CN106318450A - Hydrofining catalyst - Google Patents

Hydrofining catalyst Download PDF

Info

Publication number
CN106318450A
CN106318450A CN201610688776.6A CN201610688776A CN106318450A CN 106318450 A CN106318450 A CN 106318450A CN 201610688776 A CN201610688776 A CN 201610688776A CN 106318450 A CN106318450 A CN 106318450A
Authority
CN
China
Prior art keywords
catalyst
kit
carrier
present
gasoline
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201610688776.6A
Other languages
Chinese (zh)
Inventor
朱忠良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xishan Lvchun Plastic Products Factory
Original Assignee
Xishan Lvchun Plastic Products Factory
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xishan Lvchun Plastic Products Factory filed Critical Xishan Lvchun Plastic Products Factory
Priority to CN201610688776.6A priority Critical patent/CN106318450A/en
Publication of CN106318450A publication Critical patent/CN106318450A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C10G45/12—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
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • 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

Landscapes

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

Abstract

The invention discloses a hydrofining catalyst which comprises a carrier and an active ingredient, wherein the carrier is KIT-1, a heteroatom Co<2+> is doped into a synthesis framework structure of the KIT-1, the doping amount is 0.56%-0.75% of the weight of the KIT-1, the active ingredient is a mixture of Mo2N, W2N, Mo2C and WC, the total content of the active ingredient is 1%-15% of the weight of the carrier KIT-1, the catalyst further comprises a catalytic additive, and the catalytic additive is a mixture of TiO2, CeO2, V2O5 and NbOPO4. The catalyst reduces the total sulphur content of an FCC gasoline to be lower than 10ppm to meet the tier 5 gasoline standard. Meanwhile, the octane value of the FCC gasoline is also slightly reduced due to the adoption of the catalyst.

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.
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2, CeO2、V2O5And NbOPO4Mixing Thing.
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.
An object of the present invention also resides in the promoter providing described catalyst.Catalyst of the present invention also contains Having 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 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 TiO2, CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, Its hydrothermal stability can be significantly improved, 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, TiO2, CeO that the present invention uses2、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 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.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 help possibly together with catalysis as active component, described catalyst Agent, described catalyst aid is TiO2, CeO2、V2O5And NbOPO4Mixture so that this catalyst produce cooperative effect, to FCC The hydrodesulfurization of gasoline can control at total sulfur content less than 5ppm, and octane number reduction amplitude controls within 0.5-2% simultaneously.
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.
Embodiment 3
Containing catalyst aid TiO2, CeO in catalyst2、V2O5And NbOPO4, its content is respectively 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 15.3%.
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 2.1%.
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 2.4%.
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 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 (6)

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；
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2, CeO2、V2O5And NbOPO4Mixture.
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.
6. Hydrobon catalyst as claimed in claim 1, it is characterised in that TiO2, CeO2、V2O5And NbOPO4Respective contain Amount is respectively the 1-7%, preferably 2-4% of carrier quality.
CN201610688776.6A 2016-08-18 2016-08-18 Hydrofining catalyst Withdrawn CN106318450A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610688776.6A CN106318450A (en) 2016-08-18 2016-08-18 Hydrofining catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610688776.6A CN106318450A (en) 2016-08-18 2016-08-18 Hydrofining catalyst

Publications (1)

Publication Number Publication Date
CN106318450A true CN106318450A (en) 2017-01-11

Family

ID=57744036

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610688776.6A Withdrawn CN106318450A (en) 2016-08-18 2016-08-18 Hydrofining catalyst

Country Status (1)

Country Link
CN (1) CN106318450A (en)

Similar Documents

Publication Publication Date Title
CN106268912A (en) A kind of Hydrobon catalyst
CN106140247A (en) A kind of Hydrobon catalyst
CN106318450A (en) Hydrofining catalyst
CN106433758A (en) HDS (hydrodesulfurization) technology of FCC (fluid catalytic cracking) gasoline
CN106311314A (en) Hydrodesulphurization catalyst
CN106336895A (en) Hydrofining catalyst
CN106244196A (en) A kind of FCC gasoline hydrodesulfurization
CN106221755A (en) A kind of FCC gasoline hydrodesulfurization
CN106221748A (en) A kind of FCC gasoline hydrodesulfurization
CN106268911A (en) A kind of Hydrobon catalyst
CN106622358A (en) Composite support hydrodesulfurization catalyst
CN106221754A (en) A kind of FCC gasoline hydrodesulfurization
CN106244212A (en) A kind of FCC gasoline hydrodesulfurization
CN106378175A (en) A hydrodesulfurization catalyst
CN106190261A (en) A kind of FCC gasoline hydrodesulfurization
CN106190237A (en) A kind of FCC gasoline hydrodesulfurization
CN106268913A (en) A kind of Hydrobon catalyst
CN106281420A (en) A kind of FCC gasoline hydrodesulfurization
CN106423248A (en) Hydrofining catalyst
CN106378174A (en) A hydrofining catalyst
CN106190250A (en) A kind of FCC gasoline hydrodesulfurization
CN106318455A (en) Hydrogen desulfurization catalyst
CN106190265A (en) A kind of FCC gasoline hydrodesulfurization
CN106190243A (en) A kind of FCC gasoline hydrodesulfurization
CN106433750A (en) Hydrogenation desulfurization and denitrification process of diesel oil

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20170111