CN106268912A - A kind of Hydrobon catalyst - Google Patents

A kind of Hydrobon catalyst Download PDF

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Publication number
CN106268912A
CN106268912A CN201610657443.7A CN201610657443A CN106268912A CN 106268912 A CN106268912 A CN 106268912A CN 201610657443 A CN201610657443 A CN 201610657443A CN 106268912 A CN106268912 A CN 106268912A
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kit
catalyst
carrier
gasoline
molybdenum
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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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • 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
    • 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
    • C10G2300/20—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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

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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)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of Hydrobon catalyst, described catalyst includes that carrier and active component, described carrier are incorporation hetero atom Co in synthetic bone shelf structure2+KIT 1, its doping is 0.56% the 0.75% of KIT 1 weight；Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, the total content of described active component is 1% the 15% of carrier KIT 1 weight.Total sulfur content in FCC gasoline can be reduced to below 10ppm by this catalyst, to meet gasoline state five standard.Meanwhile, the employing of this catalyst also makes the octane number of FCC gasoline significantly reduce.

Description

A kind of Hydrobon catalyst
Technical field
The present invention relates to catalyst technical field, be specifically related to a kind of hydrodesulfurization catalyst for refining, more preferably relate to one Plant FCC gasoline hydrodesulfurization and reduce the catalyst of octane number reduction amplitude.
Background technology
Entering 21st century, demand and the use of fuel oil increase substantially, and sulfur-containing compound therein is brought Problem of environmental pollution, more cause the concern of people.The oxysulfide that sulfide in fuel oil produces through engine combustion (SOx) be discharged in air, produce acid rain and fumes of sulphuric acid type pollution etc., cause atmospheric pollution.
Sulfur is a kind of harmful substance that nature is present in gasoline, and in gasoline product, the sulfur of more than 80% carrys out self-catalysis and splits Changing (FCC) gasoline, along with constantly becoming of crude oil is heavy, the sulfur content in FCC gasoline also can be continuously increased.External gasoline is generally from FCC (34%), catalytic reforming (33%), and the technique such as alkylation, isomerization and etherificate (the most totally 33%)；And home-produced fuel 80% is from FCC gasoline.Due in gasoline the sulfur of 85%～95% from FCC gasoline so that the sulfur content in China's gasoline More than external gasoline a lot.A lot of experts have carried out the research that motor vehicle exhaust emission is affected by sulfur, and result shows: if by gasoline In sulfur content from 450 μ g g-1It is reduced to 50 μ g g-1, NO in vehicle exhaustxAverage minimizing 9%, CO averagely reduces 19%, HC averagely reduce 18%, and Toxic averagely reduces 16%.Thus, effective fuel oil hydrodesulfurization technology, to society, warp Ji, the development of environment have important effect.
Most effective, the most economical sulfur method that hydrodesulfurization (HDS) technology is well recognized as at present, especially selective hydrogenation Desulfurization technology, i.e. suppresses the saturated to reduce loss of octane number of alkene while the removing a large amount of sulfur-containing compound of gasoline as far as possible. The features such as this kind of technology has operating condition and relaxes, and yield of gasoline is high, and hydrogen consumption is low and loss of octane number is little.Hydrodesulfurization technology It is crucial that the selection of Hydrobon catalyst, the cobaltmolybdate catalyst of support type is the gasoline hydrodesulfurizationcatalyst catalyst that a class is important, It is typically cobalt molybdenum to load on porous support (such as aluminium oxide, silicon oxide, activated carbon or its complex carrier), is widely used in adding In hydrogen sweetening process, to obtain premium-type gasoline product.
Hydrodesulfurization (HDS) technology is to grow up the fifties, and the nineties, this technology welcome second improving and developing Individual peak period, its technical maturity, all the time, become sulfur, nitrogen, oxygen in removing distillate, improve oil product Practical Performance with clear The maximally efficient means of cleanliness.The activity and selectivity of catalyst is the key factor affecting hydrofinishing efficiency and the degree of depth, Economy and environmental benefit that high performance catalyst is brought are very significant, have therefore attracted numerous enterprises and researcher to put into In developing to efficient catalyst, the catalyst prod develop many function admirables, differing from one another.Hydrogenation technique is sent out rapidly The basic reason of exhibition is the development of catalyst, but alkene can be caused while routine techniques desulfurization saturated and product octane number (RON) decline, therefore desulfurization and the few selective hydrogenation new technique of loss of octane number can become what HDS method in recent years was improved Main way.
The RESOLVE technological development of Akzo Nobel company exploitation catalytic cracking reduces the RESOLVE of content of sulfur in gasoline Additive product series, uses high hydrogen transfer activity component and ADM-20, and cracking gasoline sulfur content can be made to reduce by 20%, RESOLVE-700 gasoline reduces in sulfur additives currently industrial evaluation.
Exxon research engineering company is Containing Sulfur in selectively removing FCC gasoline with Akzo Nobel company joint development The Scanfining technology of compound, and pushed this technology to industrialization in 1998.It uses traditional hydrotreating flow process, logical Cross meticulous selecting catalyst (RT-225), make loss of octane number and hydrogen consumption reach minimum.
The Prime-G technology of France's IFP exploitation, this technology, by France studying and designing institute (IFP) exploitation, uses dual catalyst System.Its process conditions relax, and hydrogenation of olefins activity is low, does not occur alkene saturated and cracking reaction, and liquid yield reaches 100%, Desulfurization degree is more than 95%, and loss of octane number is few, and hydrogen consumption is low.By FCC heavy petrol hydrodesulfurization, being in harmonious proportion the gasoline product obtained can To realize the target of sulfur content 100～150 μ g g-1；By the hydrodesulfurization respectively of FCC petroleum benzin, sulfur content 30 μ can be realized The target of g g-1.
For the feature of domestic FCC gasoline sulfur-bearing, Fushun Petrochemical Research Institute (FRIPP) develops FCC gasoline and selects Property hydrogen addition technology (OCT-M) and full distillation gasoline selective hydrogenation technology (FRS), device can produce sulfur nutrient and be not more than 150μg·g-1GB III gasoline.OCT-M technology, after Shijiazhuang Oil Refinery, China Petrochemical Corp. continuously runs 17 months, uses Two kinds of prioritization schemes that FRIPP recommends, after FCC gasoline hydrogenation, sulfur nutrient reaches GB III and IV standard.
On May 5th, 2016, the issue of seven departments such as the Committee of Development and Reform, the Ministry of Finance, Chinese Ministry of Environmental Protection " accelerates product oil quality about printing and distributing Upgrade job scheme " notice, scheme clearly expands automobile-used vapour, diesel oil state five standard performs scope.From original Jing-jin-ji region, length three Angle, region, Pearl River Delta key cities expand 11, whole eastern region provinces and cities (Beijing, Tianjin, Hebei, Liaoning, Shanghai, river to Soviet Union, Zhejiang, Fujian, Shandong, Guangdong and Hainan).Before 31 days October in 2015, eastern region is protected possesses manufacturing country five mark for enterprise Quasi-motor petrol (containing ethanol petrol blend component oil), the ability of derv fuel.On January 1st, 2016 rises, and eastern region supplies comprehensively The motor petrol (containing E10 ethanol petrol) of state five standard, derv fuel (containing B5 biodiesel) should be met.
At present, the main method reducing FCC gasoline sulfur content is catalytic desulfurhydrogenation.But hydrotreating method exists such as Lower deficiency: (1) equipment investment is big；(2) severe reaction conditions of the de-thiophenic sulfur of hydrogenation, operating cost is high；(3) alkene is de-at hydrogenation Easily occur saturated under the conditions of sulfur, not only consume a large amount of hydrogen, and cause octane number to reduce.FCC gasoline desulfurization degree requirement The highest, operating condition is the harshest, and the loss of octane number is the biggest.
A kind of Hydrobon catalyst is provided, can effectively the sulfur content in gasoline be controlled at below 10ppm, To meet state five standard, octane number loss simultaneously is less or do not lose, and is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of Hydrobon catalyst, this catalyst can be by the total sulfur in FCC gasoline Content is reduced to below 10ppm, to meet gasoline state five standard.Meanwhile, the employing of this catalyst also makes the octane of FCC gasoline Value significantly reduces.
For reaching this purpose, the present invention by the following technical solutions:
The catalyst of a kind of hydrodesulfurization, described catalyst includes carrier and active component.
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT-1.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
KIT-1 molecular sieve has one-dimensional channels and crosses each other to form three-dimensional disordered structure, and this structure is conducive to catalysis, absorption During material transmission.Pure silicon mesopore molecular sieve KIT-1 has heat stability more more preferable than MCM-241, HMS and hydrothermally stable Property.The present invention through in numerous mesoporous materials, such as KIT-1, KIT-6, MCM-22, MCM-36, MCM-48, MCM-49, MCM56 etc., carry out contrast test selection, find that only KIT-1 can reach the goal of the invention of the present invention, and other mesoporous materials are all Having such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, therefore the present invention selects to use KIT-1 is as carrier basis.
Although pure silicon KIT-1 mesopore molecular sieve hydro-thermal performance is outstanding, but inventor's research is later discovered that, it adds Hetero atom or surface are after chemical modification, and its hydrothermal stability obtains bigger raising.Therefore, it is modified by the present invention, with Increase its catalysis activity.The approach that KIT-1 mesopore molecular sieve is modified is by the present invention: in KIT-1 building-up process, adds Co2+ Saline solution, before KIT-1 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part backbone element thus embedding Enter in the skeleton of molecular sieve, improve catalysis activity, absorption and the thermodynamic stability of KIT-1 mesopore molecular sieve on the whole Can etc..
Although the method being modified KIT-1 mesopore molecular sieve or approach are a lot, inventor finds, the catalysis of the present invention Agent can only use doping Co2+KIT-1 could realize sulfur content as carrier and control and the balance of loss of octane number, inventor tastes Try to adulterate in KIT-1: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all to realize institute State effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on KIT-1 inner surfaces of pores to compare, the present invention Isomorphous substitution approach more stable.Although described mechanism is current and unclear, but this has no effect on the enforcement of the present invention, invention People is according to well-known theory and it is experimentally confirmed that there is cooperative effect between itself and the active component of the present invention.
Described Co2+Doping in KIT-1 must control within specific content range, and its doping is with weight Meter, for the 0.56%-0.75% of KIT-1 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%, 0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%, 0.74 etc..
Inventor finds, outside this range, can cause drastically reducing of octane number.More pleasurable, when Co2+When doping in KIT-1 controls in the range of 0.63%-0.72%, it is the strongest to the control of octane number, when draw with Co2+Doping is transverse axis, and during curve chart with target octane number as the longitudinal axis, in this content range, sulfur content can control extremely low Within the scope of, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier KIT-1 weight, preferably 3-12%, further preferred 5- 10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28- 0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists In the range of Gai, sulfur content in FCC gasoline can be realized and control not to be decreased obviously at below 10ppm and octane number.Also That is, four kinds of active components of the present invention are only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), Just possesses cooperative effect.Outside this molar ratio range, or omit or replace any one component, all can not realize association Same effect.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45- 0.5): (0.35-0.45): (0.8-1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0), Preferably 1:0.48:0.42:0.95.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.The typical but non-limiting example of the present invention As follows:
Sodium silicate, cetyl trimethylammonium bromide (CTAB), sodium ethylene diamine tetracetate (EDTA) and distilled water are massaged You mix the ratio than 1:0.25:1:60, load with in teflon-lined autoclave pressure, after stirring under 373K Constant temperature 24h, the pH of re-adjustments mixture are 10.5, after constant temperature 4 times, take out product, with distilled water cyclic washing to filtrate PH=7, then under 373K, constant temperature overnight, obtains the KIT-1 with surfactant.KIT-1 with surfactant is existed Roasting 1.5h under 523K, then roasting 6h in air atmosphere under 813K, obtains KIT-1 powder body.By this powder body 0.1mol/L Salpeter solution carry out pickling (control solid-to-liquid ratio is 1:10), under room temperature stir 0.5h, filter, be washed with distilled water to filtrate Dry under pH=7,373K and obtain matrix KIT-1 molecular sieve.
The catalyst of the present invention, may be used for the hydrodesulfurization of gasoline, is particularly suitable for the hydrodesulfurization of FCC gasoline.
The present invention is by choosing specific incorporation hetero atom Co2+KIT-1 as carrier, and choose the nitridation of special ratios Two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc are as active component so that this catalyst produces cooperative effect, The hydrodesulfurization of FCC gasoline can be controlled at total sulfur content less than 5ppm, simultaneously octane number reduce amplitude control 0.5-2% it In.
Detailed description of the invention
The catalyst of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Co2+Doping control in KIT-1 of KIT-1, Co2+ System is at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Total content is the 10% of carrier quality, and its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm Becoming, reaction bed temperature UGU808 type temp controlled meter is measured, the twin columns that raw material light oil is manufactured by Beijing Satellite Manufacturing Factory Plug micro pump carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-11A/ZM mass-flow gas meter control by gas cylinder Flow velocity processed, loaded catalyst is 2kg.Reacted product cools down laggard row gas-liquid separation through water-bath room temperature.
Raw materials used for full fraction FCC gasoline, it contains alkene 25.3m%, aromatic hydrocarbons 40.2m%, alkane 28.8m%, grinds The method octane number of studying carefully is 94.2, total sulfur content 660 μ g/g.
Controlling reaction condition is: temperature 370 DEG C, Hydrogen Vapor Pressure 3.0MPa, hydrogen to oil volume ratio 600, volume space velocity 3h-1。
Testing final product, its research octane number (RON) still reaches 94.0, and total sulfur content is reduced to 3ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is the KIT-1, Co2+ of the doping Co2+ doping in KIT-1 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 research octane number (RON) still reaches 94.0, and total sulfur content is reduced to 2ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, its research octane number (RON) is 80, and total sulfur content is 34ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated KIT-1, and remaining condition is constant.
Testing final product, its research octane number (RON) is 82, and total sulfur content is 37ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, its research octane number (RON) is 82, and total sulfur content is 31ppm.
Comparative example 4
Controlling at the 0.5% of carrier quality by the doping in KIT-1 of the Co2+ in embodiment 1, remaining condition is constant.
Testing final product, its research octane number (RON) is 84, and total sulfur content is 49ppm.
Comparative example 5
By the Co in embodiment 12+Doping in KIT-1 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, its research octane number (RON) is 83, and total sulfur content is 41ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion KIT-1 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+During doping difference, all reach not To the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping KIT-1 carrier and other components of catalyst Between possess cooperative effect, create unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, its research octane number (RON) is 84, and total sulfur content is 45ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, its research octane number (RON) is 83, and total sulfur content is 44ppm.
, between several active component of catalyst of the present invention, there is specific connection in above-described embodiment and the explanation of comparative example 6-7 System, is omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated which create cooperative effect.
Applicant states, the present invention illustrates the catalyst of the present invention by above-described embodiment, but the present invention does not limit to In above-mentioned catalyst, i.e. do not mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.The skill of art Art personnel are 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 adding of auxiliary element Add, concrete way choice etc., all fall within protection scope of the present invention and open within the scope of.

Claims (5)

1. the de-refined agent of hydrogenation, described catalyst includes carrier and active component, it is characterised in that
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT-1, its doping is the 0.56%-of KIT-1 weight 0.75%；
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described activity The total content of component is the 1%-15% of carrier KIT-1 weight.
2. Hydrobon catalyst as claimed in claim 1, it is characterised in that hetero atom Co2+Doping be KIT-1 weight 0.63%-0.72%.
3. Hydrobon catalyst as claimed in claim 1, it is characterised in that the total content of described active component is carrier The 3-12% of KIT-1 weight, preferably 5-10%.
4. Hydrobon catalyst 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. Hydrobon catalyst as claimed in claim 1, it is characterised in that described Hydrobon catalyst is used for FCC vapour The hydrodesulfurization of oil refines.
CN201610657443.7A 2016-08-11 2016-08-11 A kind of Hydrobon catalyst Withdrawn CN106268912A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN107570199A (en) * 2017-07-31 2018-01-12 刘义林 Catalyst of Co/MCM 41 and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107570199A (en) * 2017-07-31 2018-01-12 刘义林 Catalyst of Co/MCM 41 and preparation method thereof

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