CN106345518A - Hydrogenation and desulfurization process of coking crude benzol - Google Patents

Hydrogenation and desulfurization process of coking crude benzol Download PDF

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Publication number
CN106345518A
CN106345518A CN201610707985.0A CN201610707985A CN106345518A CN 106345518 A CN106345518 A CN 106345518A CN 201610707985 A CN201610707985 A CN 201610707985A CN 106345518 A CN106345518 A CN 106345518A
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catalyst
fixed bed
hydrogenation
hydrogen
hydrodesulfurization
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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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    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention disclsoes a hydrogenation and desulfurization process of coking crude benzol. A coking crude benzol and hydrogen mixture enters a pre-reactor from a tower top; the pre-reactor is filled with an NiMo catalyst, wherein the reaction temperature is 220 DEG C to 230 DEG C, and the hydrogenation pressure is 3.2MPa to 3.8MPa; a pre-reaction product enters a fixed bed reactor; the fixed bed reactor is filled with a hydrogenation and desulfurization catalyst, and the catalyst comprises a carrier and an active component; the carrier is KIT-1 with a synthetic framework structure doped with heteroatom Cu<2+>; the active component is a mixture of dimolybdenum nitride MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide WC; the catalyst further contains a catalytic auxiliary agent; the catalytic auxiliary agent is a mixture of Cr2O3, ZrO2, CeO2, V2O5 and NbOPO4; reaction conditions of the fixed bed reactor are as follows: the reaction temperature is 320 DEG C to 380 DEG C, the hydrogen pressure is 3.0MPa to 3.6MPa, the hydrogen-oil volume ratio is 500 to 800, and the volume space velocity is 1.5h<-1> to 2h<-1>; a product obtained by a hydrogenation reaction of the fixed bed reactor enters an extracting and distilling unit to obtain arene. By adopting the process provided by the invention, the total sulfur content in the coking crude benzol can be reduced to be lower than 0.1ppm, and the process has wide application.

Description

A kind of coking crude benzene hydrodesulfurization
Technical field
The present invention relates to a kind of hydrodesulfurization is and in particular to a kind of coking crude benzene hydrodesulfurization.
Background technology
Coking is one of major way of Coal dressing, also commonly referred to as the high-temperature retorting of coal, that is, by suitable coking Bituminous coal, after proper treatment, in coke oven, isolation air is heated to 950-1050 DEG C, through drying, pyrolysis, burns and melts, bonds, solidifying Coke is finally obtained with stages such as contractions.The volatile matter separating out in process of coking includes the chemistry such as coal gas, tar, ammonia and crude benzol and produces Product.In addition, also containing the aromatic hydrocarbons such as a certain amount of benzene in the coal tar obtaining in coking.
Coked crude benzene refining is with coking crude benzene as raw material, through the method such as physics or chemistry removing wherein sulfur-bearing, contain The harmful substances such as nitrogen, to obtain the high-purity benzene,toluene,xylene that can use etc. as raw material.At present, the industrial master of China Acid wash to be adopted and hydrodesulfurization refine to crude benzol.
Catalytic hydrogenation method as coking crude benzene chemical desulfurization method, be under hydro condition by thiophene change into hydrogen sulfide and Corresponding alkane and remove, typically in two steps, the first step: pre-hydrotreating reaction, main with conventional catalyst removal coking Unstable material in crude benzol is it is also possible to remove 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, the Japanese rising sun later Cheng company is improved to it again, defines Japanese litol high temperature, high pressure vapor hydrogen addition technology.Crude benzol is existed by this method first Be 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 of easily polymerization under the condition of high temperature is equal to It is that thing carries out hydrogenation reaction, prevents it to be polymerized in main reactor, so that catalyst activity is reduced, complete in two main reactors Hydrocracking, the de- reaction such as alkyl, desulfurization.The condensed cooling system of oil gas discharged by main reactor, the liquid isolated is Hydrogenated oil, the hydrogen isolated and low molecular hydrocarbon removing h2After s, a part is sent to hydrogenation system, and a part is sent to conversion system Hydrogen system hydrogen making.Because the alkyl on phenyl ring can be removed by litol technique, therefore purified petroleum benzin yield can reach 114%.
Because litol method needs to operate at high temperature under high pressure, have hydrogen embrittlement (hydrogen that at high temperature under high pressure, hydrogen decomposes is former again Son penetrates in steel crystal grain, so that the intercrystalline atomic binding forces of steel is reduced, thus reducing 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 There is hydrogenation reaction with carbon compound around after sub- defect), thus to equipment requirements will height, manufacture difficulty is larger, need from A complete set of introduction abroad.The nineties in 20th century, Baosteel chemical industry first stage of the project of China just once the Lay Bristol method of a complete set of Introduced from Japan high The de- alkyl hydrogenation technique of temperature, went into operation in 1986, year processes crude benzol 50,000 t, can obtain purity 99.9%, crystalline temperature 5.52 DEG C:, total sulphur content be less than lppm, thiophene content be less than 0.5ppm spy's purified petroleum benzin.Henan Shen Ma company is subsequently also a complete set of to introduce The Lay Bristol method high temperature of Japan takes off alkyl hydrogenation technique.Litol law theory yield 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 obtaining in coking crude benzene low temperature hydrogenation technique is aromatic hydrocarbon and non-aromatic hydrocarbon, industrial be difficult to directly to pass through conventional Distillating method be separated, after adding certain extractant (extractant require not formed with other components azeotropic mixture and Boiling point is higher), can significantly change each component dissolubility wherein, thus changing their relative volatility and saturation steaming Vapour pressure, then the effect separating product just can be reached 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 98.30% from the point of view of actual achievement in 2004.Liquid liquid extracts Most representational in taking technique is exactly sulfolane process, and its theoretical yield is also more than 99%.But above-mentioned process obtains All in 0.5ppm, this is to aromatic hydrocarbon product using producing considerable restraint for purified petroleum benzin sulfur content
How a kind of hydrodesulfurization is therefore provided, effectively can control the sulfur content of coking crude benzene product in 0.1ppm Hereinafter, to meet its application standard, it is the difficult problem that this area faces.
Content of the invention
It is an object of the invention to proposing 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 employs the following technical solutions:
A kind of coking crude benzene hydrodesulfurization, coking crude benzene enters pre-reactor with hydrogen mixture from tower top, pre- anti- Answer and in device, be filled with nimo catalyst, its reaction temperature is 220-230 DEG C, hydrogenation pressure is 3.2-3.8mpa, its product is subsequent Enter fixed bed reactors, be filled with Hydrobon catalyst in described fixed bed reactors, described catalyst include carrier and Active component.
Described carrier is to mix hetero atom cu in synthesis framing structure2+Kit-1.
Described active component is nitridation two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C and the mixture of tungsten carbide wc.
Described catalyst also contains catalyst aid, and described catalyst aid is cr2o3、zro2、ceo2、v2o5And nbopo4's Mixture.
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 obtaining, 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 is set using routine Standby and technique, the improvement to coking crude benzole hydrogenation sulfur removal technology for the present invention, are 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 more preferable heat stability and hydrothermally stable than mcm-241, hms 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., carries out contrast test selection, finds the goal of the invention only having kit-1 can reach the present invention, other mesoporous materials are all There is such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, the therefore present invention selects to use Kit-1 is as carrier basis.
Although pure silicon kit-1 mesopore molecular sieve hydro-thermal performance is very outstanding, inventor's research is later discovered that, its addition , after chemical modification, its hydrothermal stability obtains bigger raising for hetero atom or surface.Therefore, the present invention is modified to it, with Increase its catalysis activity.The present invention approach modified to kit-1 mesopore molecular sieve is: to the total silicon kit-1 mesoporous molecular of finished product Sieve inner surfaces of pores introduces cu2+, this approach can be by ion exchange by cu2+It is supported on the inner surface of kit-1, thus Improve catalysis activity, absorption and Thermodynamically stable performance of kit-1 mesopore molecular sieve etc. on the whole.
Although the method that kit-1 mesopore molecular sieve is modified or approach are a lot, inventor finds, the catalysis of the present invention Agent can only be using doping cu2+Kit-1 just enable sulfur content control as carrier, inventor has attempted in kit-1 doping: al3+、fe3+、zn2+、ga3+In the ion producing anionic surface center, find that not enabling total sulfur content is less than 0.1ppm's Effect.Although described mechanism is not known at present, this has no effect on the enforcement of the present invention, and inventor is according to well-known theory and reality Checking is real, and it has cooperative effect and the active component of the present invention between.
Described cu2+Must control within specific content range in the doping in kit-1, its doping is with weight Meter, be 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%th, 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 lead to being increased dramatically of the total sulfur content in product.More pleasurable It is to work as cu2+When the 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 drafting is with cu2+When doping is transverse axis, curve chart with target product total sulfur content as the longitudinal axis, sulfur content in this content range Can control within the scope of extremely low, the desulfurized effect that it produces, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15%, preferably 3-12%, further preferred 5- of carrier kit-1 weight 10%.For example, described content can for 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%th, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%th, 14%, 14.5% etc..
In the present invention, being particularly limited to active component is nitridation two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C and tungsten carbide wc Mixed proportion, inventor finds, 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), only control nitridation two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2The mol ratio of c and tungsten carbide wc exists In the range of being somebody's turn to do, sulfur content in coking crude benzene can be realized and control in below 0.1ppm.That is, the four of the present invention kinds of activity Component is 1:(0.4-0.6 only in mol ratio): (0.28-0.45): when (0.8-1.2), just possess cooperative effect.Rub except this Outside you are than scope, or omit or replace any one component, do not enable 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.
An object of the present invention also resides in the promoter providing described catalyst.Catalyst of the present invention also contains There is catalyst aid, described catalyst aid is cr2o3、zro2、ceo2、v2o5And nbopo4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, there is a catalyst aid of maturation, such as p, f and b etc., its For adjusting the property of carrier, weaken strong interaction between metal and carrier, improve the surface texture of catalyst, improve metal Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned p, f and b catalysis helps Agent in application with the carrier of the present invention with active component when, for high sulphur component, it promotes the effect of catalytic desulfurization/refined ?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounds, Find eventually to adopt cr2o3、zro2、ceo2、v2o5And nbopo4The catalyst facilitation to the present invention for the mixture of (niobium phosphate) Substantially, its hydrothermal stability can be significantly improved, and improve its anti-coking deactivation, thus improving its service life.
Described cr2o3、zro2、ceo2、v2o5And nbopo4Between there is no the ratio of fixation that is to say, that cr2o3、zro2、 ceo2、v2o5And nbopo4Each respective content reaches effective dose.Preferably, the cr that the present invention adopts2o3、zro2、 ceo2、v2o5And nbopo4Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although not having specific proportion requirement between catalyst aid of the present invention, each auxiliary agent allows for reaching To the requirement of effective dose, the content of catalyst aid effect, the 1-7% of such as carrier quality can be played.The present invention is selecting During find, omitting or replacing one or more of described auxiliary agent, the technique effect all not reaching the present invention (improves water Heat stability, reduces coking and improves service life) close that is to say, that there is specific cooperation between the catalyst aid of the present invention System.
It is true that the present invention once attempted the niobium phosphate nbopo in catalyst aid4Replace with five oxidation two girl nb2o5, Have found that while in auxiliary agent and have also been introduced nb, but its technique effect is significantly lower than niobium phosphate nbopo4, not only hydrothermal stability is slightly for it Difference, its beds coking is relatively rapid, thus leading to catalyst duct to block, beds pressure drop rise is relatively Hurry up.The present invention also once attempted introducing other phosphate, although this attempt introducing phosphate anion, but equally existed hydro-thermal Stability is relatively slightly worse, and its beds coking is relatively rapid, thus leading to catalyst duct to block, beds pressure drop Rise relatively fast.
Although present invention introduces catalyst aid has so many advantage, the present invention should be noted that, introduces catalysis Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention. Do not introduce the catalyst aid particularly niobium phosphate of the present invention,, compared to the scheme introducing catalyst aid, its defect is only phase for it To.I.e. this defect be with respect to introduce catalyst aid after defect, its with respect to other prior arts outside the present invention, Institute mentioned by the present invention is advantageous or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention Indispensable technological means, it is optimization further to technical solution of the present invention, solves new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods of routine, people in the art 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:
By sodium silicate, cetyl trimethylammonium bromide (ctab), sodium ethylene diamine tetracetate (edta) and distillation hydromassage You mix the ratio than 1:0.25:1:60, load with 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 be 1:10), stir 0.5h under room temperature, 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 passes through to choose specific catalyst, and it is miscellaneous that described catalyst passes through incorporation Atom cu2+Kit-1 as carrier, and the nitridation two molybdenum mo choosing special ratios2N, tungsten nitride w2N, molybdenum carbide mo2C and carbon Change tungsten wc as active component, described catalyst also contains catalyst aid, described catalyst aid is cr2o3、zro2、ceo2、 v2o5And nbopo4Mixture so that this catalyst produces cooperative effect, the hydrodesulfurization to coking crude benzene can control in total sulfur Content is less than 0.1ppm.
Specific embodiment
The present invention is illustrated to the hydrodesulfurization of the present invention by following embodiments.
Embodiment 1
Catalyst is prepared by infusion process, carrier is doping cu2+Kit-1, cu2+Doping control in kit-1 Make the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C's 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 is entered fixed bed reactors, the reaction tube of described reactor is by the stainless steel of internal diameter 50mm Become, reaction bed temperature is measured with ugu808 type temp controlled meter, the twin columns that raw material light oil is manufactured by Beijing Satellite Manufacturing Factory Plug micro pump continuous conveying, hydrogen is supplied by gas cylinder and uses Beijing Sevenstar-HC d07-11a/zm gas mass flow gauge control Flow velocity processed, loaded catalyst is 2kg.
Coking crude benzene enters pre-reactor with hydrogen mixture from tower top, is 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 obtaining with Enter extractive distillation unit afterwards, extractant adopts sulfolane, and extraction temperature controls at 100 DEG C, and extracting pressure controls 200kpa.
Test final product, its total sulfur content is reduced to 0.07ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is doping cu2+Kit-1, cu2+Doping control in kit-1 Make the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C's 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 Example 1.
Test final product, its total sulfur content is reduced to 0.05ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-al2o3, remaining condition is constant.
Test final product, its total sulfur content is 12ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated kit-1, remaining condition is constant.
Test final product, its total sulfur content is 9ppm.
Comparative example 3
Cu by embodiment 12+Replace with zn2+, remaining condition is constant.
Test final product, its total sulfur content is 10ppm.
Comparative example 4
By the cu in embodiment 12+Doping in kit-1 controls the 0.5% of carrier quality, and remaining condition is constant.
Test final product, its total sulfur content is 18ppm.
Comparative example 5
By the cu in embodiment 12+Doping in kit-1 controls the 0.8% of carrier quality, and remaining condition is constant.
Test final product, its total sulfur content is 14ppm.
Embodiment 1 and comparative example 1-5 show, certain content scope and certain loads metal ions that the application adopts Kit-1 carrier, when replacing with other known carriers of this area, or carrier is identical but cu2+When doping is different, all reach not To the technique effect of the present invention, the therefore cu of the certain content scope of the present invention2+Doping kit-1 carrier and catalyst other components Between possess cooperative effect, described hydrodesulfurization creates unforeseeable technique effect.
Comparative example 6
Omit the mo in embodiment 12N, remaining condition is constant.
Test final product, its total sulfur content is 11ppm.
Comparative example 7
Omit the wc in embodiment 1, remaining condition is constant.
Test final product, its total sulfur content is 17ppm.
Above-described embodiment and the explanation of comparative example 6-7, several activearm of catalyst of the hydrodesulfurization of the present invention divides it Between exist 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 its product Give birth to cooperative effect.
Embodiment 3
Catalyst aid cr is contained in catalyst2o3、zro2、ceo2、v2o5And nbopo4, its content be respectively 1%, 1.5%, 2%th, 1% and 3%, remaining is same as Example 1.
Test final product, after it uses 3 months, beds pressure drop is not any change, use compared to same The beds pressure drop of time embodiment 1 reduces 17.6%.
Comparative example 8
Compared to embodiment 3, by nbopo therein4Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time The beds pressure drop applying example 1 only reduces 3.4%.
Comparative example 9
Compared to embodiment 3, by ceo therein2Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time The beds pressure drop applying example 1 only reduces 3.6%.
Embodiment 3 and comparative example 8-9 show, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted One of or several groups of timesharing, all can not reach the present invention and add minimizing coking during catalyst aid thus stoping catalyst bed The high technique effect of lamination falling-rising.That is, it demonstrates the service life that the catalyst aid of the present invention can improve described catalyst, And other catalyst aid effects are not so good as this specific catalyst aid.
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, that is, do not 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, the equivalence replacement to each raw material of product of the present invention 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 (7)

1. a kind of coking crude benzene hydrodesulfurization is it is characterised in that coking crude benzene is pre- anti-from tower top entrance with hydrogen mixture Answer device, in pre-reactor, be filled with nimo catalyst, its reaction temperature is 220-230 DEG C, 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 to mix hetero atom cu in synthesis framing structure2+Kit-1；Described active component For nitrogenizing two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C and the mixture of tungsten carbide wc；Described catalyst also contains catalysis to be helped Agent, described catalyst aid is cr2o3、zro2、ceo2、v2o5And nbopo4Mixture；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 is it is characterised in that hetero atom cu2+Doping be kit-1 weight 0.63%-0.72%.
3. hydrodesulfurization as claimed in claim 1 is 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 is 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 is 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 is it is characterised in that described fixed bed reactors include 1-5 catalysis Agent bed, preferably includes 2-3 beds.
7. hydrodesulfurization as claimed in claim 1 is it is characterised in that cr2o3、zro2、ceo2、v2o5And nbopo4Each Content be respectively carrier quality 1-7%, preferably 2-4%.
CN201610707985.0A 2016-08-23 2016-08-23 Hydrogenation and desulfurization process of coking crude benzol Pending CN106345518A (en)

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