CN106281428A - A kind of coking crude benzene hydrodesulfurization - Google Patents

A kind of coking crude benzene hydrodesulfurization Download PDF

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CN106281428A
CN106281428A CN201610657468.7A CN201610657468A CN106281428A CN 106281428 A CN106281428 A CN 106281428A CN 201610657468 A CN201610657468 A CN 201610657468A CN 106281428 A CN106281428 A CN 106281428A
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fixed bed
hydrogen
hydrodesulfurization
kit
bed reactors
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朱忠良
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Xishan Lvchun Plastic Products Factory
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Xishan Lvchun Plastic Products Factory
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of coking crude benzene hydrodesulfurization, coking crude benzene and hydrogen mixture enter pre-reactor from tower top, pre-reactor is filled with NiMo catalyst, its reaction temperature is 220 230 DEG C, hydrogenation pressure is 3.2 3.8MPa, the product of pre-reaction enters fixed bed reactors, is filled with Hydrobon catalyst in described fixed bed reactors, and described catalyst includes carrier and active component；Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT 1；Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc；The reaction condition of described fixed bed reactors is: reaction temperature is 320 380 DEG C, Hydrogen Vapor Pressure 3.0 3.6MPa, hydrogen to oil volume ratio 500 800, volume space velocity 1.5 2h‑1；The reacted product of fixed bed hydrogenation enters extractive distillation unit, obtains aromatic hydrocarbons.Total sulfur content in coking crude benzene can be reduced to below 0.1ppm by this technique, can meet its purposes widely.

Description

A kind of coking crude benzene hydrodesulfurization
Technical field
The present invention relates to a kind of hydrodesulfurization, be specifically related to a kind of coking crude benzene hydrodesulfurization.
Background technology
Coking is the high-temperature retorting of one of major way of Coal dressing, also commonly referred to as coal, i.e. by applicable coking Bituminous coal, after suitably processing, completely cuts off air in coke oven and is heated to 950-1050 DEG C, melts through being dried, be pyrolyzed, burning, bond, solidifies Coke is finally prepared with stages such as contractions.The volatile matter separated out in process of coking includes that the chemistry such as coal gas, tar, ammonia and crude benzol produce Product.It addition, the coal tar obtained in coking also contains the aromatic hydrocarbons such as a certain amount of benzene.
Coked crude benzene refining is with coking crude benzene as raw material, through the method such as physics or chemistry remove wherein sulfur-bearing, contain The harmful substances such as nitrogen, in order to obtain the high-purity benzene,toluene,xylene etc. that can use as raw material.At present, the industrial master of China Crude benzol is refined by acid wash to be used and hydrodesulfurization.
Catalytic hydrogenation method as coking crude benzene chemical desulfurization method, be under hydro condition, thiophene is changed into hydrogen sulfide and Corresponding alkane and remove, the most in two steps, the first step: pre-hydrotreating reaction, the catalyst removal coking of main routine Unstable material in crude benzol, it is also possible to removing part sulphur-containing substance；Second step, main hydrogenation reaction, thiophene in removing coking crude benzene The Major Sulfides such as fen, Carbon bisulfide and organic nitrogen compound.Crude benzole hydrogenation technique is divided into high-temperature hydrogenation according to catalytic reaction temperature With two kinds of techniques of low temperature hydrogenation.
In high-temperature catalytic hydrogenation technique, most typically is exactly Lay Bristol method, i.e. Litol method, and this technique is in the sixties in 20th century A kind of high temperature crude benzole hydrogenation method for refining successfully developed by U.S. Hu Deli (Hondry) Air Products Company, later Japan's rising sun It is improved again by Cheng company, defines Japan Litol high temperature, high pressure vapor hydrogen addition technology.First crude benzol is existed by this method Being separated into light benzene and heavy benzol in prefractionator, light benzene enters after vaporizer mixes with circulating hydrogen through high-pressure pump, aromatic hydrocarbon steam with Hydrogen mixture enters pre-reactor from tower top.The hydroconversion condition of this method is: pre-reactor temperature is 230 DEG C, and pressure is 5.7MPa, catalyst is CoMo catalyst；Main reactor temperature isPressure is 5l0MPa, and catalyst is Cr Series catalysts.Pre-reactor is at a lower temperatureThe styrene equivalent of easily polymerization under the condition of high temperature It is that thing carries out hydrogenation reaction, prevents it to be polymerized in main reactor, make catalyst activity reduce, complete in two main reactors Hydrocracking, the de-reaction such as alkyl, desulfurization.The condensed cooling system of oil gas discharged by main reactor, isolated liquid is Hydrogenated oil, isolated hydrogen and low molecular hydrocarbon removing H2After S, a part is sent to hydrogenation system, and a part is sent to convert system Hydrogen system hydrogen making.Owing to the alkyl on phenyl ring can be removed by Litol technique, therefore purified petroleum benzin productivity can reach 114%.
Owing to Litol method needs to operate at high temperature under high pressure, (hydrogen that at high temperature under high pressure, hydrogen decomposes is former again hydrogen embrittlement Son penetrates in steel crystal grain, makes the intercrystalline atomic binding forces of steel reduce, thus reduces elongation percentage and the section receipts of steel Shrinkage) and hydrogen-type corrosion (at high temperature under high pressure, hydrogen molecule and hydrogen atom slowly penetrate into the fault location of steel material, assemble composition With the hydrogenation reaction of carbon compound generation around after sub-defect), so equipment requirements is wanted height, manufacture difficulty is relatively big, need from External a complete set of introduction.The nineties in 20th century, the Lay Bristol method of Baosteel chemical industry first stage of the project of China the most a complete set of Introduced from Japan is high The de-alkyl hydrogenation technique of temperature, went into operation in 1986, and year processes crude benzol 50,000 t, can obtain purity 99.9%, crystalline temperature 5.52 DEG C:, total sulphur content less than lppm, thiophene content less than spy's purified petroleum benzin of 0.5ppm.Henan Shen Ma company is the most a complete set of to introduce The Lay Bristol method high temperature of Japan takes off alkyl hydrogenation technique.Litol law theory productivity 91.53%, but in terms of actual achievement in 2004 But only have 88.96%.
Low temperature hydrogenation method mainly includes three essential elements: (purity is more than the pure hydrogen of coke-stove gas pressure-variable adsorption system 99.9%)；Hydrobon process (pre-hydrogenation and main hydrogenation)；Product purification process (extraction or extractive distillation).Due to The product mainly obtained in coking crude benzene low temperature hydrogenation technique is aromatic hydrocarbon and non-aromatic hydrocarbon, industrial very difficult directly by routine Distillating method be separated, after adding certain extractant (extractant require with other component formed azeotropic mixture and Boiling point is higher), each component dissolubility wherein can be changed significantly, thus change their relative volatility and saturated steaming Vapour pressure, more just can reach to separate the effect of product by the method for distillation, technique can be divided into extractive distillation and liquid liquid extraction Take.
Extractive distillation hydrogenation method theoretical yield is 99.41%, but only has 98.30% from the point of view of actual achievement in 2004.Liquid liquid extracts The most representational in taking technique is exactly sulfolane process, and its theoretical yield is also more than 99%.But above-mentioned process obtains Purified petroleum benzin sulfur content is all at about 0.5ppm, and this produces considerable restraint to the use of aromatic hydrocarbon product
A kind of hydrodesulfurization is provided, can effectively the sulfur content of coking crude benzene product be controlled at 0.1ppm Hereinafter, to meet its application standard, it it is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of coking crude benzene hydrodesulfurization, this technique can be by coking crude benzene Total sulfur content is reduced to below 0.1ppm, minimum to 0.05ppm, to meet the application requirement of product.
For reaching this purpose, the present invention by the following technical solutions:
A kind of coking crude benzene hydrodesulfurization, coking crude benzene and hydrogen mixture enter pre-reactor from tower top, pre-instead Answering and be filled with NiMo catalyst in device, its reaction temperature is 220-230 DEG C, and hydrogenation pressure is 3.2-3.8MPa, and its product is subsequently Enter fixed bed reactors, described fixed bed reactors are filled with Hydrobon catalyst, described catalyst include carrier and Active component.
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT-1.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
The reaction condition of described fixed bed reactors is: reaction temperature is 320-380 DEG C, Hydrogen Vapor Pressure 3.0-3.6MPa, Hydrogen to oil volume ratio 500-800, volume space velocity 1.5-2h-1。
The reacted product of fixed bed hydrogenation enters extractive distillation unit, obtains aromatic hydrocarbons.
Through detection, in the aromatic hydrocarbons obtained, total sulphur content is less than 0.1ppm, and the purity of product is also greater than 99.9%.
It should be noted that in the coking crude benzene hydrodesulfurization of present invention employing, pre-hydrotreating reaction uses routine to set Standby and technique, the present invention improvement to coking crude benzole hydrogenation sulfur removal technology, be more embodied in the design of main hydrogenation reaction.
KIT-1 molecular sieve has one-dimensional channels and crosses each other to form three-dimensional disordered structure, and this structure is conducive to catalysis, absorption During material transmission.Pure silicon mesopore molecular sieve KIT-1 has heat stability more more preferable than MCM-241, HMS and hydrothermally stable Property.The present invention through in numerous mesoporous materials, such as KIT-1, KIT-6, MCM-22, MCM-36, MCM-48, MCM-49, MCM56 etc., carry out contrast test selection, find that only KIT-1 can reach the goal of the invention of the present invention, and other mesoporous materials are all Having such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, therefore the present invention selects to use KIT-1 is as carrier basis.
Although pure silicon KIT-1 mesopore molecular sieve hydro-thermal performance is outstanding, but inventor's research is later discovered that, it adds Hetero atom or surface are after chemical modification, and its hydrothermal stability obtains bigger raising.Therefore, it is modified by the present invention, with Increase its catalysis activity.The approach that KIT-1 mesopore molecular sieve is modified is by the present invention: in KIT-1 building-up process, adds Co2+ Saline solution, before KIT-1 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part backbone element thus embedding Enter in the skeleton of molecular sieve, improve catalysis activity, absorption and the thermodynamic stability of KIT-1 mesopore molecular sieve on the whole Can etc..
Although the method being modified KIT-1 mesopore molecular sieve or approach are a lot, inventor finds, the catalysis of the present invention Agent can only use doping Co2+KIT-1 could realize sulfur content as carrier and control and the balance of loss of octane number, inventor tastes Try to adulterate in KIT-1: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all to realize institute State effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on KIT-1 inner surfaces of pores to compare, the present invention Isomorphous substitution approach more stable.Although described mechanism is current and unclear, but this has no effect on the enforcement of the present invention, invention People is according to well-known theory and it is experimentally confirmed that there is cooperative effect between itself and the active component of the present invention.
Described Co2+Doping in KIT-1 must control within specific content range, and its doping is with weight Meter, for the 0.56%-0.75% of KIT-1 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%, 0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%, 0.74 etc..
Inventor finds, outside this range, can cause being increased dramatically of the total sulfur content in product.More pleasurable It is to work as Co2+When doping in KIT-1 controls in the range of 0.63%-0.72%, it is the strongest to the control of total sulfur content, When drawing with Co2+Doping is transverse axis, during curve chart with target product total sulfur content as the longitudinal axis, and sulfur content in this content range Can control within the scope of extremely low, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier KIT-1 weight, preferably 3-12%, further preferred 5- 10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28- 0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists In the range of Gai, sulfur content in coking crude benzene can be realized and control at below 0.1ppm.It is to say, the four of the present invention kinds of activity Component is only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just possess cooperative effect.Rub except this Outside you are than scope, or omit or replace any one component, all can not realize cooperative effect.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45- 0.5): (0.35-0.45): (0.8-1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0), Preferably 1:0.48:0.42:0.95.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.The typical but non-limiting example of the present invention As follows:
Sodium silicate, cetyl trimethylammonium bromide (CTAB), sodium ethylene diamine tetracetate (EDTA) and distilled water are massaged You mix the ratio than 1:0.25:1:60, load with in teflon-lined autoclave pressure, after stirring under 373K Constant temperature 24h, the pH of re-adjustments mixture are 10.5, after constant temperature 4 times, take out product, with distilled water cyclic washing to filtrate PH=7, then under 373K, constant temperature overnight, obtains the KIT-1 with surfactant.KIT-1 with surfactant is existed Roasting 1.5h under 523K, then roasting 6h in air atmosphere under 813K, obtains KIT-1 powder body.By this powder body 0.1mol/L Salpeter solution carry out pickling (control solid-to-liquid ratio is 1:10), under room temperature stir 0.5h, filter, be washed with distilled water to filtrate Dry under pH=7,373K and obtain matrix KIT-1 molecular sieve.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 340-360 DEG C, Hydrogen Vapor Pressure 3.2- 3.4MPa, hydrogen to oil volume ratio 600-800, volume space velocity 1.5-1.8h-1。
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The coking crude benzene hydrodesulfurization of the present invention is by choosing specific catalyst, and described catalyst is miscellaneous by mixing Atom Co2+KIT-1 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and carbon Change tungsten WC as active component so that this catalyst produces cooperative effect, and the hydrodesulfurization to coking crude benzene can control at total sulfur Content is less than 0.1ppm.
Detailed description of the invention
The hydrodesulfurization of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Co2+KIT-1, Co2+Doping control in KIT-1 System is at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Total content is the 10% of carrier quality, and its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm Becoming, reaction bed temperature UGU808 type temp controlled meter is measured, the twin columns that raw material light oil is manufactured by Beijing Satellite Manufacturing Factory Plug micro pump carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-11A/ZM mass-flow gas meter control by gas cylinder Flow velocity processed, loaded catalyst is 2kg.
Coking crude benzene and hydrogen mixture enter pre-reactor from tower top, are filled with NiMo catalyst in pre-reactor, its Reaction temperature is 230 DEG C, and hydrogenation pressure is 3.5MPa, and its product subsequently enters described fixed bed reactors.Control primary response bar Part is: reaction temperature is 340 DEG C, Hydrogen Vapor Pressure 3.4MPa, hydrogen to oil volume ratio 650, volume space velocity 1.5h-1.The product obtained with Rear entrance extractive distillation unit, extractant uses sulfolane, and extraction temperature controls at 100 DEG C, and extracting pressure controls 200kPa。
Testing final product, its total sulfur content is reduced to 0.07ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+KIT-1, Co2+Doping control in KIT-1 System is at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Total content is the 10% of carrier quality, and its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, its total sulfur content is reduced to 0.04ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, its total sulfur content is 12ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated KIT-1, and remaining condition is constant.
Testing final product, its total sulfur content is 15ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, its total sulfur content is 13ppm.
Comparative example 4
By the Co in embodiment 12+Doping in KIT-1 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, its total sulfur content is 17ppm.
Comparative example 5
By the Co in embodiment 12+Doping in KIT-1 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, its total sulfur content is 11ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion KIT-1 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+During doping difference, all reach not To the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping KIT-1 carrier and other components of catalyst Between possess cooperative effect, described hydrodesulfurization creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, its total sulfur content is 12ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, its total sulfur content is 9ppm.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrodesulfurization of the present invention it Between there is specific contact, be omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that it produces Give birth to cooperative effect.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (6)

1. a coking crude benzene hydrodesulfurization, it is characterised in that coking crude benzene and hydrogen mixture are pre-instead from tower top entrance Answering device, be filled with NiMo catalyst in pre-reactor, its reaction temperature is 220-230 DEG C, and hydrogenation pressure is 3.2-3.8MPa, in advance The product of reaction enters fixed bed reactors, is filled with Hydrobon catalyst, described catalyst in described fixed bed reactors Including carrier and active component；Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT-1；Described active component For nitrogenizing two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc；The reaction bar of described fixed bed reactors Part is: reaction temperature is 320-380 DEG C, Hydrogen Vapor Pressure 3.0-3.6MPa, hydrogen to oil volume ratio 500-800, volume space velocity 1.5-2h-1；The reacted product of fixed bed hydrogenation enters extractive distillation unit, obtains aromatic hydrocarbons.
2. hydrodesulfurization as claimed in claim 1, it is characterised in that hetero atom Co2+Doping be KIT-1 weight 0.63%-0.72%.
3. hydrodesulfurization as claimed in claim 1, it is characterised in that the total content of described active component is carrier KIT- The 3-12% of 1 weight, preferably 5-10%.
4. hydrodesulfurization as claimed in claim 1, it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5): (0.35-0.45): (0.8-1.0), more preferably 1: (0.45-0.48): (0.4-0.45): (0.9-1.0), most preferably 1:0.48:0.42:0.95.
5. hydrodesulfurization as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is: Reaction temperature is 340-360 DEG C, Hydrogen Vapor Pressure 3.2-3.4MPa, hydrogen to oil volume ratio 600-800, volume space velocity 1.5-1.8h-1。
6. hydrodesulfurization as claimed in claim 1, it is characterised in that described fixed bed reactors include 1-5 catalysis Agent bed, preferably includes 2-3 beds.
CN201610657468.7A 2016-08-11 2016-08-11 A kind of coking crude benzene hydrodesulfurization Pending CN106281428A (en)

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