CN106244203A - A kind of coking crude benzene hydrodesulfurization - Google Patents

A kind of coking crude benzene hydrodesulfurization Download PDF

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CN106244203A
CN106244203A CN201610696984.0A CN201610696984A CN106244203A CN 106244203 A CN106244203 A CN 106244203A CN 201610696984 A CN201610696984 A CN 201610696984A CN 106244203 A CN106244203 A CN 106244203A
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catalyst
fixed bed
hydrodesulfurization
hydrogen
mcm
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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
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
    • 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
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • 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
    • 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
    • C10G2300/70—Catalyst aspects

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (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+MCM 41；Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc；Described catalyst is possibly together with catalyst aid, and described catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixture；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+MCM-41.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
Described catalyst is possibly together with 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 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.
MCM-41 is ordered into mesoporous material, and its duct is that six side's ordered arrangement, size are uniform, aperture size can with synthesis time The difference adding directed agents and synthetic parts changes between 1.5～10nm, lattice parameter about 4.5nm, specific pore volume about 1mL/g, MCM-41 uniform pore diameter, has higher specific surface area (1000m2/ g) and big adsorption capacity (0.7mL/g), the most organic The free diffusing of molecule.The present invention through in numerous mesoporous materials, such as MCM-22, MCM-36, MCM-48, MCM-49, MCM56, carries out contrast test selection, finds that only MCM-41 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 MCM-41 is as carrier basis.
The acidity of silica MCM-41 own is the most weak, is directly used as catalyst activity relatively low.Therefore, it is changed by the present invention Property, to increase its catalysis activity.The approach that MCM-41 mesopore molecular sieve is modified is by the present invention: in MCM-41 building-up process, Add Co2+Saline solution, before MCM-41 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part skeleton unit Element thus embed in the skeleton of molecular sieve, improve on the whole MCM-41 mesopore molecular sieve catalysis activity, absorption and heat Mechanical stability can wait.
Although the method being modified MCM-41 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges Agent can only use doping Co2+MCM-41 could realize sulfur content as carrier and control and the balance of loss of octane number, invention People has attempted adulterating in MCM-41: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all can not Realize described effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on MCM-41 inner surfaces of pores to compare, The isomorphous substitution approach of the present invention is more stable.Although described mechanism is current and unclear, but this has no effect on the reality of the present invention Executing, inventor 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 MCM-41 must control within specific content range, and its doping is with weight Meter, for the 0.56%-0.75% of MCM-41 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 MCM-41 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 MCM-41 weight, preferably 3-12%, further preferably 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 three of the purpose of the present invention are to provide the promoter of described catalyst.Catalyst of the present invention possibly together with Catalyst aid, described catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its For regulating the character of carrier, weaken interaction strong 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 application with the carrier of the present invention with active component time, for high-sulfur 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, compounding, Find eventually to use Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) the catalyst facilitation to the present invention Substantially, its hydrothermal stability can be significantly improved, and improve its anti-coking deactivation, thus improve its service life.
Described Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that Cr2O3、ZrO2、 CeO2、V2O5And NbOPO4Each respective content reaches effective dose.Preferably, the Cr that the present invention uses2O3、ZrO2、 CeO2、V2O5And NbOPO4Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass 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 causes catalyst duct to block, and beds pressure drop rise is relatively Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce 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. Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid, Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
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.
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+MCM-41 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and Tungsten carbide wc is as active component, and described catalyst is possibly together with catalyst aid, and described catalyst aid is Cr2O3、ZrO2、CeO2、 V2O5And NbOPO4Mixture so that this catalyst produce cooperative effect, 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+MCM-41, Co2+Doping in MCM-41 Control 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 carrier quality 10%, 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 0.05ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+MCM-41, Co2+Doping in MCM-41 Control 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 carrier quality 10%, 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 1.5ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated MCM-41, and remaining condition is constant.
Testing final product, its total sulfur content is 2ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, its total sulfur content is 3ppm.
Comparative example 4
By the Co in embodiment 12+Doping in MCM-41 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, its total sulfur content is 5ppm.
Comparative example 5
By the Co in embodiment 12+Doping in MCM-41 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, its total sulfur content is 6ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion MCM-41 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+During doping difference, all reach Less than the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping MCM-41 carrier and catalyst other Possessing cooperative effect between component, 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 1.8ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, its total sulfur content is 1.9ppm.
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.
Embodiment 3
Containing catalyst aid Cr in catalyst2O3、ZrO2、CeO2、V2O5And NbOPO4, its content is respectively 2%, 1%, 1.5%, 1% and 3%, remaining is same as in Example 1.
Testing final product, after it uses 3 months, beds pressure drop is not any change, and uses compared to same The beds pressure drop of time embodiment 1 reduces 16.6%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same The beds pressure drop executing example 1 only reduces 3.2%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same The beds pressure drop executing example 1 only reduces 3.5%.
Embodiment 3 shows with comparative example 8-9, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted When one of them or several component, all can not reach the minimizing coking when present invention adds catalyst aid thus stop catalyst bed The technique effect that lamination falling-rising is high.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst, And other catalyst aid effects are not 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, 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 (7)

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+MCM-41；Described active component For nitrogenizing two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc；Described catalyst helps possibly together with catalysis 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, it is characterised in that hetero atom Co2+Doping be MCM-41 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 MCM- The 3-12% of 41 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.
7. hydrodesulfurization as claimed in claim 1, it is characterised in that Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Each Content be respectively the 1-7%, preferably 2-4% of carrier quality.
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