CN107916126B - The method that fatty acid and/or aliphatic ester prepare hydrocarbons - Google Patents
The method that fatty acid and/or aliphatic ester prepare hydrocarbons Download PDFInfo
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- CN107916126B CN107916126B CN201610882442.2A CN201610882442A CN107916126B CN 107916126 B CN107916126 B CN 107916126B CN 201610882442 A CN201610882442 A CN 201610882442A CN 107916126 B CN107916126 B CN 107916126B
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- fatty acid
- aliphatic ester
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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
- C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
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- 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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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of methods that fatty acid and/or aliphatic ester prepare hydrocarbons, and mainly solving the problem of the prior art, there are the high high production cost of energy consumption.The present invention is by using being included under conditions of non-hydrogen, the step of fatty acid and/or aliphatic ester contact in fixed bed reactors with catalyst；The catalyst include a) 0.1~5 weight % selected from least one of Pt, Pd and Ru active component；And b) technical solution of the carrier of 95~99.9 weight % preferably solves the problems, such as this, can be used for fatty acid and/or aliphatic ester is prepared in the industrial production of hydrocarbons.
Description
Technical field
The present invention relates to a kind of methods that fatty acid and/or aliphatic ester prepare hydrocarbons.
Background technique
The energy resource structure of the world today using coal, petroleum, natural gas as the fossil energy of representative mainly by being constituted.This
A little fossil energies need just be formed by millions of year time, substantially belong to non-renewable energy resources.At the same time, change
The use of the stone energy also brings the problem of many reality.On the one hand, a small amount of S, N are inevitably contained in fossil energy
Equal elements, can generate environmentally harmful oxygen sulfur compound and oxynitrides after burning；On the other hand, combustion process itself is arranged
The great amount of carbon dioxide put can also bring the greenhouse effects in global range to the mankind.Therefore, in Copenhagen meeting in 2009
In view, representatives of various countries promise to undertake that CO is greatly reduced in 2012~the year two thousand twenty2Discharge.
Bioenergy is CO2Emission reduction provides a possible approach, and biomass is with CO2It is grown for base stock, by place
Biodiesel, the CO generated after burning are obtained after reason2The growth that biomass can be supplied again therefore can be substantially using biodiesel
Reduce CO2Discharge.
The main component of first generation biodiesel is the fatty acid methyl ester prepared using glyceride as raw material.With conventional diesel phase
Than having many advantages, such as that the harmful elements content such as S, N is low, bio-compatibility is good.But due to wherein containing a large amount of oxygen atom,
Cause the disadvantages of thermal efficiency ratio is lower, and power is inadequate in burning.On this basis, second generation biodiesel is developed both at home and abroad
Technology, i.e. hydrogenation deoxidation method.This method be with contain in animal and plant fat a large amount of triglycerides (triglycerides be by glycerol and
The ester type compound that long chain fatty acids are formed) it is raw material, the oxygen in triglycerides molecule is removed by hydrogenation deoxidation technology path
And long chain alkane is obtained, further obtain biodiesel.Second generation biodiesel overcomes first generation biodiesel oxygen content
High disadvantage, quality, which has reached, has been even more than traditional petrifaction diesel, while remaining the nocuousness such as first generation biodiesel S, N
The low advantage of constituent content, at present Small Scale Industry.
However, there is also the defects of itself for this technology.The process requirement of hydrogenation deoxidation consumes a large amount of hydrogen, generates 1
Molecule long chain alkane need to consume 4 molecule H2, lead to the high process cost, economy is not good enough.Meanwhile the grease that China is discarded
In, other than the aliphatic esters such as triglycerides, there is also a large amount of free fatty acids, if waste grease not purified essence
Refining, hydrogenation deoxidation technique will be difficult to be applied directly on these waste greases.This virtually improves being produced into for the technique again
This.
Decarboxylation method directly removes the carboxyl in grease molecules by decarboxylic reaction, is converted into hydrocarbon compound.Document
CN102876350A discloses one kind and prepares the combustion of high cetane number alkane by vegetable oil or long chain fatty acids on Ru series catalysts
The method of material, the invention are intermittent still reaction, need to face hydrogen and reaction dissolvent, and reaction pressure is higher, and energy consumption is high, are produced into
This height.
Summary of the invention
The technical problem to be solved by the present invention is to the prior arts there are energy consumption height, the problem of high production cost, provide one
The method that kind new fatty acid and/or aliphatic ester prepare hydrocarbons.Low energy consumption for this method, and production cost is low, process is simple,
Green.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of fatty acid and/or aliphatic ester system
The method of standby hydrocarbons, is included under conditions of non-hydrogen, fatty acid and/or aliphatic ester in fixed bed reactors with catalysis
The step of agent contacts；
The catalyst include a) 0.1~5 weight % selected from least one of Pt, Pd and Ru active component；And b)
The carrier of 95~99.9 weight %.
In above-mentioned technical proposal, the hydrocarbons are C12-C18Long chain alkane.
In above-mentioned technical proposal, the carrier is selected from SiO2、Al2O3、ZrO2、ZnO、CeO2And TiO2At least one of.
In above-mentioned technical proposal, fatty acid and aliphatic ester are C12-C18In straight chain fatty acid aliphatic ester corresponding with its
At least one.Preferably, the fatty acid is selected from soft ester acid, oleic acid, palmitinic acid, lauric acid, stearic acid, linoleic acid and flax
At least one of oleic acid；The aliphatic ester is selected from the methyl esters or ethyl ester of the fatty acid.It is highly preferred that the fatty acid
Selected from lauric acid；The aliphatic ester is selected from methyl laurate.
In above-mentioned technical proposal, fatty acid and/or aliphatic ester contact under inert gas atmosphere with catalyst.It is preferred that
Ground, the inert gas are selected from least one of VIII group rare gas and nitrogen.
In above-mentioned technical proposal, the volume space velocity of the inert gas is 1000~30000 hours-1。
In above-mentioned technical proposal, Contact Temperature is 100~400 DEG C, and pressure is normal pressure, fatty acid and/or aliphatic ester
Mass space velocity is 0.1~50 hour-1。
In above-mentioned technical proposal, fatty acid and/or aliphatic ester and catalyst are not required to solvent when contacting.
The present invention also provides a kind of hydrocarbon of method preparation that hydrocarbons are prepared according to the fatty acid and/or aliphatic ester
The purposes of substance.Application of the hydrocarbons of the preparation as biodiesel fuel.
Catalyst provided in the method for the present invention can be used any method appropriate that active metal component is made to be distributed to oxygen
On compound carrier.For example, the soluble-salt of the metal as active metal component is dissolved in solvent, carrier oxygen is added in the solution
Compound powder boils off solvent, and obtained solid is then obtained the catalyst by drying, roasting, reduction treatment.
The method of the present invention passes through under conditions of atmospheric fixed bed non-hydrogen using fatty acid and/or aliphatic ester as raw material
The inert gas of flowing takes product progress decarboxylic reaction out of and obtains high-carbon linear paraffin, compared with prior art, is guaranteeing C12-C18
Under the premise of the selectivity of long chain alkane, have and do not consume hydrogen, does not have to pressurization, the advantages of low energy consumption, reduce biodiesel
Production cost converts preparation biodiesel for low-grade grease low cost and provides important technological means, achieves preferable
Technical effect.
The present invention will be further described below by way of examples.
Specific embodiment
[Examples 1 to 3]
SiO2The noble metal catalyst of load:
SiO2For Chinese medicines group purchase.
Weigh 0.5g SiO2Carrier is added chloroplatinic acid, palladium chloride or chlorination ruthenium solution 10mL, ultrasonic 0.5h and promotes SiO2
Dispersion, then boil off solvent in 60 DEG C of water-baths, 120 DEG C of dry 12h, 300 DEG C of roasting temperature 4h, 200 DEG C with 5% hydrogen argon
Gaseous mixture restores 1 hour, and content of metal is 1 weight %.
The catalyst that above-mentioned preparation is inserted in fixed bed reactors is passed through inert gas Ar and is heated to 300 DEG C, Ar gas
Body volume space velocity 10000h-1；It is passed through lauric acid, mass space velocity 30h-1.It the results are shown in Table 1.
[embodiment 4~9]
The Pt catalyst of different carriers load:
SiO2For Chinese medicines group purchase.
Al2O3Using Na2CO3Precipitation method preparation: aluminum nitrate is dissolved in the solution that water is configured to 0.33M, in 70 DEG C of water-bath
Under the Na of isometric 1.05M is added dropwise2CO3Solution continues to keep 2h in a water bath after being added dropwise.Obtained sediment
Foreign ion is removed by filtration washing, in 120 DEG C of drying overnight, then in 500 DEG C of roasting 4h.
ZrO2It is prepared using ammonia water precipitating: zirconium oxychloride is dissolved in the solution that water is configured to 1M, added dropwise under stiring
Enter concentrated ammonia liquor to pH=8, continues to stir half an hour after being added dropwise.Obtained sediment by filtration washing remove impurity from
Son, in 120 DEG C of drying overnight, then in 500 DEG C of roasting 4h.
ZnO uses Na2CO3The precipitation method preparation: zinc nitrate is dissolved in the solution that water is configured to 1M, under 70 DEG C of water-bath by
It is added dropwise to the Na of isometric 1.05M2CO3Solution continues to keep 2h in a water bath after being added dropwise.Obtained sediment passes through
Filtration washing removes foreign ion, in 120 DEG C of drying overnight, then in 500 DEG C of roasting 4h.
CeO2Carrier is prepared using the method for urea gel co-precipitation: by (NH4)2Ce(NO3)6It is jointly molten with precipitating reagent urea
In deionized water, wherein the total concentration of metal ion is 0.5M to solution, and the molar ratio of urea and metal ion total amount is 20.Solution
The heating stirring 6h in 100 DEG C of oil baths.It filters, precipitating is washed with deionized 6 times, the dry 12h at 120 DEG C, 550 DEG C of roastings
4h obtains CeO2Carrier.
TiO2Carrier is prepared using sol-gal process: by 30mL ethyl alcohol, 15mL water, the dense HNO of 3mL3Solution is uniformly mixed, system
Obtain solution A；17g butyl titanate is dissolved in 40mL ethyl alcohol, solution B is slowly added into solution A under stiring by obtained solution B
In, 2h is stirred at room temperature, obtains homogeneous and transparent colloidal sol.Two days are stood at 40 DEG C, obtains gel.Obtained gel is placed in
Dry 12h, 550 DEG C of roasting 4h at 120 DEG C.
Catalyst is all made of infusion process preparation: weighing the above-mentioned carrier of 0.5g, platinum acid chloride solution 10mL is added, ultrasonic 0.5h promotees
Into support dispersion, solvent is then boiled off in 60 DEG C of water-baths, 120 DEG C of dry 12h, 300 DEG C of roasting temperature 4h, 200 DEG C with 5%
Hydrogen-argon-mixed reduction 1 hour, respectively Pt/SiO2、Pt/Al2O3、Pt/ZrO2、Pt/ZnO、Pt/CeO2、Pt/TiO2, Pt is negative
Carrying capacity is 1%.
It is Ar, gas volume air speed 10000h that reaction, which is passed through gas,-1, 300 DEG C of reaction temperature, lauric mass space velocity is
30h-1.It the results are shown in Table 1.
[embodiment 10~12]
The Pt/ZrO of different loads amount2Catalyst:
Catalyst is all made of infusion process preparation: weighing the above-mentioned ZrO of 0.5g2Platinum acid chloride solution 10mL, ultrasound is added in carrier
0.5h promotes support dispersion, then boils off solvent in 60 DEG C of water-baths, 120 DEG C of dry 12h, 300 DEG C of roasting temperature 4h, and 200
DEG C with 5% it is hydrogen-argon-mixed reduction 1 hour, the load capacity of Pt is respectively 0.5%, 1% and 2%.It is Ar, gas that reaction, which is passed through gas,
Body volume space velocity 10000h-1, 300 DEG C of reaction temperature, lauric mass space velocity is 30h-1.It the results are shown in Table 1.
[embodiment 13]
Use the catalyst in [embodiment 11].It is Ar, gas volume air speed 10000h that reaction, which is passed through gas,-1, reaction temperature
300 DEG C of degree, the mass space velocity of methyl laurate are 30h-1.It the results are shown in Table 1.
[embodiment 14]
Use the catalyst in [embodiment 11].It is Ar, gas volume air speed 10000h that reaction, which is passed through gas,-1, reaction temperature
300 DEG C of degree, the mass space velocity of palmitic acid are 30h-1.It the results are shown in Table 1.
[embodiment 15]
Use the catalyst in [embodiment 11].It is Ar, gas volume air speed 20000h that reaction, which is passed through gas,-1, reaction temperature
300 DEG C of degree, lauric mass space velocity are 30h-1.It the results are shown in Table 1.
[embodiment 16]
Use the catalyst in [embodiment 11].It is Ar, gas volume air speed 10000h that reaction, which is passed through gas,-1, reaction temperature
350 DEG C of degree, lauric mass space velocity are 30h-1.It the results are shown in Table 1.
[embodiment 17]
Use the catalyst in [embodiment 11].It is Ar, gas volume air speed 10000h that reaction, which is passed through gas,-1, reaction temperature
300 DEG C of degree, lauric mass space velocity are 20h-1.It the results are shown in Table 1.
Table 1
aAlkane in [embodiment 14] is n-pentadecane, is in the remaining embodiments n-undecane.
Claims (11)
1. a kind of method that fatty acid and/or aliphatic ester prepare hydrocarbons, is included under conditions of non-hydrogen, fatty acid and/
Or aliphatic ester the step of being contacted in fixed bed reactors with catalyst, fatty acid and/or aliphatic ester are contacted with catalyst
Shi Buxu solvent；
The catalyst include a) 0.1~5 weight % selected from least one of Pt, Pd and Ru active component；And b) 95~
The carrier of 99.9 weight %.
2. the method that fatty acid and/or aliphatic ester prepare hydrocarbons according to claim 1, which is characterized in that described
Hydrocarbons are C12-C18Long chain alkane.
3. the method that fatty acid and/or aliphatic ester prepare hydrocarbons according to claim 1, which is characterized in that described
Carrier is selected from SiO2、Al2O3、ZrO2、ZnO、CeO2And TiO2At least one of.
4. the method that fatty acid and/or aliphatic ester prepare hydrocarbons according to claim 1, which is characterized in that fat
Acid and aliphatic ester are C12-C18At least one of straight chain fatty acid aliphatic ester corresponding with its.
5. the method that fatty acid and/or aliphatic ester prepare hydrocarbons according to claim 4, which is characterized in that described
Fatty acid is selected from least one of soft ester acid, oleic acid, palmitinic acid, lauric acid, stearic acid, linoleic acid and linolenic acid；It is described
Aliphatic ester is selected from the methyl esters or ethyl ester of the fatty acid.
6. the method that fatty acid and/or aliphatic ester prepare hydrocarbons according to claim 5, which is characterized in that described
Fatty acid is lauric acid；The aliphatic ester is methyl laurate.
7. the method that fatty acid and/or aliphatic ester prepare hydrocarbons according to claim 1, which is characterized in that fat
Acid and/or aliphatic ester contact under inert gas atmosphere with catalyst.
8. the method that fatty acid and/or aliphatic ester prepare hydrocarbons according to claim 7, which is characterized in that described
Inert gas is selected from least one of VIII group rare gas and nitrogen.
9. the method that fatty acid and/or aliphatic ester prepare hydrocarbons according to claim 7, which is characterized in that described
The volume space velocity of inert gas is 1000~30000 hours-1。
10. the method that fatty acid and/or aliphatic ester prepare hydrocarbons according to claim 1, which is characterized in that contact
Temperature is 100~400 DEG C, and pressure is normal pressure, and the mass space velocity of fatty acid and/or aliphatic ester is 0.1~50 hour-1。
11. application of the hydrocarbons of claim 1~10 either method preparation as biodiesel fuel.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538195A (en) * | 2009-04-23 | 2009-09-23 | 上海华谊丙烯酸有限公司 | Acrylaldehyde preparation method by glycerin dehydration under inert gas dilution |
| CN105132192A (en) * | 2014-05-29 | 2015-12-09 | 中国石油化工股份有限公司 | Biodiesel preparation method |
| CN105861162A (en) * | 2015-01-22 | 2016-08-17 | 中国石油化工股份有限公司 | Preparation method of aliphatic ester by using solid catalyst |
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- 2016-10-10 CN CN201610882442.2A patent/CN107916126B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538195A (en) * | 2009-04-23 | 2009-09-23 | 上海华谊丙烯酸有限公司 | Acrylaldehyde preparation method by glycerin dehydration under inert gas dilution |
| CN105132192A (en) * | 2014-05-29 | 2015-12-09 | 中国石油化工股份有限公司 | Biodiesel preparation method |
| CN105861162A (en) * | 2015-01-22 | 2016-08-17 | 中国石油化工股份有限公司 | Preparation method of aliphatic ester by using solid catalyst |
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