CN106085496A - A kind of biodiesel hydrogenation deoxidation technique - Google Patents
A kind of biodiesel hydrogenation deoxidation technique Download PDFInfo
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- CN106085496A CN106085496A CN201610666301.7A CN201610666301A CN106085496A CN 106085496 A CN106085496 A CN 106085496A CN 201610666301 A CN201610666301 A CN 201610666301A CN 106085496 A CN106085496 A CN 106085496A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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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
- 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
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (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+MCM 41;Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc;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
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+MCM-41.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
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。
MCM-41 is ordered into mesoporous material, and its duct is that six side's ordered arrangement, size are uniform, aperture size can with synthesis time
The difference adding directed agents and synthetic parts changes between 1.5~10nm, lattice parameter about 4.5nm, specific pore volume about 1mL/g,
MCM-41 uniform pore diameter, has higher specific surface area (1000m2/ g) and big adsorption capacity (0.7mL/g), the most organic
The free diffusing of molecule.The present invention through in numerous mesoporous materials, such as MCM-22, MCM-36, MCM-48, MCM-49,
MCM56, carries out contrast test selection, finds that only MCM-41 can reach the goal of the invention of the present invention, and other mesoporous materials are all
Having such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, therefore the present invention selects to use
MCM-41 is as carrier basis.
The acidity of silica MCM-41 own is the most weak, is directly used as catalyst activity relatively low.Therefore, it is changed by the present invention
Property, to increase its catalysis activity.The approach that MCM-41 mesopore molecular sieve is modified is by the present invention: in MCM-41 building-up process,
Add Co3+Saline solution, before MCM-41 framework of molecular sieve structure is formed, by isomorphous substitution by Co3+Replace part skeleton unit
Element thus embed in the skeleton of molecular sieve, improve on the whole MCM-41 mesopore molecular sieve catalysis activity, absorption and heat
Mechanical stability can wait.
Although the method being modified MCM-41 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges
Agent can only use doping Co3+MCM-41 could realize sulfur content as carrier and control and the balance of loss of octane number, invention
People has attempted adulterating in MCM-41: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all can not
Realize described effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on MCM-41 inner surfaces of pores to compare,
The isomorphous substitution approach of the present invention is more stable.Although described mechanism is current and unclear, but this has no effect on the reality of the present invention
Executing, inventor is according to well-known theory and it is experimentally confirmed that there is cooperative effect between itself and the active component of the present invention.
Described Co2+Doping in MCM-41 must control within specific content range, and its doping is with weight
Meter, for the 0.56%-0.75% of MCM-41 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%,
0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%,
0.74 etc..
Inventor finds, outside this range, can cause catalyst service life and active the drastically reducing of catalysis.But order
People is joyful, works as Co2+When doping in MCM-41 controls in the range of 0.63%-0.72%, its service life and urging
Change activity the strongest, when drawing with Co2+Doping is transverse axis, during curve chart with service life as the longitudinal axis, urges 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
Less than technique effect.
The total content of described active component is the 1%-15% of carrier MCM-41 weight, preferably 3-12%, further preferably
5-10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28-
0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
In the range of Gai, 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.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine
The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 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+
MCM-41 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 so that this catalyst produces cooperative effect, can control the hydrogenation deoxidation of biodiesel in higher deoxidation
500 hours catalysis activity of 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+MCM-41, Co2+Doping in MCM-41
Control at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Becoming, reaction bed temperature UGU808 type temp controlled meter is measured, the twin columns that raw material light oil is manufactured by Beijing Satellite Manufacturing Factory
Plug micro pump carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-11A/ZM mass-flow gas meter control by gas cylinder
Flow velocity processed, loaded catalyst is 2kg.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
99.7%.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+MCM-41, Co2+Doping in MCM-41
Control at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, its 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 80%, and after device runs 500 hours continuously, DNA vaccine is only 60%.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated MCM-41, and remaining condition is constant.
Testing final product, its DNA vaccine reaches 83%, and after device runs 500 hours continuously, DNA vaccine is only 71%.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, its DNA vaccine reaches 71%, and after device runs 500 hours continuously, DNA vaccine is only 53%.
Comparative example 4
By the Co in embodiment 12+Doping in MCM-41 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, its DNA vaccine reaches 83%, and after device runs 500 hours continuously, DNA vaccine is only 73%.
Comparative example 5
By the Co in embodiment 12+Doping in MCM-41 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, its DNA vaccine reaches 71%, 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
MCM-41 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+During doping difference, all reach
Less than the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping MCM-41 carrier and catalyst other
Possessing cooperative effect between component, described 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 62%, and after device runs 500 hours continuously, DNA vaccine is only 50%.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, its DNA vaccine reaches 82%, and after device runs 500 hours continuously, DNA vaccine is only 62%.
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.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in
Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art
Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool
Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (7)
1. a 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+MCM-41;
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc;
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 MCM-41 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 MCM-
The 3-12% of 41 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.
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