CN103102911A - Hydrogenation method for producing low aromatic hydrocarbon solvent oil from biological oil - Google Patents

Abstract

The present invention relates to a hydrogenation method for producing a low aromatic hydrocarbon solvent oil from a biological oil. The method is characterized in that a biological oil is adopted as a raw material oil; under a hydrogenation operation condition, the raw material oil and hydrogen gas pass through a first stage hydrogenation reaction zone containing at least two hydrogenation reactors, wherein the raw material oil and the hydrogen gas pass through a low temperature operation reactor, and then pass through a high temperature operation reactor; hydrogen-rich gas separated from the stream generated from hydrogenation is recycled, and the separated liquid enters a second stage hydrocracking reaction zone; sub-hydrogen gas separated from the stream generated from hydrocracking is recycled, and the separated liquid product is subjected to fractionation to obtain various solvent oil products; and a sulfur-containing material is supplied to the reaction material so as to maintain a hydrogen sulfide content in the circulation gas. Compared to the method in the prior art, the method of the present invention has the following advantages that: low aromatic hydrocarbon solvent oil production methods are increased, activity stability of the catalyst can be ensured, and stable and long period device operation can be ensured.

Description

Bio-oil is produced the method for hydrotreating of low aromatic solvent naphtha

Technical field

The invention belongs to the production method of renewable energy source, relate to a kind of method of hydrotreating, particularly a kind of take bio-oil as stock oil, the method for hydrotreating of direct production low aromatic solvent naphtha.

Background technology

The world economy sustainable development, at present in global range, the main source of Chemicals is fossil energy, wherein most importantly oil and coal.These two kinds of fossil energies all belong to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality aggravation, difficulty of processing and tooling cost increase gradually, except being improved, existing oil Refining Technologies seeks new oil substitutes, produce satisfactory product with minimum cost, especially the development and utilization of renewable resources obtains paying attention to more and more widely.

Bio-oil is as renewable resources, and chief component is carbon, hydrogen and oxygen, and very similar to the composition of alkane, alcohol, ether etc., each research unit and enterprise are all making great efforts to carry out it as the research of clean energy.Utilizing the method production biofuel (being generally fatty acid methyl ester) of transesterify has been proven technique, but because the fatty acid methyl ester oxygen level is high, although many countries and regions have been put into effect the standard of biofuel successively, and be not suitable for all oil engines.Bio-oil is produced automotive fuel by the method for hydrogenation, and soon oxygen is all removed or partly removed and produce the product that meets the automotive fuel standard, and this method can directly satisfy the requirement of existing market.

existing animal-plant oil hydrogenation method is produced the processing technology of automotive fuel, US20060186020, EP1693432, CN101321847A, CN200710012090.6, CN200680045053.9, CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and CN101029245A etc. disclose the vegetables oil hydroconversion process, adopt the coker gasoline cut, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil), the petroleum hydrocarbon cuts such as wax oil cut and bio-oil are mixed into the hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses vegetables oil such as containing unsaturated fatty acids, fat and animal oil mixing back end hydrogenation is produced the diesel oil blending component of diesel oil distillate scope.EP1741767 and EP1741768 disclose a kind of method of producing the low freezing point diesel fuel cut with animal-plant oil.

Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter that runs into is that the bed carbon distribution causes shortening running period, the more catalyst changeout of need to often stopping work, and also the main purpose product of these technology is automotive fuel.

Solvent oil is important petroleum products, and its added value is higher than fuel product, and particularly the added value of high-grade low aromatic solvent naphtha is higher.High-grade low aromatic solvent naphtha raw materials for production are limited at present (generally only limits to gasoline fraction or the kerosene(oil)fraction of paraffinic crude, perhaps reforming raffinate oil etc.), owing to requiring aromaticity content lower (some solvent oil index request aromaticity content is lower than 0.1%), therefore need to adopt complicated processing route, condition is harsh, production cost is high, has limited the production of high-grade low aromatic solvent naphtha.

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of bio-oil and produce the method for hydrotreating of low aromatic solvent naphtha, can be separately take bio-oil as stock oil, the method for direct production low aromatic solvent naphtha under the condition of hydrogenation, has hydrogenation process stable, the characteristics such as running period is long.

The method of hydrotreating that bio-oil of the present invention is produced low aromatic solvent naphtha comprises following content:

(a) one or more in bio-oil are stock oil;

(b) under the hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone of at least two hydrogenators, load hydrogenation catalyst in hydrogenator, stock oil and hydrogen is the hydrogenator by cold operation at first, then the hydrogenator by high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and the Co of sulphided state;

(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles after processing, liquid phase with enter the second segment reaction zone that uses hydrocracking catalyst after circulation gas mixes, under response behaviour, the active metal component of hydrocracking catalyst is one or more in W, Mo, Ni and the Co of sulphided state;

(d) gas phase of second segment reaction zone reaction effluent recycles, and liquid phase fractionation in separation column of second segment reaction zone reaction effluent obtains the low aromatic solvent oil distillate;

(e) replenish S-contained substance in reaction mass, to keep hydrogen sulfide content in circulation gas.

In the inventive method step (a), the bio-oil that uses can comprise vegetables oil or animal grease, vegetables oil comprises one or more in soybean oil, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, sesame oil, Oleum Gossypii semen, sunflower seed oil and rice bran wet goods, and animal grease comprises one or more in butter, lard, sheep oil and fish oil etc.

In the inventive method step (b), the hydroprocessing condition of the hydrogenator of cold operation is generally reaction pressure 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and the cumulative volume air speed is 0.3h^-1~ 6.0h^-1, 120 ℃ ~ 280 ℃ of average reaction temperature; The operational condition of the hydrogenator of high-temperature operation is reaction pressure 2.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.3h^-1~ 6.0h^-1, average reaction temperature than the hydrogenator of cold operation high 50 ℃ ~ 300 ℃, preferred high 80 ~ 220 ℃.Between the hydrogenator of cold operation and the hydrogenator of high-temperature operation, process furnace or interchanger are set, with the temperature of reaction of the hydrogenator of adjusting high-temperature operation.

In the inventive method step (b), reaction mass is at first by in the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is take the weight content of oxide compound as 3%～20%.Reaction mass continues the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses in the hydrogenator of high-temperature operation counts 15%～40% with oxide weight.In the hydrogenator of preferred high-temperature operation, the active component content of catalyzer is higher than 3～25 percentage points of catalyzer in the cold operation hydrogenator.Reactor generally can arrange 2 ~ 5, is preferably 2.A kind of catalyzer can be loaded in each hydrogenator, also multiple catalysts can be loaded.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent simultaneously, as P, Si, B, Ti, Zr etc.Can adopt the commercial catalyst, also can be by the existing method preparation in this area.The hydrogenation activity component is the catalyzer of oxidation state, carries out conventional sulfidizing before using, and makes the hydrogenation activity component be converted into sulphided state.the business hydrogenation catalyst mainly contains, as 3926 of Fushun Petrochemical Research Institute (FRIPP) development, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS, the hydrogenation catalysts such as FZC-41, the HR-416 of Inst Francais Du Petrole, the hydrogenation catalysts such as HR-448, the ICR174 of CLG company, ICR178, the hydrogenation catalysts such as ICR179, Uop Inc. is newly developed HC-P, HC-K UF-210/220, the TK-525 of Topsor company, TK-555, the hydrogenation catalysts such as TK-557, the KF-752 of AKZO company, KF-840, KF-848, KF-901, the hydrogenation catalysts such as KF-907.

In the inventive method step (c), the operational condition of second segment reaction zone is generally reaction pressure 2.0MPa ~ 20.0MPa, common (herein identical finger identical pressure rating identical with the first paragraph reaction zone, Pressure Drop due to Flow of Goods and Materials, second segment reaction zone reaction pressure can be a little less than the first paragraph reaction zone), hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h^-1~ 6.0h^-1, 180 ℃ ~ 465 ℃ of average reaction temperature; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h^-1~ 4.0h^-1, 200 ℃ ~ 445 ℃ of average reaction temperature.

In the inventive method step (c), the hydrocracking catalyst of second segment reaction zone has the cracking function, as contains the components such as Y zeolite and/or ZSM-5 molecular sieve.The hydrogenation active metals component of hydrocracking catalyst is generally 5%～40% in the weight content of oxide compound.The weight content of molecular sieve component in hydrocracking catalyst is generally 5%～60%.Can contain simultaneously other refractory inorganic oxides in hydrocracking catalyst.The commercial catalysts that the second segment reaction zone uses mainly contains, as Fushun Petrochemical Research Institute (FRIPP) develop 3971,3976, FC-12, FC-18, FC-24, FC-26, FC-32, FC-46, FC-50, FDW-1 etc.

In the inventive method step (d), the low aromatic solvent naphtha that obtains is the mixed solvent oil distillate, can continue according to the actual requirements fractionation and obtain one or more in vegetable oil extraction solvent, No. 90 solvent oils, No. 120 solvent oils, No. 200 solvent oils, the trade mark low aromatic solvent naphthas such as D30, D40.Specifically can determine according to the boiling range of mixed solvent oil.

In the inventive method step (d), at low conversion rate in 100% the time, the unconverted oil that fractionates out in separation column can loop back first paragraph reaction zone or second segment reaction zone, preferred cycle is returned the second segment reaction zone, and the quality that loops back the unconverted oil of reactive system is 5%～50% of fresh feed (raw material that refers to the first reaction zone).

In the inventive method, first paragraph reaction zone (refining reaction district) and second segment reaction zone (cracking reaction district) hydrogenation activity component are the catalyzer of oxidation state, carried out conventional sulfidizing before using, make the hydrogenation activity component be converted into sulphided state, perhaps use the outer good catalyzer of prevulcanized of device.

In the inventive method, the sulfur-containing medium that replenishes in reaction mass (optimum is dosed in stock oil) can be the compound of sulfur-bearing, as DMDS, and CS₂Deng, can be also the oil light-end products of sulfur-bearing, as the boat coal of sulfur-bearing, diesel oil etc.By replenishing of sulphur, can guarantee that the hydrogen sulfide content in circulation gas is not less than 0.005v%, preferred 0.01v%～2.0v%.

In the inventive method, can be at the appropriate Hydrobon catalyst that replenishes of arranging at last of hydrocracking catalyst bed, with material hydrogenation such as issuable a small amount of rare hydrocarbon in hydrocracking process.

In prior art bio-oil usually by separately or with the method for the method production automotive fuel of other petroleum products mixings back end hydrogenations.The present invention uses grating technology and the operational condition of catalyzer by optimization, first paragraph hydrofining (hydrogenation catalyst of grating), and the second segment hydrocracking can be directly take bio-oil as the raw material production low aromatic solvent naphtha.Expanded the raw material sources of high added value low aromatic solvent naphtha, and production cost is low, can further improves added value of product.

Description of drawings

Fig. 1 is the method for hydrotreating principle flow chart that bio-oil of the present invention is produced low aromatic solvent naphtha.

Embodiment

method of the present invention is specific as follows: the mixing oil of one or more in the bio-oil is as stock oil, under the hydroprocessing condition, stock oil and hydrogen are by cold operation and the high-temperature operation hydrogenation first paragraph reaction zone of loading catalyst, the hydrogenated oil that obtains separates the dehydration that obtains in high-pressure separator (abbreviation high score) after, gas circulation is used, also can go out system, the liquid fractionation that obtains and hydrogen are mixed into and comprise the second segment reaction zone with cracking performance hydrocracking catalyst, obtain the hydrocracking logistics and separate the gas circulation use that obtains in high-pressure separator (abbreviation high score), also can go out system, the liquid fractionation obtains all kinds of SOLVENTS oil production, during low conversion rate, unconverted oil is circulated to the second segment reaction zone.The bio-oil that embodiment uses is the commercially available prod, filtering solid impurity before using.

Further illustrate particular case of the present invention below by embodiment.

The chief component of table 1 hydrogenation catalyst and character.

Catalyzer	Catalyzer 1	Catalyzer 2	Catalyzer 3	Cracking catalyst 1	Cracking catalyst 2
						Catalyzer forms	?	?	?	?	?
MoO3，wt%	7.0	15.7	24.5	10.0	20.0
						NiO，wt%	2.0	?	3.8	2.1	4.6
CoO，wt%	?	2.4	?	?	?
						ZSM-5 molecular sieve, wt%	?	?	?	13.6	?
Y molecular sieve, wt%	?	?	?	?	20.5
						Alumina supporter, wt%	Surplus	Surplus	Surplus	Surplus	Surplus
The main character of catalyzer	?	?	?	?	?
						Specific surface, m2/g	>160	>160	>160	>160	>160
Pore volume, ml/g	>0.30	0.32	0.33	>0.34	>0.34

Table 2 embodiment processing condition and test-results.

First paragraph reaction zone processing condition	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					Stock oil	Soybean oil	Rapeseed oil	Oleum Gossypii semen	Oleum Gossypii semen
The cold operation reactor	?	?	?	?
					Catalyzer	Catalyzer 1	Catalyzer 1/ catalyzer 2	Catalyzer 1/ catalyzer 2	Catalyzer 2
The catalyst volume ratio	100	20:80	50:50	100
					Reaction pressure, MPa	17.0	4.0	12.0	8.0
The entrance hydrogen to oil volume ratio	2000:1	300:1	1000:1	800:1
					The cumulative volume air speed, h-1	2.0	1.5	0.8	0.4
Average reaction temperature, ℃	240	180	200	150
					The high-temperature operation reactor	?	?	?	?
Catalyzer	Catalyzer 3	Catalyzer 3	Catalyzer 3	Catalyzer 3
					Reaction pressure, MPa	17.0	4.0	14.0	8.0
The entrance hydrogen to oil volume ratio	2000:1	300:1	1000:1	1000:1
					The cumulative volume air speed, h-1	2.0	1.8	0.5	0.5
Average reaction temperature, ℃	380	350	360	320
					Second segment reaction zone processing condition	?	?	?	?
Stock oil	The first paragraph product liquid	The first paragraph product liquid	The first paragraph product liquid	First paragraph product liquid+15% unconverted oil
					Catalyzer	Cracking catalyst 1	Cracking catalyst 1	Cracking catalyst 2	Cracking catalyst 2
Reaction pressure, MPa	17.0	4.0	12.0	8.0
					The entrance hydrogen to oil volume ratio	1500	500	800	1000
Volume space velocity, h-1	2.0	4.5	1.5	3.0
					Average reaction temperature, ℃	320	360	310	290
Sulfur-containing medium	DMDS	DMDS	CS2	CS2
					Hydrogen sulfide content in circulation gas, μ L/L	20000	400	4000	1000
The solvent oil cut	?	?	?	?
					Yield, quality %	88	82	89	88
Aromaticity content	Do not detect	Do not detect	Do not detect	Do not detect
					Sulphur content, μ g/g	<0.5	<0.5	<0.5	<0.5
The boiling range scope, ℃	65～174	63～153	62～126	60～95

Table 3 embodiment processing condition and test-results.

First paragraph reaction zone processing condition	Embodiment 5	Comparative example 1	Comparative example 2	Comparative example 3
					Stock oil	Oleum Gossypii semen	Oleum Gossypii semen	Oleum Gossypii semen	Oleum Gossypii semen
The cold operation reactor	?	?	?	?
					Catalyzer	Catalyzer 1	?	?	?
Reaction pressure, MPa	10.0	?	?	?
					The entrance hydrogen to oil volume ratio	2000:1	?	?	?
The cumulative volume air speed, h-1	2.0	?	?	?
					Average reaction temperature, ℃	200	?	?	?
The high-temperature operation reactor	?	?	?	?
					Catalyzer	Catalyzer 3	Catalyzer 3/ cracking catalyst 1	Catalyzer 3/ cracking catalyst 1	Catalyzer 3/ cracking catalyst 1
Reaction pressure, Mpa	10.0	10.0	10.0	10.0
					The entrance hydrogen to oil volume ratio	1000:1	1000:1	1000:1	1000:1
The cumulative volume air speed, h-1	0.8	0.46	0.46	0.46
					Average reaction temperature, ℃	330	330	330	340
Second segment reaction zone processing condition	?	?	?	?
					Catalyzer	Cracking catalyst 1	?	?	?
Reaction pressure, Mpa	10.0	?	?	?
					The entrance hydrogen to oil volume ratio	1000:1	?	?	?
The cumulative volume air speed, h-1	2.5	?	?	?
					Average reaction temperature, ℃	330	?	?	?
Sulfur-containing medium	CS2	CS2	CS2	CS2
					Hydrogen sulfide content in circulation gas, μ L/L	500	500	500	500
Runtime, h	1000	200	300	500
					Pressure Drop, MPa	0	0.1	0.3	0.6
The solvent oil cut	?	?	?	?
					Yield, quality %	86	86	61	38
Aromaticity content	Do not detect	Do not detect	Do not detect	Do not detect
					Sulphur content, μ g/g	<0.5	<0.5	<0.5	<0.5
The boiling range scope, ℃	61～170	65～170	65～170	65～170

Yield is take the second segment reaction zone feeds as benchmark.Comparative example catalyzer 3 consumptions are identical with the total consumption of catalyzer 3 with embodiment 5 catalyzer 1, and comparative example cracking catalyst 1 consumption is identical with embodiment 5 cracking catalyst 1 consumptions.

Can be found out by embodiment, the method for hydrotreating of bio-oil by present technique can the various low aromatic solvent oil productions of direct production, by selecting different bio-oils, can produce high-quality low aromatic solvent naphtha, and running are stable.

Claims (10)

1. a bio-oil is produced the method for hydrotreating of low aromatic solvent naphtha, it is characterized in that comprising following process:

(a) one or more in bio-oil are stock oil;

(b) under the hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone of at least two hydrogenators, load hydrogenation catalyst in hydrogenator, stock oil and hydrogen is the hydrogenator by cold operation at first, then the hydrogenator by high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and the Co of sulphided state;

(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles after processing, liquid phase with enter the second segment reaction zone that uses hydrocracking catalyst after circulation gas mixes, under response behaviour, the active metal component of hydrocracking catalyst is one or more in W, Mo, Ni and the Co of sulphided state;

(d) gas phase of second segment reaction zone reaction effluent recycles, and liquid phase fractionation in separation column of second segment reaction zone reaction effluent obtains the low aromatic solvent oil distillate;

(e) replenish S-contained substance in reaction mass, to keep hydrogen sulfide content in circulation gas.

2. it is characterized in that in accordance with the method for claim 1: the bio-oil described in step (a) comprises vegetables oil or animal grease.

3. in accordance with the method for claim 1, it is characterized in that: in step (b), the reaction pressure of the hydrogenator of cold operation is 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and the cumulative volume air speed is 0.3h^-1~ 6.0h^-1, average reaction temperature is 120 ℃ ~ 280 ℃; The reaction pressure of the hydrogenator of high-temperature operation is 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h^-1~ 6.0h^-1, average reaction temperature than the hydrogenator of cold operation high 50 ℃ ~ 300 ℃, preferred high 80 ~ 220 ℃.

4. according to the described method of claim 1 or 3, it is characterized in that: step (b) reaction mass is at first by in the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is take the weight content of oxide compound as 3%～20%; Reaction mass continues the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses in the hydrogenator of high-temperature operation counts 15%～40% with oxide weight.

5. in accordance with the method for claim 4, it is characterized in that: in step (b), in the hydrogenator of high-temperature operation, the active component content of catalyzer is higher than 3～25 percentage points of the catalyzer in the cold operation hydrogenator.

6. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of second segment reaction zone is 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h^-1~ 6.0h^-1, 180 ℃ ~ 465 ℃ of average reaction temperature; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h^-1~ 4.0h^-1, 200 ℃ ~ 445 ℃ of average reaction temperature.

7. in accordance with the method for claim 1, it is characterized in that: in step (c), the hydrocracking catalyst of second segment reaction zone has the cracking function, hydrocracking catalyst contains Y zeolite and/or ZSM-5 molecular sieve component, the hydrogenation active metals component of hydrocracking catalyst is take the weight content of oxide compound as 5%～40%, and the weight content of molecular sieve component in hydrocracking catalyst is 5%～60%.

8. in accordance with the method for claim 1, it is characterized in that: in step (d), unconverted oil is circulated to the first paragraph reaction zone, perhaps is circulated to the second segment reaction zone, and turning oil accounts for 5%～50% of fresh feed quality.

9. in accordance with the method for claim 1, it is characterized in that: in step (e), the sulfur-containing medium that replenishes in reaction mass is the compound of sulfur-bearing, the oil light-end products of sulfur-bearing.

10. according to the described method of claim 1 or 10, it is characterized in that: in step (e), the hydrogen sulfide content in circulation gas is not less than 0.005v%, preferred 0.01v%～2.0v%.

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