therefore a district hot high score fluid body 1L is preferably mainly comprised of high boiling component, such as mainly by conventional boiling point higher than the cut of 350 ℃ or main by conventional boiling point the fractions consisting higher than 450 ℃, that is to say that the service temperature of a district thermal high separate part 1HHPS is unsuitable too low.The operational condition of one district thermal high separate part 1HHPS is: temperature is generally 250～400 ℃, is generally 280～350 ℃, and it is 6.0～30.0MPa that pressure is generally, be generally 12.0～25.0MPa.

According to the present invention, at the second hydroconversion reaction zone 2R, under hydrogen He Er district hydrogenation catalyst 2RC existence condition, at least a portion hydrocarbon raw material completes the reaction of deep hydrogenation upgrading, generates one and forms Er district reaction effluent 2RP by hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon.

The hydro-upgrading reaction of described Er district, difference because of the difference of its raw material (hydro carbons in a district reaction effluent 1RP) character (sulphur content, nitrogen content, aromaticity content, boiling range, proportion, carbon residue content) and the hydro-upgrading degree of depth (hydrogenating desulfurization, hydrodenitrification, hydrogenation are saturated, hydrofining " cracking " to a certain degree, hydrocracking), the variation range of its operational condition is very wide, should determine according to concrete enabling objective.

The second described hydroconversion reaction zone 2R, use Er district hydrogenation catalyst 2RC can be the series combination of one or two or more catalyzer and load in mixture.Two district hydrogenation catalyst 2RC can be Hydrobon catalyst and the combinations thereof such as hydrogen desulfurization agent, hydrodenitrification agent, the agent of hydrogenation aromatic saturation.At afterbody or the rear portion of reaction process, can use hydrocracking catalyst (comprise and relax cracking catalyst) and combination thereof.A kind of a particular job mode of the present invention is: deep hydrofinishing reaction, the second hydroconversion reaction zone 2R that the first hydroconversion reaction zone 1R carries out coal tar carry out hydrocracking reaction.Can select the amorphous hydrocracking catalyst of not fusion molecular sieve or the amorphous hydrocracking catalyst of a small amount of fusion molecular sieve, to strengthen as far as possible the adaptive faculty to organic nitrogen compound in raw material, improve diesel component productive rate.As required, the component that affects quality product that rear portion Hydrobon catalyst bed produces hydrocracking process is set conventionally after hydrocracking catalyst bed as mercaptan is completed to hydrofining.

According to the present invention, separated two district reaction effluent 2RP obtain hydrogen-rich gas 2VHe bis-district hydrogenated oil 2RPO, and at least a portion hydrogen-rich gas 2V enters hydro-upgrading reactive moieties.

The separate part of two district reaction effluent 2RP, conventionally comprise two district cold anticyclone separate part 2LHPS, described two district reaction effluent 2RP are cooling and be separated into one and on volume, mainly by hydrogen, form Er district cold high score gas gas 2LHPSV and one and mainly by conventional liq hydrocarbon, form Er district cold high score fluid body 2LHPSL.Described Er district cold anticyclone separate part 2LHPS, its separator operation pressure is that the second hydroconversion reaction zone 2R pressure deducts true pressure and falls, described true pressure falls, unsuitable too low or too high, is generally 0.3～1.2MPa, is preferably 0.5～0.8MPa.The service temperature of two district cold anticyclone separate part 2LHPS is generally 20～80 ℃, is generally 30～70 ℃.The separating of oil part of the cold high score in Er district, the separated two cold high score oil in district obtain the narrow fraction oil product that comprises diesel oil distillate.Er district cold high score oil 2LHPSL separate part, first two district cold high score oil 2LHPSL reduce pressure conventionally, Pressure Drop to 0.5～4.0MPa forms gas, the logistics of liquid mixed phase conventionally, then through separated with or the process of fractionation complete separated, be conventionally separated into gas, liquefied gas, naphtha fraction (or light naphthar and heavy naphtha), diesel oil distillate (or low freezing point diesel fuel and high freezing point diesel fuel) (or solar oil and heavy gas oil) and the more last running that may exist as products such as hydrogenation wax oil or hydrogenation tail oils.As required, two district reaction effluent 2RP can arrange water filling and wash ammonia step.Described Er district cold high score gas gas 2LHPSV, its density of hydrogen value, should not be too low (causing device working pressure to rise), generally should be not less than 70% (v), should be not less than 80% (v), be preferably not less than 85% (v).As previously mentioned at least a portion, be generally 85～100% described two district cold high score gas gas 2LHPSV return the first hydroconversion reaction zone 1R and or the second hydroconversion reaction zone 2R form circulating hydrogen (making reactor inlet hydrogen and cold hydrogen), so that the necessary amounts of hydrogen in hydroconversion reaction zone and hydrogen concentration to be provided.According to the present invention, new hydrogen enter the first hydroconversion reaction zone 1R and or the second hydroconversion reaction zone 2R, the hydrogen consuming with postreaction process, recommends all new hydrogen to enter the first hydroconversion reaction zone 1R, at utmost to improve reaction process density of hydrogen.New hydrogen hydrogen concentration is more high better, generally should not, lower than 95% (v), preferably be not less than 99% (v).

When the present invention is applied to coal tar hydrogenation modification process, according to the present invention, two district reaction effluent 2RP bis-district thermal high separate part 2HHPS can be set, in this flow process, two district reaction effluent 2RP are introduced into service temperature and are generally 150～400 ℃, be generally 200～380 ℃ bis-district thermal high separate part 2HHPS and be separated into one on volume, mainly by hydrogen, forms that Er district hot high score gas gas 2HHPSV and one is mainly comprised of conventional liq hydrocarbon contain dissolved hydrogen Er district hot high score fluid body 2HHPSL, two district hot high score gas gas 2HHPSV enter two district cold anticyclone separate part 2LHPS.The separating of oil part of two district's hot high score oil hot high scores in 2HHPSL Er district (comprising separated and or the process of fractionation) is isolated narrow fraction oil product.The separating of oil part of two district's cold high scores in the separating of oil part Yu Er of hot high score district, can partial common or all shared.

Two district hydrogenated oil 2RPO of the present invention, refer to two district reaction effluent 2RP and isolate the hydrocarbon liquid that hydrogen-rich gas 2V process obtains.When the separate part of Dang Er district reaction effluent 2RP adopts two district cold anticyclone separate part 2LHPS separated, hydrogen-rich gas 2V is two district cold high score gas gas 2LHPSV, two district hydrogenated oil 2RPO and is two district cold high score fluid body 2LHPSL.When the separate part of Dang Er district reaction effluent 2RP adopts two thermal high separate part 2HHPS He Er district, district cold anticyclone separate part 2LHPS separated, hydrogen-rich gas 2V is two district cold high score gas gas 2LHPSV, two district hydrogenated oil 2RP and comprises two hot high score fluid body 2HHPSL He Er district, district cold high score fluid body 2LHPSL.

Metal, oxygen, sulphur, the nitrogen of the typical coal tar hydrogenating conversion process of the present invention in can effective elimination coal tar, make alkene wherein, most of fused ring compound saturated, the cracking reaction of concurrent first portion macromole, make oil property obtain expectedly significantly improving, the first raw material hydrocarbon hydrogenation final product naphtha fraction can be used as high-quality catalytic reforming raw material component, and the first raw material hydrocarbon hydrogenation final product diesel oil distillate can be used as fine-quality diesel oil blending component.When the present invention is applied to coal tar hydrogenating conversion process, its minimum reaction depth should possess MIN industrial significance: the diesel oil distillate of producing expection character, the cetane value of the full cut of diesel oil in general two district reaction effluent 2RP is usually above 28, generally higher than 35, and 20 ℃ of density of the full cut of diesel oil in general two district reaction effluent 2RP are usually less than 900 kilograms/cubic metre, generally lower than 890 kilograms/cubic metre.

Compare with the direct tandem process of the second hydroconversion reaction zone 2R with conventional the first hydroconversion reaction zone 1R, the invention has the advantages that:

1. at 1R, utilize wide aperture catalyst for hydro-upgrading coal tar 1F to be realized on the basis of whole shallow degree hydro-upgradings, control doing of 2R raw material hydrocarbon, guarantee operational cycle and the hydrogenated oil quality of 2R;

2. be particularly suitable for processing and comprise the oil product that conventional boiling point is greater than the coal tar component that the coal tar component of 530 ℃ and conventional boiling point be less than 530 ℃ simultaneously;

3. accidental state one district hot high score oil 1L all discharges hydrogenation reaction system in time.

The present invention is according to the component molecular size reasonable arrangement hydrogenation degree of depth in the first raw material hydrocarbon, and flow process is brief, is beneficial to the function of each district's catalyzer of performance, and centering low temperature low grade coal tar can be realized hydrogenation of total effluent and transform.

Embodiment mono-

Middle coalite tar character in Table 1, table 2, the purification coal tar that coal tar A obtains after filtration, dehydration, desalination step, as the first raw material hydrocarbon 1F, is processed according to the present invention:

1. at the first hydroconversion reaction zone 1R, successively with olefins hydrogenation catalyzer, Hydrodemetalation catalyst, removal of ccr by hydrotreating catalyzer, (the desulfurization of appropriateness of shallow degree Hydrobon catalyst, denitrogenation, aromatic saturation) contact, complete district hydro-upgrading reaction, the first hydroconversion reaction zone 1R operational condition is: temperature is 180～220 ℃ of olefins hydrogenation beds, 250～320 ℃ of Hydrodemetalation catalyst beds, 310～360 ℃ of removal of ccr by hydrotreating beds, 330～380 ℃ of shallow degree Hydrobon catalysts, pressure is 14.0～18.0MPa, the volume space velocity of the shallow degree Hydrobon catalyst in one district hydrogenation catalyst 1RC is 0.35～0.6hr^-1, hydrogen/stock oil volume ratio is 1500: 1～2000: 1, the hydrogen consumption of coal-tar middle oil the first raw material hydrocarbon accounts for 35～45% (1.63～2.09% centering temperature coal tar weight) of the first raw material hydrocarbon total hydrogen consumption, the olefin saturated rate of coal tar is greater than 95%, the oxygen extrusion rate of coal tar is greater than 88%, in one district reaction effluent 1RP, amount of metal is with the ratio of hydrocarbon group component lower than 4/1000000ths, and the carbon residue decreasing ratio of coal tar is 45～65%,

② mono-district thermal high separate part 1HHPS, district's thermal high separate part operational condition is: pressure is that 14.0～18.0MPa service temperature is 320～365 ℃; One district hydrogenation reaction effluent 1RP is separated into contain low boiling hydrocarbon and foreign gas Yi district hot high score gas gas 1V and who is mainly comprised of hydrogen on volume and mainly by conventional liq hydrocarbon, forms Yi district hot high score fluid body 1L;

The separating of oil part 1FRAC of the ③ mono-hot high score in district, one district hot high score oil 1L is depressurized to and enters low pressure separate part 1HLPS after 2.0MPa and be separated into low minute gas 1HLPSV and low minute oily 1HLPSL, low minute oily 1HLPSL is separated into mainly the hydrogenating materials 1LL that is comprised of lower than the hydrocarbon component of 515 ℃ conventional boiling point and the main heavy oil 1LH being comprised of higher than the hydrocarbon component of 515 ℃ conventional boiling point through the fractionating step that comprises separation column, heavy oil 1LH quantity is 6～7% of the first raw material hydrocarbon 1F, can be used as oil fuel and sells;

4. at the second hydroconversion reaction zone 2R, under Er district hydrogenation catalyst existence condition, one district hot high score gas gas 1V contacts with hydrogenating materials 1LLYu bis-district's hydrogenation catalysts, carry out two districts hydro-upgradings reactions, beds is in series by Hydrobon catalyst bed, hydrodenitrogenation catalyst bed, hydrogenation polycyclic aromatic hydrocarbons saturation catalyst bed successively; The second hydro-upgrading reactive moieties 2R operational condition is: temperature is that 350～400 ℃, pressure are that 14.0～18.0MPa, two district's hydrogenation catalyst 2RC volume space velocities are 0.3～0.6hr^-1, hydrogen/stock oil volume ratio is 1500: 1～2000: 1; The hydrogen consumption of two district's raw material hydrocarbon accounts for 55～65% (2.56～3.02%) of the first raw material hydrocarbon total hydrogen consumption; Er district cold anticyclone separate part 2LHPS, water filling Hou Er district reaction effluent 2RPW is cooled to 40～55 ℃, at working pressure, be under 14.0～18.0MPa condition, be separated into one on volume mainly by hydrogen forms Er district cold high score gas gas 2LHPV, one mainly by conventional liq hydrocarbon form Er district cold high score fluid body 2LHPL and one main by water, formed contain ammonia components Er district cold high score water liquid 2LHPW; At least a portion two district cold high score gas gas 2LHPV enter hydroconversion reaction zone as hydrogen-rich gas 2V; The character of the full cut of diesel oil of two district cold high score fluid body 2LHPL: cetane value higher than 28, sulphur content is 880～900 kilograms/cubic metre lower than 20PPm, nitrogen content lower than 100PPm, 20 ℃ of density.

Table 1 coal tar true boiling point distillation data

Coal tar numbering	A
		Component	Mass yield %
Water	3.07
		＜170℃	4.30
170℃～210℃	1.48
		210℃～230℃	4.81
230℃～300℃	14.93
		300℃～500℃	59.28
＞500℃	12.13
		＞530℃	～6

[0134]table 2 coal tar character

Coal tar numbering	A
		Bottle density (20 ℃), kg.m-3	1.0658
Boiling range, ℃, 95% point/do	542/595
		Sulphur, μ g.g-1	1800
Nitrogen, μ g.g-1	6101
		C，％	81.36
H，％	8.21
		Condensation point, ℃	30
Carbon residue, %	9.77
		Moisture, %	4.1
Throw out, %	0.48
		Flash-point (remaining silent), ℃	126
Heavy metal, μ g.g-1	?
		Fe/Na/Ni/Mg	108.70/5.74/1.39/56.32
Ca/V/K/Pb	362.4/0.17/16.25/11.43
		Co/Cu/Mn/Zn/Mo	0.77/0.21/4.24/6.84/0.02
Mass spectrum forms, %	?
		Colloid	33.5
Paraffinic hydrocarbons	11.5
		Naphthenic hydrocarbon	5.2
Monocycle/dicyclo/tri-ring/Fourth Ring	2.7/0.7/1.3/0.5
		Aromatic hydrocarbons	49.8
Monocycle/dicyclo/tri-ring/Fourth Ring/five rings	13.8/16.4/8.3/5.0/0.6
		Total thiophene/do not identify	4.4/1.3

[0136]table 3 the first hydrofining reaction partly forms with partially catalyzed agent

Table 4 the second hydrofining reaction is partly used the physico-chemical property of partially catalyzed agent

Embodiment bis-

Compare with embodiment mono-, at the second hydroconversion reaction zone 2R, after existing hydrogenation catalyst bed, serial hydrocracking catalyzer, macromole aromatic hydrocarbons is carried out to selectivity and relax cracking, preferentially improve conventional boiling point higher than the wax oil component of 350 ℃, improve conventional boiling point lower than the character of the diesel component of 350 ℃ simultaneously.

The conventional boiling point that separated two district hydrogenated oil 2RPO obtain is higher than the wax oil HD of 350 ℃, can partly or entirely circulate contact component part with the hydrocracking catalyst of the second hydroconversion reaction zone 2R and circulate or the cracking flow process that all circulates.

Embodiment tri-

Compare with embodiment mono-, the separating of oil part 1FRAC of the hot high score in Yi district, 75% heavy oil 1LH is circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC contact, and heavy oil 1LH quantity is 2～3% of the first raw material hydrocarbon 1F.

Embodiment tetra-

Compare with embodiment mono-, the conventional boiling point that separated two district hydrogenated oil 2RPO obtain is higher than the wax oil HD of 350 ℃, part or all of wax oil HD can be introduced to the 3rd 3RJi hydrocracking reaction district, hydroconversion reaction zone and carry out hydrocracking, Hydrobon catalyst bed is set before and after hydrocracking catalyst bed.The hydrogenation reaction effluent 3RP of the 3rd hydroconversion reaction zone 3R, can remove the separate part of the first hydroconversion reaction zone 1R or the second hydroconversion reaction zone 2RHuo bis-district reaction effluent 2RP.

The physico-chemical property of catalyzer for table 5 the 3rd hydroconversion reaction zone 3R

Although only enumerate four embodiment herein, be enough to show effect of the present invention.

Claims (22)

1. the high aromatic hydrogenation method for modifying of high nitrogen, is characterized in that comprising following steps:

1. at the first hydroconversion reaction zone 1R, under hydrogen He Yi district hydrogenation catalyst 1RC existence condition, high aromatic hydrocarbons the first raw material hydrocarbon 1F of high nitrogen completes district hydro-upgrading reaction, generates one and forms Yi district reaction effluent 1RP by hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon;

② mono-district thermal high separate part 1HHPS, a district reaction effluent 1RP is separated into contain low boiling hydrocarbon and foreign gas Yi district hot high score gas gas 1V and who is mainly comprised of hydrogen on volume and mainly by conventional liq hydrocarbon, forms Yi district hot high score fluid body 1L;

The separating of oil part 1FRAC of the ③ mono-hot high score in district, a district hot high score oil 1L is separated into hydrogenating materials 1LL and main by the heavy oil 1LH that is difficult to be formed by the macromole of the second hydroconversion reaction zone 2R hydrocracking;

4. at the second hydroconversion reaction zone 2R, under Er district hydrogenation catalyst 2RC existence condition, one district hot high score gas gas 1VYu bis-district hydrogenation catalyst 2RC contacts, hydrogenating materials 1LLYu bis-district hydrogenation catalyst 2RC contacts, carry out the hydro-upgrading reaction of 2nd district, generate one and form Er district reaction effluent 2RP by hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon; Separated two district reaction effluent 2RP obtain hydrogen-rich gas 2VHe bis-district hydrogenated oil 2RPO, and hydroconversion reaction zone is returned at least a portion hydrogen-rich gas 2V circulation.

2. method according to claim 1, is characterized in that:

The separating of oil part 1FRAC of the ③ mono-hot high score in district, after one district hot high score oil 1L step-down, enter low pressure separate part 1HLPS and be separated into low minute gas 1HLPSV and low minute oily 1HLPSL, low minute oily 1HLPSL through the fractionating step that comprising separation column be separated into mainly the hydrogenating materials 1LL that formed lower than the hydrocarbon component of 500 ℃ by conventional boiling point and main by conventional boiling point, higher than the hydrocarbon component of 500 ℃, formed comprise conventional boiling point higher than the heavy oil 1LH of the hydrocarbon component of 530 ℃.

3. method according to claim 1, is characterized in that:

1. the first raw material hydrocarbon is middle coalite tar.

The separating of oil part 1FRAC of the ③ mono-hot high score in district, at least a portion heavy oil 1LH is circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC contact.

4. method according to claim 1, is characterized in that:

1. the first raw material hydrocarbon is middle coalite tar.

The separating of oil part 1FRAC of the ③ mono-hot high score in district, at least a portion heavy oil 1LH obtains pyrogenic reaction effluent through coking, separated pyrogenic reaction effluent obtains mainly the hydrogenating materials 1LHL being comprised of lower than the hydrocarbon component of 530 ℃ conventional boiling point, and hydrogenating materials 1LHL is circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC and contacts.

5. method according to claim 1, is characterized in that:

1. the first raw material hydrocarbon is middle coalite tar.

The separating of oil part 1FRAC of the ③ mono-hot high score in district, at least a portion heavy oil 1LH obtains pyrogenic reaction effluent through coking, separated pyrogenic reaction effluent obtains mainly the hydrogenating materials 1LHL being comprised of lower than the hydrocarbon component of 530 ℃ conventional boiling point, and hydrogenating materials 1LHL is circulated to the second hydroconversion reaction zone 2RYu bis-district hydrogenation catalyst 2RC and contacts.

6. according to the method described in claim 1 or 2 or 3 or 4 or 5, it is characterized in that:

1. the first hydroconversion reaction zone 1R operational condition is: temperature is that 180～440 ℃, pressure are that 6.0～30.0MPa, district's Hydrobon catalyst volume space velocity are 0.05～15hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 250～400 ℃, pressure are 6.0～30.0MPa;

4. the second hydroconversion reaction zone 2R operational condition is: temperature is that 280～460 ℃, pressure are that 6.0～30.0MPa, two district's Hydrobon catalyst volume space velocities are 0.05～15hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1.

7. method according to claim 6, is characterized in that:

1. the first hydroconversion reaction zone operational condition is: temperature is that 180～360 ℃, pressure are that 12.0～25.0MPa, district's Hydrobon catalyst volume space velocity are 0.15～2.0hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 280～350 ℃, pressure are 12.0～25.0MPa;

4. the second hydroconversion reaction zone operational condition is: temperature is that 320～440 ℃, pressure are that 12.0～25.0MPa, two district's Hydrobon catalyst volume space velocities are 0.15～2.0hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1.

8. according to the method described in claim 1 or 2 or 3 or 4 or 5, it is characterized in that:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is 2～13%, hydrogen consumption at the first hydroconversion reaction zone 1R accounts for 25～65% of the first raw material hydrocarbon total hydrogen consumption, the olefin saturated rate of coal tar is greater than 90%, the oxygen extrusion rate of coal tar is greater than 90%, in one district reaction effluent 1RP, amount of metal is with the ratio of hydrocarbon group component lower than 4/1000000ths, and the carbon residue decreasing ratio of coal tar is greater than 35%;

The cetane value of the full cut of diesel oil in ④Er district reaction effluent 2RP is higher than 28.

9. method according to claim 8, is characterized in that:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is 2～10%, hydrogen consumption at the first hydroconversion reaction zone 1R accounts for 35～55% of the first raw material hydrocarbon total hydrogen consumption, the olefin saturated rate of coal tar is greater than 95%, the oxygen extrusion rate of coal tar is greater than 95%, in one district reaction effluent 1RP, amount of metal is with the ratio of hydrocarbon group component lower than 2/1000000ths, and the carbon residue decreasing ratio of coal tar is greater than 45%;

The cetane value of the full cut of diesel oil in ④Er district reaction effluent 2RP is higher than 32.

10. according to the method described in claim 1 or 2 or 3 or 4 or 5, it is characterized in that:

④ bis-district cold anticyclone separate part 2LHPS, water filling Hou Er district reaction effluent 2RPW be separated into one on volume mainly by hydrogen forms Er district cold high score gas gas 2LHPSV, one mainly by conventional liq hydrocarbon form Er district cold high score fluid body 2LHPSL and one main by water, formed contain ammonia components Er district cold high score water liquid 2LHPSW; At least a portion two district cold high score gas gas 2LHPSV enter hydro-upgrading reactive moieties as hydrogen-rich gas 2V; Two district's heat separate part 2LHPS service temperature of colding pressing is 20～70 ℃.

11. methods according to claim 10, is characterized in that:

④ bis-district thermal high separate part 2HHPS, two district reaction effluent 2RP are separated into one and on volume, mainly by hydrogen, form Er district hot high score gas gas 2HHPSV and one and mainly by conventional liq hydrocarbon, form Er district hot high score fluid body 2HHPSL, and at least a portion two district hot high score gas gas 2HHPSV enter two district cold anticyclone separate part 2LHPS; Two district's thermal high separate part 2HHPS service temperatures are 200～380 ℃.

12. according to method described in claim 11, it is characterized in that:

④Er district thermal high separate part 2HHPS service temperature is 280～350 ℃.

13. according to method described in claim 1 or 2 or 3 or 4 or 5, it is characterized in that:

Separated two district hydrogenated oil 2RPO obtain two district's narrow fraction oil products, and at least a portion two district's narrow fraction oil products are circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC contact.

14. according to method described in claim 13, it is characterized in that:

Separated two district hydrogenated oil 2RPO obtain two district's narrow fraction oil products, and at least a portion is mainly greater than the component of 350 ℃ by conventional boiling point and forms Er district narrow fraction oil product and be circulated to the first hydroconversion reaction zone 1RYu mono-district hydrogenation catalyst 1RC and contact.

15. according to method described in claim 1 or 2 or 3 or 4 or 5, it is characterized in that:

Separated two district hydrogenated oil 2RPO obtain two district's narrow fraction oil products, and at least a portion two district's narrow fraction oil products are circulated to the second hydroconversion reaction zone 2RYu bis-district hydrogenation catalyst 2RC contacts.

16. according to method described in claim 15, it is characterized in that:

Separated two district hydrogenated oil 2RPO obtain two district's narrow fraction oil products, and at least a portion is mainly greater than the component of 350 ℃ by conventional boiling point and forms Er district narrow fraction oil product and be circulated to the second hydroconversion reaction zone 2RYu bis-district hydrogenation catalyst 2RC and contact.

17. methods according to claim 1, is characterized in that:

1. in the first raw material hydrocarbon 1F, aromaticity content is greater than 40 % by weight, and conventional boiling point is greater than 20 % by weight higher than the aromaticity content of 350 ℃, and Conradson carbon residue is 2～13%.

18. according to method described in claim 1 or 2 or 3 or 4 or 5, it is characterized in that:

1. the first raw material hydrocarbon completes deep hydrofinishing reaction at the first hydroconversion reaction zone 1R, and the cetane value of the full cut of diesel oil in a district reaction effluent 1RP is higher than 24;

4. the second hydroconversion reaction zone 2R is used hydrocracking catalyst to carry out hydrocracking reaction to the raw material hydrocarbon of the second hydroconversion reaction zone 2R; The cetane value of the full cut of diesel oil in two district reaction effluent 2RP is higher than 32.

19. according to method described in claim 18, it is characterized in that:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is that the 2～13%, first hydroconversion reaction zone 1R operational condition is: temperature is that 180～440 ℃, pressure are that 10.0～25.0MPa, district's Hydrobon catalyst volume space velocity are 0.05～1.25hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1, the cetane value of the full cut of diesel oil in a district reaction effluent 1RP is higher than 26;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 250～400 ℃, pressure are 10.0～25.0MPa;

4. the second hydroconversion reaction zone 2R operational condition is: temperature is that 300～460 ℃, pressure are that 6.0～30.0MPa, two district's hydrocracking catalyst volume space velocities are 0.15～3.0hr^-1, hydrogen/stock oil volume ratio is 400: 1～4000: 1; The cetane value of the full cut of diesel oil in two district reaction effluent 2RP is higher than 38.

20. according to method described in claim 19, it is characterized in that:

1. in the first raw material hydrocarbon, the carbon residue of coalite tar is that the 2～10%, first hydroconversion reaction zone 1R operational condition is: temperature is that 180～440 ℃, pressure are that 12.0～18.0MPa, district's Hydrobon catalyst volume space velocity are 0.15～0.65hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1, the cetane value of the full cut of diesel oil in a district reaction effluent 1RP is higher than 32;

②Yi district thermal high separate part 1HHPS operational condition is: temperature is that 280～350 ℃, pressure are 12.0～18.0MPa;

4. the second hydroconversion reaction zone 2R operational condition is: temperature is that 330～420 ℃, pressure are that 12.0～18.0MPa, two district's hydrocracking catalyst volume space velocities are 0.25～2.0hr^-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1; The cetane value of the full cut of diesel oil in two district reaction effluent 2RP is higher than 42.

21. according to the method described in claim 1 or 2 or 3 or 4 or 5, it is characterized in that:

1. the first raw material hydrocarbon is greater than the oil product of the coal tar component that the coal tar component of 530 ℃ and conventional boiling point be less than 530 ℃ for comprise conventional boiling point simultaneously, is selected from the full cut of coal-tar middle oil or the full cut of coalite tar or coal-tar middle oil part cut or coalite tar part cut.

22. methods according to claim 21, is characterized in that:

1. the first raw material hydrocarbon is the coal tar that removes specific components, is selected from and removes the coal tar of phenol component or remove the coal tar of naphthalene component or remove the coal tar of anthracene component.