CN106221724A - A kind of biodiesel hydrogenation deoxidation technique - Google Patents

A kind of biodiesel hydrogenation deoxidation technique Download PDF

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Publication number
CN106221724A
CN106221724A CN201610709676.7A CN201610709676A CN106221724A CN 106221724 A CN106221724 A CN 106221724A CN 201610709676 A CN201610709676 A CN 201610709676A CN 106221724 A CN106221724 A CN 106221724A
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hydrogenation deoxidation
catalyst
technique
fixed bed
bed reactors
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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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • 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
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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

Abstract

The invention discloses biodiesel hydrogenation deoxidation technique, it is characterised in that described technique uses fixed bed reactors, is filled with hydrogenation deoxidation catalyst in fixed bed reactors, and 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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixture；The reaction condition of described fixed bed reactors is: reaction temperature is 300 450 DEG C, Hydrogen Vapor Pressure 2.5 3.5MPa, hydrogen to oil volume ratio 500 800, volume space velocity 1.0 2.5h‑1.The hydrogenation deoxidation of biodiesel can be controlled at higher DNA vaccine (more than 99.8%) and run 500 hours catalysis activity continuously without being decreased obviously by this technique.

Description

A kind of biodiesel hydrogenation deoxidation technique
Technical field
The present invention relates to biodiesel hydrogenation deoxidation technique.
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.
In order to solve increasingly serious environmental problem, reduce the Fossil fuel pollution to environment, since a recent period of time, with Based on vegetable oil, make full use of reproducible resource as fuel, just becoming focus.
The eighties in last century, American Graham Quick introduces diesel engine oleum lini oleic acid methyl ester for the first time and makes With, hereafter, the fatty-acid monoester compounds obtained through ester exchange reaction is defined as biodiesel.This fatty-acid monoester Compounds can be used alone, it is also possible to is used in mixed way with conventional fossil diesel oil, has caused people to biodiesel from this Research boom.
Being found by research, the primary chemical composition in vegetable oil is basically identical, and therefore any vegetable oil can Biodiesel fuel is changed into, such as soybean oil, Oleum Brassicae campestris and waste oil etc. as raw material.People concentrates and have studied with fat Acid compounds is the synthesis technique of target product, has prepared with fatty acid methyl ester for representing the biodiesel of component. Nineteen ninety, Austria goes into operation and has built up world's head set ton fatty methyl ester production device with Oleum Brassicae campestris as raw material, thereafter, Production of biodiesel is flourish, and the most only in Europe, biodiesel production capacity alreadys more than 13,000,000 tons.It follows that it is biological Diesel oil is that in oil and fat chemical, yield is maximum, fastest-rising kind.
Compared with petrifaction diesel, biodiesel possesses lot of advantages: using renewable oils and fats is raw material, not by raw material reserves Limit；The harmful element content such as S, N are low, little to atmospheric pollution after burning；Having higher Cetane number, unit product contains energy High；Containing O element, contribute to burning fully, the most effectively reduce the discharge of CO；Flash-point is high, transport with use safer.But Along with the extensive application of biodiesel, its defect existed the most more and more is found: containing not in vegetable and animals oils fat raw material Congener fatty acid, its production technology will not change degree of unsaturation, and degree of unsaturation is high, and such as Oleum Gossypii semen, Oleum Brassicae campestris etc. are raw The biodiesel that output is come, containing substantial amounts of carbon-to-carbon unsaturated bond in molecular structure, in accumulating and use, easily oxidation causes Rotten, if degree of unsaturation is low, as industrial lard, Adeps Bovis seu Bubali etc. produce the biodiesel obtained, its freezing point is higher than petrifaction diesel Going out a lot, even if being used in mixed way with petrifaction diesel with relatively low ratio, it is when low temperature times such as autumn and winters, easily separates out and causes Pipeline blockage, even can damage electromotor time serious.Although people have carried out numerous studies and improvement, but the molecule of biodiesel Structure does not change, and therefore its defect remains on existence.
In recent years, the synthetic route with deep hydrogenation as core prepares biodiesel, carries out biodiesel in other words Modification, has obtained increasing concern.This technique notes by oils and fats is carried out hydrogenation deoxidation reaction and hysomer Reaction, the final saturated alkane obtaining long-chain.The biodiesel that this technique obtains is at molecular structure and aspect of performance and fossil bavin Oil more closely, more convenient in product use, have begun to large-scale industrialization at present and promotes.
The deoxidization technique of present stage comparative maturity has: direct hydrogenation deoxidization technique, and hydrogenation deoxidation isomerization processes again, diesel oil is mixed Sweetening process, hydrogenation deoxidation technique.Wherein, activity and the life-span of catalyst is key influence factor.Owing to reaction mechanism is similar to, one As hydrogenation deoxidation catalyst be to grow up based on the basis of the catalyst such as traditional hydrodesulfurization, hydrodenitrogeneration.But Due to the essential distinction of reaction, for adapting to hydrogenation deoxidation reaction condition, whole production technology need to be improved.
A kind of hydrogenation deoxidation technique is provided, can effectively realize hydrogenation deoxidation reaction, and make catalyst as far as possible Holding hydrogenation activity, improve its service life simultaneously, be a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of biodiesel hydrogenation deoxidation technique, this technique can realize biodiesel Hydrogenation deoxidation, and its hydrogenation activity can be made to keep for a long time.
For reaching this purpose, the present invention by the following technical solutions:
A kind of biodiesel hydrogenation deoxidation technique, described technique uses fixed bed reactors, loads in fixed bed reactors Hydrogenation deoxidation catalyst, described catalyst is had to include 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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4's Mixture.
The reaction condition of described fixed bed reactors is: reaction temperature is 300-450 DEG C, Hydrogen Vapor Pressure 2.5-3.5MPa, Hydrogen to oil volume ratio 500-800, volume space velocity 1.0-2.5h-1。
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 Co3+ Saline solution, before KIT-1 framework of molecular sieve structure is formed, by isomorphous substitution by Co3+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 Co3+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 catalyst service life and active the drastically reducing of catalysis.But order People is joyful, works as Co2+When doping in KIT-1 controls in the range of 0.63%-0.72%, its service life and catalysis Activity is the strongest, when drawing with Co2+Doping is transverse axis, during curve chart with service life as the longitudinal axis, and catalysis in this content range The service life of agent is little constantly without substantially reducing 500, and it produces service life, effect was far beyond expection, belonged to expectation not The technique effect arrived.
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, the raising in DNA vaccine and service life can be realized.It is to say, the four of the present invention kinds of active components only exist Mol ratio is 1:(0.4-0.6): (0.28-0.45): time (0.8-1.2), just possess cooperative effect.Except this molar ratio range it Outward, 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.
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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its For regulating the character of carrier, weaken interaction strong between metal and carrier, improve the surface texture of catalyst, improve metal Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps Agent application with the carrier of the present invention with active component time, for high-sulfur component, it promotes the effect of catalytic desulfurization/refined ?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounding, Find eventually to use Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) the catalyst facilitation to the present invention Substantially, its hydrothermal stability can be significantly improved, and improve its anti-coking deactivation, thus improve its service life.
Described Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that Cr2O3、ZrO2、 CeO2、V2O5And NbOPO4Each respective content reaches effective dose.Preferably, the Cr that the present invention uses2O3、ZrO2、 CeO2、V2O5And NbOPO4Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5, Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it Difference, its beds coking is relatively rapid, thus causes catalyst duct to block, and beds pressure drop rise is relatively Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce catalysis Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention. Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid, Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.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.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 300-350 DEG C, Hydrogen Vapor Pressure 3.0- 3.5MPa, hydrogen to oil volume ratio 600-750, volume space velocity 1.0-2.0h-1。
Preferably, described technological process includes, after biodiesel mixes with hydrogen, through optional heat exchanger heat exchange, then warp Entering fixed bed reactors after heating furnace heating and carry out hydrogenation deoxidation, product separates through gas-liquid separation tower.Optionally, gas phase Returning and mix with biodiesel and hydrogen, liquid phase can further be refined, and such as amine washes, strip and fractional distillation etc..
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrogenation deoxidation technique of the present invention is by choosing specific catalyst, and described catalyst is by mixing hetero atom Co2+ KIT-1 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc As active component, described catalyst is possibly together with catalyst aid, and described catalyst aid is Cr2O3、ZrO2、CeO2、V2O5With NbOPO4Mixture so that this catalyst produces cooperative effect, can control the hydrogenation deoxidation of biodiesel higher de- 500 hours catalysis activity of oxygen rate (more than 99.8%) and continuously operation are without being decreased obviously (reaction yield is without substantially reduction).
Detailed description of the invention
The hydrogenation deoxidation technique of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Co2+KIT-1, Co2+Doping control in KIT-1 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.
The raw materials used biodiesel prepared for Oleum Gossypii semen.
Controlling reaction condition is: reaction temperature is 300 DEG C, Hydrogen Vapor Pressure 3.0MPa, hydrogen to oil volume ratio 600, volume space velocity 1.0h-1。
Testing final product, its DNA vaccine reaches 99.9%, and after device runs 500 hours continuously, DNA vaccine still reaches 99.4%.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+KIT-1, Co2+Doping control in KIT-1 System 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 is the 10% of carrier quality, and its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, its DNA vaccine reaches 99.85%, and after device runs 500 hours continuously, DNA vaccine still reaches 99.5%.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, its DNA vaccine reaches 83%, and after device runs 500 hours continuously, DNA vaccine is only 60%.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated KIT-1, and remaining condition is constant.
Testing final product, its DNA vaccine reaches 81%, and after device runs 500 hours continuously, DNA vaccine is only 70%.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, its DNA vaccine reaches 78%, and after device runs 500 hours continuously, DNA vaccine is only 52%.
Comparative example 4
By the Co in embodiment 12+Doping in KIT-1 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, its DNA vaccine reaches 79%, and after device runs 500 hours continuously, DNA vaccine is only 70%.
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 DNA vaccine reaches 77%, and after device runs 500 hours continuously, DNA vaccine is only 68%.
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, described hydrogenation deoxidation technique creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, its DNA vaccine reaches 72%, and after device runs 500 hours continuously, DNA vaccine is only 57%.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, its DNA vaccine reaches 78%, and after device runs 500 hours continuously, DNA vaccine is only 64%.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrogenation deoxidation technique of the present invention it Between there is specific contact, be omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that it produces Give birth to cooperative effect.
Embodiment 3
Containing catalyst aid Cr in catalyst2O3、ZrO2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 2%, 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 13.6%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same The beds pressure drop executing example 1 only reduces 3.5%.
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 4.3%.
Embodiment 3 shows with comparative example 8-9, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted When one of them or several component, all can not reach the minimizing coking when present invention adds catalyst aid thus stop catalyst bed The technique effect that lamination falling-rising is high.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst, And other catalyst aid effects are not as this specific catalyst aid.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (8)

1. a biodiesel hydrogenation deoxidation technique, it is characterised in that described technique uses fixed bed reactors, fixed bed reaction Being filled with hydrogenation deoxidation catalyst in device, 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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixing Thing；
The reaction condition of described fixed bed reactors is: reaction temperature is 300-450 DEG C, Hydrogen Vapor Pressure 2.5-3.5MPa, hydrogen oil Volume ratio 500-800, volume space velocity 1.0-2.5h-1。
2. hydrogenation deoxidation technique as claimed in claim 1, it is characterised in that hetero atom Co2+Doping be KIT-1 weight 0.63%-0.72%.
3. hydrogenation deoxidation technique as claimed in claim 1, it is characterised in that the total content of described active component is carrier KIT- The 3-12% of 1 weight, preferably 5-10%.
4. hydrogenation deoxidation technique 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. hydrogenation deoxidation technique as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is: Reaction temperature is 300-350 DEG C, Hydrogen Vapor Pressure 3.0-3.5MPa, hydrogen to oil volume ratio 600-750, volume space velocity 1.0-2.0h-1, excellent Choosing, the reaction condition of described fixed bed reactors is: reaction temperature is 300 DEG C, Hydrogen Vapor Pressure 3.0MPa, hydrogen to oil volume ratio 600, volume space velocity 1.0h-1。
6. hydrogenation deoxidation technique as claimed in claim 1, it is characterised in that described technological process includes, biodiesel and hydrogen After gas mixing, through optional heat exchanger heat exchange, then after the heating of heated stove, entrance fixed bed reactors carry out hydrogenation deoxidation, reaction Product separates through gas-liquid separation tower.
7. hydrogenation deoxidation technique 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.
8. hydrogenation deoxidation technique as claimed in claim 1, it is characterised in that Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Each Content be respectively the 1-7%, preferably 2-4% of carrier quality.
CN201610709676.7A 2016-08-23 2016-08-23 A kind of biodiesel hydrogenation deoxidation technique Pending CN106221724A (en)

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