A kind of hydrogenation-dechlorination method of ionic liquid alkylate oilTechnical field
The present invention relates to a kind of hydrogenation-dechlorination methods of alkylate oil, specifically lead to the alkylate oil of high chlorine contentsIt crosses and hydrogen and dechlorination processing is added to carry out dechlorination, the generation oil particularly suitable for ionic liquid alkylation process.
Background technique
Alkylate oil is a kind of common high-knock rating gasoline blend component, with octane number is high, the capability of antidetonance is good, steamForce down, sulfur-bearing is low and not olefin-containing and the features such as aromatic hydrocarbons, be ideal clean gasoline blending component.Alkylate oil generally passes throughIsobutane and olefins react generation under the action of acid catalyst.The technology type of alkylate oil is more, by the phase of catalystIt divides, liquid acid alkylation and solid acid alkylating two major classes can be divided into.Liquid acid alkylation techniques include hydrofluoric acid, sulfuric acid andThree kinds of ionic acid；Solid acid is mainly dedicated zeolite catalyst.
Currently, liquid acid alkylation processes are the most common methods, wherein ionic liquid alkylation is recent development in recent yearsAlkylation process technology.Ionic liquid has non-volatile, vapour pressure close to zero, is non-ignitable, thermal stability is high and liquid existing forThe advantages that temperature range is wide is acknowledged as a kind of environmental-friendly system；Because having the highdensity reaction of liquid acid to live simultaneouslyThe fixedness of property and solid acid, receives significant attention in recent years.The companies such as CHEVRON, SHELL and University of Petroleum and colleges and universities pairIonic liquid alkylation techniques have carried out a lot of research work.The ionic liquid alkylation techniques of University of Petroleum's exploitation are in September, 2013In Shandong Deyang, Chemical Co., Ltd. is constructed and put into operation.
Ionic liquid catalyst alkylation process includes pretreatment of raw material, alkylated reaction and product separation, ionic liquid regeneration threeA part.The main active of ionic liquid is aluminium chloride, while cationic portion contains the metallic compounds such as Cu, therefore is alkylatedGenerating in oil makes the piece safeties such as automotive oil tank, engine since chloride ion corrosion is stronger containing chloride ion or chlorohydrocarbonWith there are major hidden dangers, it is necessary to which motor petrol blend component could be used as by being removed.
Currently, the dechlorination research for alkylate oil produce with isobutane and olefins by chain reaction is less, mainlyUsing adsorbing and removing method.For example, CN204918487U discloses a kind of alkylate oil dechlorination equipment, which includes dechlorination apparatusA and dechlorination apparatus B.The alkylate oil containing chlorine to come is conveyed from reaction unit, passes through the dechlorinated device material inlet of feed lineInto the dechlorination apparatus for being filled with antichlor, when passing through from the antichlor in dechlorination apparatus, alkylate oil containing chlorine is carried residualOrganochlorine is stayed to be absorbed into antichlor.Qualified alkylate oil after removing organochlorine is arranged from dechlorination apparatus material outletOut, into alkylate oil products pot.After dechlorinated, the chloride content in alkylate oil is reduced to 1ppm hereinafter, meeting market pairThe requirement of oil quality.But limited by the organochlorine adsorption capacity of solid absorbent, frequent regeneration is needed, technique is increasedOperation difficulty and cost.
In addition to adsorbing and removing method, hydrogenation and removing method can be also used.Such as CN106995720A discloses one kind containing chlorineThe liquid phase dechlorination method of alkylate oil, method includes the following steps: (1) liquid-phase hydrogenatin: under hydroconversion condition, chlorine alkyl will be containedCarburetion, which is reacted under liquid phase state with hydrogen and hydrogenation catalyst, generates the hydrogenation products containing HCl；(2) liquid phase adsorption: will be describedHydrogenation products containing HCl contact under liquid phase state with adsorbent, after adsorbing HCl, obtain removing the hydrogenation products after HCl: (3)Oil-gas Separation: by it is described removing HCl after hydrogenation products and hydrogen separate, obtain dechlorination alkylate oil.The liquid phase dechlorination method is adoptedWith liquid-phase hydrogenatin, operating condition is mild, and hydrogen-oil ratio is low, it is not necessary to which setting plus the equipment such as hydrogen charging plus heating furnace may be implementedThe complete conversion of machine chlorine.But since the hydrogenation products containing HCl contact under liquid phase state with adsorbent, HCl expands in the liquid phaseScattered rate is slower, and HCl content is few in hydrogenation products (being not more than 500ppm), causes the adsorbent hydroxyl aluminum for needing to grow very muchMost of HCl could be removed, to influence the dechlorination efficiency of alkylate oil.
CN103025687A discloses a kind of hydrogenation-dechlorination of hydrocarbon products derived from ionic liquid.This method will derive from ionOne or more hydrocarbon products hydrogenation-dechlorinations of liquid catalyst hydrocarbon conversion reaction, so that dechlorination product and the exhaust gas containing HCl are provided,The chloride content of gained dechlorination product is less than 50 ppm, typically less than 10 ppm.Although this method also can achieve dechlorinationPurpose, but the process requirement gas-liquid separation generates after separation and contains HCl, H2、C1-C5The exhaust gas of hydrocarbon, it is also in need further to returnReceive or separate HCl.Entire process flow is more complicated, and investment and operating cost are also relatively high.
In addition, in the start-up process of hydrogenation-dechlorination device, since reaction condition and catalyst performance not up to react instituteThe state needed, therefore hydrogenation-dechlorination product is typically up to less than quality index.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of hydrogenation-dechlorination methods of ionic liquid alkylate oil.The partyMethod not only can satisfy the oily chlorinity of alkylation generation and meet the requirement of motor petrol blend component, and improve dechlorination effectRate, while solving the problems, such as that the hydrogenation-dechlorination device product quality caused by initial stage that goes into operation is not up to standard, effectively solve in cross-line valveThe problem of product caused by leakage is unqualified or device operation cycle shortens.
The present invention provides a kind of hydrogenation-dechlorination methods of ionic liquid alkylate oil, including following content: alkylated reactionAfter isolate ionic liquid catalyst, obtain alkylation mix products, to be directly entered hydrogenation-dechlorination anti-for alkylation mix productsDevice is answered, then hydrogenation-dechlorination generates the hydrogenation products containing HCl, enters back into absorption dechlorination apparatus and carries out to the HCl in hydrogenation productsAbsorption is passed through rectifying column and carries out rectifying after the completion of absorption；
When setting cross-line is used to for hydrogenation-dechlorination reaction, absorption dechlorination apparatus being isolated with alkylation system, alkylation mixing is producedObject is introduced directly into rectifying column, and cross-line is the pipeline before hydrogenation-dechlorination reactor inlet is arranged in and between rectifying column inlet lineConnecting pipeline；
Leakproof pipeline is set, leakproof pipeline one end is connected to cross-line, and the other end is connected to the compressor outlet pipeline of hydrogen feed,First valve is set on leakproof pipeline；The cross-line two sides of cross-line and leakproof pipeline communicating position are respectively arranged with the second valve, theThree valves；When normal operation, at least one valve in the second valve, third valve is closed, preferably by the second valve, theThree valves are turned off, and the first valve is in the open state, and liquid phase pressure is higher than liquid phase pressure in cross-line in leakproof pipeline, preferablyHigher than liquid phase pressure 0.1 MPa~0.3 MPa in cross-line.
In the method for the present invention, when hydrogenation-dechlorination reactor goes into operation, alkylation mix products are introduced into rectifying column and carry out essenceIt evaporates, the materials at bottom of tower of rectifying column is then introduced into hydrogenation-dechlorination reactor and carries out hydrogenation-dechlorination, then by absorption dechlorinationDevice is adsorbed, and when being passed through rectifying column 5 minutes~24 hours after the completion of absorption, preferably 1~10 hour, is stopped alkylation is mixedIt closes product to be passed directly into rectifying column and stop the materials at bottom of tower of rectifying column introducing hydrogenation-dechlorination reactor, alkylation mixing is producedObject is introduced directly into hydrogenation-dechlorination reactor, carries out normal hydrogenation-dechlorination reaction process.
In the method for the present invention, hydrogenation-dechlorination uses liquid phase reactor state, i.e., at reaction conditions, at least partly alkylation is mixedClosing product (alkylate oil) is liquid phase state.
In the method for the present invention, the tower bottom reboiler of rectifying column setting provides heat source for rectifying column, introduces hydrogenation-dechlorination reactionThe rectifying materials at bottom of tower of device is drawn after tower bottom reboiler, it is preferable that the rectifying bottoms drawn after tower bottom reboilerThe temperature of material is 100 DEG C~200 DEG C.
In the method for the present invention, device for transporting objects is arranged in the tower bottom of rectifying column, by device for transporting objects by rectifying towerThe material of bottom outlet is delivered to the pipeline before hydrogenation-dechlorination reactor inlet.
In the method for the present invention, heat exchanger and gas-liquid mixed are disposed on entering the pipeline before hydrogenation-dechlorination reactorDevice, heat exchanger are used for heat mix products, and air and liquid mixer is used to carry out hydrogen and alkylation mix products abundantMixing, air and liquid mixer are preferably static mixer or dynamic mixer, and static mixer is selected from SV type static mixer, SK typeOne of static mixer, SX type static mixer, SH type static mixer, SL type static mixer or several combinations,Dynamic mixer can one or several kinds of combinations in mixing pump, overcritical mixer, mixer.
In the method for the present invention, the 4th valve is provided on the pipeline before air and liquid mixer.
In the method for the present invention, it is provided with the materials at bottom of tower of connection rectifying column and the first pipeline of heat exchanger import, the first pipeRoad is equipped with the 5th valve.
In the method for the present invention, cross-line is connected to the pipeline before the 4th valve.
In the method for the present invention, it is provided with the isobutane outlet of connection rectifying column and the second pipeline of air and liquid mixer entrance,6th valve is installed on the second pipeline.
In the method for the present invention, the reaction condition of hydrogenation-dechlorination is as follows: reaction pressure is 0.5MPa~6.0MPa, preferablyThe MPa of 1.2MPa~3.0；Reaction temperature is 100 DEG C~200 DEG C, preferably 120 DEG C~170 DEG C；Volume space velocity is 1.0 h-1~10. 0h-1, preferably 2.0 h-1~6.0 h-1；Hydrogen to oil volume ratio is 50:1 hereinafter, preferably 2:1~10:1.
In the method for the present invention, the Hydrodechlorinating catalyst used can be commodity Hydrodechlorinating catalyst, it is preferred to use withNoble metal is the Hydrodechlorinating catalyst of active component, and Hydrodechlorinating catalyst is generally using aluminium oxide as carrier, such as Fushun petroleumThe FHDA-10 catalyst of chemical research institute's development and production.Preferably, using Pt and/or Pd as active component, active component is with weightThe content of meter in the catalyst is not less than 0.1%, generally 0.1%~1.5%.For alkylate oil raw material, add hydrogen de- using being somebody's turn to doThe organic chloride that chlorine catalyst can be such that alkylation generates in oil is reduced to 1ppm hereinafter, meeting high-quality motor petrol reconciliation groupThe requirement divided.
In the method for the present invention, absorption dechlorination apparatus loads regular industrial antichlor, is the oxide of alkaline-earth metal,Preferably calcium oxide and/or magnesia.
In the method for the present invention, the operating condition for adsorbing dechlorination apparatus is as follows: adsorptive pressure can be with hydrogenation-dechlorination reactor temperatureDegree, pressure can be identical or different, adsorb dechlorination apparatus adsorption temp be 100 DEG C~200 DEG C, adsorptive pressure be 0.5~6.0MPa, the preferably MPa of 1.2 MPa~3.0.
In the method for the present invention, at the initial stage of going into operation, the outer materials at bottom of tower for getting rid of rectifying column in part, the alkylation after obtaining dechlorinationOil.
In the method for the present invention, hydrogenation-dechlorination reactor uses up flow type mode of operation, i.e. reaction mass is anti-from hydrogenation-dechlorinationIt answers device lower part to enter and carries out hydrogenation-dechlorination reaction in reactor, refined oil is by that can be directly entered gasoline pool after separator.Add hydrogenDechlorination reaction device can also use downflow operation mode, i.e. reaction mass enters in reactor from hydrogenation-dechlorination reactor headCarry out hydrogenation-dechlorination reaction.
It is the alkylated reaction using ionic liquid catalyst for alkylated reaction, iso-butane is anti-in the method for the present inventionShould be usually excessive in the process, the molar ratio of isobutane and butene is preferably (2~40): 1, further preferably (5~20): 1.Reaction temperature can determine at -20~100 DEG C, generally 0~50 DEG C；The selection of reaction pressure should be to guarantee under reaction conditionIt is lower limit that reaction raw materials, which keep liquid condition, generally can be 0.1~1.6MPa.
Compared with prior art, advantageous effects of the invention are as follows:
(1) if cross-line valve slightly in leakage, the materials at bottom of tower chlorinity of rectifying column will obviously rise, and valves leakage be compared withGenerally, more difficult to find, be difficult to the problem eradicated completely, if being intended to thoroughly solve valves leakage, higher cost need to be paid.The present inventionIn, ingenious to use leakproof pipeline designs, in conjunction with the actual features of the device, i.e. the compressor delivery pressure of hydrogen feed compares cross-linePressure is slightly higher, after introducing leakproof pipeline, pressure in a little higher than cross-line of liquid phase pressure in leakproof pipeline, in this state, even ifOn cross-line valve slightly in leakage and leakproof pipeline in material (hydrogen) leak into hydrogenation-dechlorination reactor or leak into essenceTower is evaporated, and hydrogen does not influence hydrogenation-dechlorination reaction, nor affects on the distillation process of the alkylate oil of rectifying column, therefore regardless of which kind ofInterior leakage does not influence final products property and chlorinity, it is ingenious solve material chlorinity caused by valves leakage will it is obvious onThe problem of rising.The method of the present invention is skillfully constructed, it is easy to accomplish, maintenance cost is low, is conducive to device long period steady running.
(2) the method for the present invention, alkylation mix products directly carry out hydrogenation-dechlorination without isolation, generate containing HCl plus hydrogenProduct, the hydrogenation products containing HCl are adsorbed by adsorbing dechlorination apparatus, and rectifying column is passed through after absorption and carries out rectifying；Such alkaneHCl can be stripped off in unreacted excess isobutane gas from liquid phase in base mix products, thus with absorption dechlorinationWhen adsorbent in device adsorbs, it can soon be diffused, adsorb, to improve the HCl removal efficiency of hydrogenation products.ThisOutside, by carrying out hydrogenation-dechlorination and absorption dechlorination to alkylation mix products, iso-butane, normal butane are then isolated by rectifyingWith the gases such as hydrogen, to will not generate after dechlorination containing HCl, H2、C1-C5The exhaust gas of hydrocarbon.
At the initial stage of going into operation, it is alkylated mix products and is introduced into rectifying column progress rectifying, then by the materials at bottom of tower of rectifying columnIt is introduced into hydrogenation-dechlorination reactor, carries out hydrogenation-dechlorination, then rectifying column is reentered by absorption dechlorination apparatus, both may be used in this wayTo guarantee initial production quality requirement, product unqualified stationary phase is avoided, and the tower bottom reboiler that can use rectifying column is quickHeating alkylation mix products, reach the temperature requirement of hydrogenation-dechlorination, without increasing additional heater, and overcome and changeThe hot device disadvantage slow in the initial stage heat exchange unstability that goes into operation, heating, and subsequent normal hydogenation reaction process is not influenced.
(3) the method for the present invention, the characteristics of taking full advantage of the low temperature high hydrogenation activity of noble metal hydrogenation catalyst, using liquidHydrogenated dechlorination process process is fed under phase, reduces cost of investment, and high chlorine alkylation may be implemented directly as motor petrol tuneWith the requirement of component, the generation oil after dechlorination is directly entered motor petrol pond and dispatches from the factory as qualified products without being further processed.
(4) for the alkyl plant of oil refining enterprise, need to only increase between the sedimentation tower and rectifying column of alkyl plantOne hydrogenation-dechlorination reactor and an absorption dechlorination apparatus, it is not necessary to individually create a set of hydrogenation-dechlorination device, technique streamJourney is simple, and operating condition more mitigates, and exploitativeness is strong, and investment and operating cost can be greatly lowered.
Detailed description of the invention
Fig. 1 is the schematic diagram of the hydrogenation-dechlorination of alkylate oil of the invention；
Wherein: 1- iso-butane tank, 2- butylene tank, 3- ion flow container, the first air and liquid mixer of 4-, 5- alkylation reactor, 6- are heavyTank, 7- heat exchanger, the second air and liquid mixer of 8-, 9- compressor, 10- hydrogenation-dechlorination reactor, the absorption dechlorination dress of 11- first dropIt sets, 12- second adsorbs dechlorination apparatus, 13- rectifying column, 14- reboiler, the first valve of 15-, the second valve of 16-, 17- third valveDoor, the 4th valve of 18-, the 5th valve of 19-, the 6th valve of 20-.
Specific embodiment
The method of the present invention is described in detail in the following with reference to the drawings and specific embodiments.
For the new device using the method for the present invention, cross-line is set as shown in Figure 1: and is used for hydrogenation-dechlorination reactor10, when the first absorption dechlorination apparatus 11 is isolated with alkylation system, alkylation mix products are introduced directly into rectifying column 13, cross-lineFor the connecting pipeline being arranged between 13 import of the pipeline before 10 entrance of hydrogenation-dechlorination reactor and rectifying column；Anti- fistulae is setLine, leakproof pipeline one end are connected to cross-line, and the other end is connected to 13 bottoming cycle pump discharge pipeline of rectifying column, are arranged on leakproof pipelineFirst valve 15；The cross-line two sides of cross-line and leakproof pipeline communicating position are respectively arranged with the second valve 16, third valve 17；JustOften when operating, at least one of valve in the second valve 16, third valve 17 is closed, preferably by the second valve 16, thirdValve 17 is turned off, and the first valve 15 is in the open state, and liquid phase pressure is higher than liquid phase pressure in cross-line in leakproof pipeline, preferablyGround is higher than liquid phase pressure 0.1 MPa~0.3 MPa in cross-line.
In this way since 13 bottoming cycle pump discharge pressure of rectifying column is more slightly higher than cross-line pressure, after introducing leakproof pipeline, anti-fistulaePressure in a little higher than cross-line of liquid phase pressure in line, in this state, even if the slightly interior leakage of valve and leakproof pipeline on cross-lineInterior material passes through the valve that leaks and enters hydrogenation-dechlorination reactor or into rectifying column because in leakproof pipeline material be throughHydrotreating is crossed, the chlorinity in material is low-down, therefore leakage does not influence final products property in which kind of and chlorine containsAmount is ingenious to solve the problems, such as that material chlorinity caused by valves leakage obviously rise.
Alkyl plant goes into operation as shown in Figure 1: go into operation with hydrogenation plant after, the isobutane and butene tank 2 in iso-butane tank 1Butylene be passed through the first air and liquid mixer 4, be then mixed into alkylation reactor 5 with the ionic liquid in ion flow container 3 again, insteadEnter settling tank 6 after answering, sedimentation separation goes out ionic liquid and alkylation mix products, closes the first valve 15, the 4th valve18, third valve 16, third valve 17 are opened, alkylation mix products are directly entered rectifying column 13, by the bottom of rectifying column 13Pump enters reboiler 14 and is heated to reaction required temperature, opens the 5th valve 19, while being selectively opened the 6th valve 20,Material by heating returns to heat exchanger 7, the hydrogen-rich then come in the second air and liquid mixer 8 with iso-butane, the conveying of compressor 9Gas 5 is sufficiently mixed, and is entered after mixing from the bottom of hydrogenation-dechlorination reactor 10, is contacted with noble metal hydrogenation catalyst,Hydrogenation-dechlorination reaction is carried out under conditions of hydrogenation-dechlorination, and the organic chloride in alkylate oil is made to be converted into butter,After reaction, the product containing iso-butane, hydrogen, HCl enters the first absorption dechlorination apparatus 11, adsorbing and removing butter(HCl), then dechlorination product is again introduced into rectifying column 13 and carries out rectifying, and tower bottom obtains the alkylate oil of dechlorination, middle part obtains justButane, top obtain iso-butane, top obtains other gases.
The alkylate oil that tower bottom obtains dechlorination can completely or partially be passed through hydrogenation-dechlorination reactor 10, and tower bottom exceptionally arranges alkaneWhen base carburetion, the dechlorination alkylate oil at the available initial stage that goes into operation is used directly for gasoline blend component, or further takes offChlorine processing.
After hydrogenation-dechlorination reactor 10 enters nominal situation, the second valve 16, third valve 17, the 5th valve 19 are closedWith the 6th valve 20, the first valve 15, the 4th valve 18 are opened, hydrogenation-dechlorination part enters the normal technological process of production, thisFlexible process flow avoids the initial production that goes into operation unqualified stationary phase.Meanwhile at the initial stage of going into operation, it is selectively passed through rectifyingIso-butane afterwards, the HCl that hydrogenation-dechlorination can be made to generate enters isobutane gas, and iso-butane can carry out essence by rectifying column againIt evaporates, does not need extra means and separated, nor affect on and subsequent normally go into operation.Liquid phase pressure is higher than in cross-line in leakproof pipelinePressure 0.1 MPa~0.3 MPa, it is ingenious to solve the problems, such as that material chlorinity caused by valves leakage obviously rise.
After antichlor reaches saturation in the first absorption dechlorination apparatus 11, the valve of the first absorption dechlorination apparatus 11 is closed,The valve that valve second adsorbs dechlorination apparatus 12 is opened, into the second absorption dechlorination apparatus 12, while to the first absorption dechlorination dressIt sets antichlor in 11 to be replaced or regenerated, it is ensured that this dechlorination unit realizes continuous and steady operation.
The dechlorination cell process process is simple, and solving alkylate oil cannot asking directly as motor petrol blend componentTopic.Oil is generated by the alkylation that the method for the present invention is handled, product can achieve following property: refined oil chlorinity is less than1ppm.Other properties meet the requirement of high-quality motor petrol blend component.
The following examples illustrate the present invention further.
Experiment is the Hydrodechlorinating catalyst of industrial application using catalyst, is Fushun Petrochemical Research Institute's development and productionFHDA-10 hydrogenation catalyst, physicochemical property index is shown in Table 1.
The physicochemical property index of 1 catalyst of table
| Catalyst number | FHDA-10 |
| Metal composition | Pt-Pd |
| Physical property | |
| Kong Rong, mL/g | ≮0.45 |
| Specific surface area, m2/g | ≮170 |
| Compressive resistance, N/cm | ≮90 |
| Shape | Cylinder bar shaped |
Embodiment 1
Alkyl plant is created by the present invention program.After alkylated reaction, ionic liquid is separated through settling tank 6, is then passed throughAfter feed pump, heat exchanger 7 and hydrogen are sufficiently mixed dissolution in SX type static mixer, into hydrogenation-dechlorination reactor 10, insteadAnswer condition are as follows: volume space velocity 3.8h when reaction pressure 1.5MPa ﹑ liquid-1, 143 DEG C of reaction temperature.After reaction, after reactionInto the first absorption dechlorination apparatus 11, adsorbing and removing butter.Filling regular industrial is used in first absorption dechlorination apparatus 11Antichlor, main component include calcium oxide.The adsorption temp for adsorbing dechlorination apparatus is 142 DEG C, adsorptive pressure 1.4MPa.Then absorption dechlorination product enter rectifying column 13 carry out rectifying, tower bottom obtains the alkylate oil of dechlorination, middle part obtains normal butane, onPortion obtains iso-butane, top obtains other gases.The property and essence of the alkylate oil in mix products are alkylated before hydrogenation-dechlorinationIt evaporates final products-alkylate oil property that tower obtains and is listed in table 2.
The processing that goes into operation is carried out to hydrogenation plant using the method for the present invention, when going into operation, is first introduced into alkylation mix productsRectifying column 13 carries out rectifying, the materials at bottom of tower (temperature for the rectifying materials at bottom of tower drawn after tower bottom reboiler of rectifying column 13It is 143 DEG C) hydrogenation-dechlorination reactor 10 is introduced, meanwhile, it is anti-to hydrogenation-dechlorination to pass through the second air and liquid mixer 8 to the property of can chooseIt answers device 10 to introduce the iso-butane of circulation, carries out hydrogenation-dechlorination, then by the first absorption dechlorination apparatus 11 or the second absorption dechlorinationDevice 12 is adsorbed, absorption complete material enter rectifying column 5 hours after, stop introduce rectifying column 13 materials at bottom of tower andIso-butane, and stop directly being passed through alkylation mix products to rectifying column 13, it is switched to normal operating process.
Liquid phase pressure is higher than 0.2 MPa of pressure in cross-line in leakproof pipeline, ingenious can solve object caused by valves leakageThe problem of material chlorinity will obviously rise.
As can be seen from Table 2, alkylation can be made to generate oil using the technology in hydrogenation-dechlorination device normal operatingChlorinity is reduced to 1ppm hereinafter, and entirely start-up process product quality also keeps stable.
Embodiment 2
Alkyl plant is created by the present invention program.After alkylated reaction, separate ionic liquid through settling tank, then by intoAfter material pump, heat exchanger and hydrogen are sufficiently mixed dissolution in SX type static mixer, into hydrogenation-dechlorination reactor, reaction conditionAre as follows: volume space velocity 4.2h when reaction pressure 1.6MPa ﹑ liquid-1, 157 DEG C of reaction temperature.After reaction, into the first absorption dechlorinationDevice 11, adsorbing and removing butter.First absorption dechlorination apparatus 11 loads regular industrial antichlor, mainly groupDivide including magnesia etc..The adsorption temp for adsorbing dechlorination apparatus is 156 DEG C, 1.5 MPa of adsorptive pressure.Then dechlorination product is adsorbedRectifying is carried out into rectifying column 13, tower bottom obtains the alkylate oil of dechlorination, middle part obtains normal butane, top obtains iso-butane, topPortion obtains other gases.The property and final products property of alkylate oil before hydrogenation-dechlorination are listed in table 2.
The processing that goes into operation is carried out to hydrogenation plant using the method for the present invention, when going into operation, is first introduced into alkylation mix productsRectifying column carries out rectifying, and (temperature for the rectifying materials at bottom of tower drawn after tower bottom reboiler is 157 to the materials at bottom of tower of rectifying columnDEG C) hydrogenation-dechlorination reactor 10 is introduced, meanwhile, pass through to the property of can choose the second air and liquid mixer 8 to hydrogenation-dechlorination reactor10 introduce the iso-butane of circulation, carry out hydrogenation-dechlorination, then by the first absorption dechlorination apparatus 11 or the second absorption dechlorination apparatus12 are adsorbed, and after the material that absorption is completed enters rectifying column 4 hours, stop the materials at bottom of tower and isobutyl that introduce rectifying column 13Alkane, and stop directly being passed through alkylation mix products to rectifying column 13, it is switched to normal operating process.
Liquid phase pressure is higher than 0.2 MPa of pressure in cross-line in leakproof pipeline, ingenious can solve object caused by valves leakageThe problem of material chlorinity will obviously rise.
As can be seen from Table 2, alkylation can be made to generate oil using the technology in hydrogenation-dechlorination device normal operatingChlorinity is reduced to 1ppm hereinafter, and entirely start-up process product quality also keeps stable.
Comparative example 1
According to the scheme of embodiment 1, only when going into operation, will alkylation mix products be directly entered hydrogenator, directly intoRow normal operating.In start-up process, hydrogenation reaction product has to be not achieved quality index (more than 10 ppm) for about 30 hours, andAnd more than 50 ppm in the 5 hours initial stages that go into operation.
The property and test result of 2 hydrogenation-dechlorination raw material of table
| Project | Embodiment 1 | Embodiment 2 |
| Process conditions | | |
| Reaction temperature, DEG C | 143 | 157 |
| Reaction pressure, MPa | 1.5 | 1.6 |
| Volume space velocity when liquid, h-1 | 3.8 | 4.2 |
| Oil property | | |
| Alkylate oil chlorinity before hydrogenation-dechlorination, ppm | 750 | 579 |
| It goes into operation initial stage, alkylate oil chlorinity after dechlorination, ppm | < 10 | < 10 |
| Normal operating, alkylate oil chlorinity, ppm after dechlorination | < 1.0 | < 1.0 |
Embodiment 3
During trial run, the second valve 16, the third valve 17 on cross-line are opened, and make the second valve 16, third valve17 keep very little aperture, simulate valves leakage operating condition, when not enabling leakproof pipeline (not opening the first valve 15), alkane after dechlorinationThe chlorinity of base carburetion is greater than 10 ppm, and after enabling leakproof pipeline (opening the first valve 15), the chlorine of alkylate oil after dechlorinationStable content, down to 1.0 ppm.
By calculating, under certain operating conditions, when catalyst performance is good (product index is far below Con trolling index), ifThere is the interior leakage of 1.7wt%, the chlorinity of alkylate oil is greater than 10 ppm after dechlorination；It (is alkylated after dechlorination in catalyst using the later periodThe chlorinity of oil is close to quality index), slightly in leakage, it is not up to standard to will result in product chlorinity.