CN106433757A - Coking crude benzene hydrodesulfurization technology - Google Patents

Coking crude benzene hydrodesulfurization technology Download PDF

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Publication number
CN106433757A
CN106433757A CN201610689454.3A CN201610689454A CN106433757A CN 106433757 A CN106433757 A CN 106433757A CN 201610689454 A CN201610689454 A CN 201610689454A CN 106433757 A CN106433757 A CN 106433757A
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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
    • C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • 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
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

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

Abstract

The invention discloses a coking crude benzene hydrodesulfurization technology; a coking crude benzene and hydrogen gas mixture enters a pre-reactor from a tower top, a product of pre-reaction enters a fixed bed reactor, and the fixed bed reactor is filled with a hydrodesulfurization catalyst, wherein the catalyst comprises a carrier and an active component; the carrier is MCM-41 formed by doping a heteroatom Co<2+> into a synthetic skeleton structure; the active component is a mixture of dimolybdenum nitride Mo2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide WC; the catalyst also contains a catalytic auxiliary agent, the catalytic auxiliary agent is a mixture of TiO2, CeO2, V2O5 and NbOPO4; the fixed bed reactor comprises the reaction conditions that the reaction temperature is 320-380 DEG C, the hydrogen gas pressure is 3.0-3.6 MPa, the hydrogen-oil volume ratio is 500-800, and the volume space velocity is 1.5-2 h<-1>; a product after fixed bed hydrogenation reaction enters an extractive distillation unit to obtain aromatic hydrocarbons. The process enables the total sulfur content in the coking crude benzene is reduced to 0.1 ppm or less, and can meet an extensive use.

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 one of major way of Coal dressing, also commonly referred to as the high-temperature retorting of 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, melt through drying, pyrolysis, burning, bond, solidify Finally prepare coke with the stage such as contraction.The volatile matter separating out in process of coking includes that the chemistry such as coal gas, tar, ammonia and crude benzol produce Product.In addition, the coal tar obtaining 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, typically in two steps, the first step：Pre-hydrotreating reaction, main with conventional catalyst removal coking 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 disulfide 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's 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 evaporimeter 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 is 610～630 DEG C, and pressure is 5l0MPa, and catalyst is Cr system Catalyst.Pre-reactor be at a lower temperature (200～250 DEG C) homologues such as the styrene of easily polymerization under the condition of high temperature Carry out hydrogenation reaction, prevent it to be polymerized in main reactor, make catalyst activity reduce, in two main reactors, complete hydrogenation Cracking, the de-reaction such as alkyl, desulfurization.The condensed cooling system of oil gas discharged by main reactor, isolated liquid is hydrogenation Oil, isolated hydrogen and low molecular hydrocarbon remove H2After S, a part is sent to hydrogenation system, and a part is sent to reforming hydrogen manufacturing system 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 wanting height to equipment requirement, 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 just once 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 the 99.9%th, crystalline temperature 5.52 ℃：, total sulphur content less than lppm, thiophene content less than spy's purified petroleum benzin of 0.5ppm.Henan Shen Ma company is also a complete set of subsequently 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 obtaining 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 components formed azeotropic mixture and Boiling point is higher), each component solubility 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 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 use to aromatic hydrocarbon product produces considerable restraint
It how therefore a kind of hydrodesulfurization is provided, effectively can control the sulfur content of coking crude benzene product at 0.1ppm Hereinafter, it to meet its application standard, is the difficult problem that this area faces.
Content 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, and minimum to 0.05ppm, the application to meet product requires.
For reaching this purpose, the present invention is 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 being 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 TiO2、CeO2、V2O5And NbOPO4Mixing Thing.
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 uses routine to set Standby and technique, the improvement to coking crude benzole hydrogenation sulfur removal technology for the present invention, 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 arrangements, size are uniform, aperture size can with synthesis when The difference of addition 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), beneficially 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, and discovery only has 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 very 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+Salting liquid, before MCM-41 framework of molecular sieve structure is formed, by same order elements by Co2+Replace part skeleton unit Element thus in the skeleton of embedded molecular sieve, improve catalysis activity, absorption and the heat of MCM-41 mesopore molecular sieve on the whole Mechanical stability can wait.
Although the method be modified to 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 control and the balance of loss of octane number, invention as carrier People has attempted adulterating in MCM-41:Al3+、Fe3+、Zn2+、Ga3+In the ion producing anionic surface center, discovery 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 same order elements 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, is the 0.56%-0.75% of MCM-41 weight, for example the 0.57%th, the 0.58%th, the 0.59%th, the 0.6%th, the 0.61%th, the 0.62%th, 0.63%th, the 0.64%th, the 0.65%th, the 0.66%th, the 0.67%th, the 0.68%th, the 0.69%th, the 0.7%th, the 0.71%th, the 0.72%th, the 0.73%th, 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 drafting is with Co2+Doping is transverse axis, during curve map 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 producing, 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%.For example, the 2%th, the 2.5%th, the 3%th, the 3.5%th, the 4%th, the 4.5%th, the 5%th, the 5.5%th, the 6%th, the 6.5%th, described content can be 7%th, the 7.5%th, the 8%th, the 8.5%th, the 9%th, the 9.5%th, the 10%th, the 10.5%th, the 11%th, the 11.5%th, the 12%th, the 12.5%th, the 13%th, 13.5%th, the 14%th, 14.5% etc..
It in the present invention, 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), 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 Gai, can realize that in coking crude benzene, sulfur content controls at below 0.1ppm.It is to say, the four of the present invention kinds of activity Component is only 1 in mol ratio:(0.4-0.6):(0.28-0.45):(0.8-1.2), when, just possesses 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 co-catalyst of described catalyst.Catalyst of the present invention possibly together with Catalyst aid, described catalyst aid is TiO2、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 in application with the carrier of the present invention with active component when, 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, compounds, Discovery eventually uses TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improve its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that TiO2、CeO2、V2O5With NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention uses2、CeO2、V2O5And NbOPO4 Respective 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 content of catalyst aid effect, the 1-7% of such as carrier quality i.e. can be played.The present invention is selecting During discovery, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water Heat endurance, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and close specific cooperation 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 also once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal Stability is relatively 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 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 introducing 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, 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 alternatives, 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 TiO2、CeO2、V2O5With NbOPO4Mixture so that this catalyst produce cooperative effect, the hydrodesulfurization to coking crude benzene can control at total sulfur content Less than 0.1ppm.
Detailed description of the invention
The present invention is illustrated by the hydrodesulfurization to the present invention for the following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Co2+MCM-41, Co2+Doping in MCM-41 Control 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 be the 10% of carrier quality, 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 used by gas cylinder 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 main reaction 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 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 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 be the 10% of carrier quality, 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 and comparative example 1-5 show, the 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+When doping is different, 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
Catalyst contains catalyst aid TiO2、CeO2、V2O5And NbOPO4, the 1%th, its content be respectively the 1.5%th, 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%.
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 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 5%.
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 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 high technique effect of lamination falling-rising.That is, its catalyst aid demonstrating the present invention can improve the service life of 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, 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 each raw material 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, being 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 TiO2、CeO2、V2O5And NbOPO4Mixture；The reaction condition of described fixed bed reactors is：Instead Temperature is answered to be 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；Fixed bed Product after hydrogenation reaction 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 TiO2、CeO2、V2O5And NbOPO4Respective content It is respectively the 1-7%, preferably 2-4% of carrier quality.
CN201610689454.3A 2016-08-16 2016-08-16 Coking crude benzene hydrodesulfurization technology Pending CN106433757A (en)

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