CN103361101A - Catalytic conversion method for obtaining long-chain alkane from glycerin - Google Patents
Catalytic conversion method for obtaining long-chain alkane from glycerin Download PDFInfo
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- CN103361101A CN103361101A CN2012101025543A CN201210102554A CN103361101A CN 103361101 A CN103361101 A CN 103361101A CN 2012101025543 A CN2012101025543 A CN 2012101025543A CN 201210102554 A CN201210102554 A CN 201210102554A CN 103361101 A CN103361101 A CN 103361101A
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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
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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
- 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
Abstract
The invention relates to a catalytic conversion method for obtaining long-chain alkane from glycerin by virtue of hydrogenolysis and intermolecular condensation of glycerin molecules under an acidic condition. The catalytic conversion method comprises the following steps of: mixing the glycerin with an aqueous solution of inorganic acid to obtain a mixed solution, wherein the molar ratio of the glycerin to the inorganic acid is 1-2; and adding catalytic amount of catalyst in the mixed solution, and reacting at the temperature of 120 DEG C-350 DEG C and under hydrogen gas pressure to obtain liquid fuel which primarily contains long-chain alkane with carbon atom number of 6-24, wherein the liquid fuel is synthesized with Fischer-Tropsch to obtain a fuel-similar component with a much narrower component range. The catalytic conversion method for obtaining long-chain alkane from glycerin is not only beneficial to solving a conversion problem of glycerin generated in a biodiesel production process, but also capable of providing an effective way for synthesizing fuel oil by a renewable material. The catalyst comprises main catalyst metal (Ir or Rh) loaded on the vector and assistant catalytic metal (any one or two of Re, W and Mo).
Description
Technical field
The present invention relates to by hydrogenolysis and the intermolecular condensation method that obtain the catalyzed conversion of middle long chain alkane of glycerol molecule under acidic conditions.
Background technology
The energy is divided into Nonrenewable energy resources and renewable energy source.Nonrenewable energy resources comprise coal, oil and natural gas.Renewable energy source comprises water energy, wind energy, sun power, tidal energy, sea wave energy, Geothermal energy, ocean heat, Hydrogen Energy, nuclear energy, bioenergy.In 2007, global coal turnout was 6.5 * 10
9T, and the amount of whole world coal is 9.09 * 10
11T that is to say if according to this speed, coal only enough 140 years.The a large amount of pollution of the annual discharging in coal power station: 1.1 * 10
7The t carbonic acid gas, 3 * 10
4The t oxynitride, 1.6 * 10
4T sulfurous gas, 1 * 10
3T dust and other a small amount of picture calcium, potassium, the chemical substances such as titanium and arsenic.With the production rate of present oil, global oil at most can only be with 50 years.1996, the reserves of global Sweet natural gas were 1.412 * 10
15m
3, use only more than 60 year.So it is necessary and urgent greatly developing renewable energy source.
The renewable energy sources such as water energy, wind energy, sun power, tidal energy, sea wave energy, Geothermal energy, ocean heat are subjected to the impact of geographical environment very large, and efficient is not high yet.And Hydrogen Energy say in principle can not be as a kind of energy because hydrogen electrolysis from water needs to use a lot of energy in this process, the energy of being emitted by combustion of hydrogen all can not remedy the energy in the electrolytic process.So it is very unpractical replacing top fossil energy by these energy separately.Most potential should be nuclear energy and bioenergy.Bioenergy generally is divided into two classes---first-generation bioenergy and s-generation bioenergy.First-generation bioenergy (such as bio-ethanol and biofuel) is to develop from carbohydrate and vegetables oil; S-generation bioenergy then is to develop from biomass (comprising timber, stalk, grass etc.).The comparative maturity of first-generation Bioenergy development now, carries out transesterify production biofuel with vegetables oil and has obtained significant progress.But in the process of production biofuel, can produce a large amount of glycerin by-products, so the research work around transformation of glycerol has much now, more typically have by glycerine and obtain propylene glycol, such as L.Ma[L.Ma et al.Catalysis Communications, 2008,9:2489-2495] and Yoshinao Nakagawa[Yoshinao Nakagawa et al, Journal of Catalysis, 2010,272:191-194] scheme that proposes, and obtain propenal by glycerine, as the clear people (CN 101426754A) of grade of the wild political affairs of Austria and nearly rattan be good for etc. the scheme that proposes of people (CN 101619019A).
The present invention is a new reaction system, and glycerine can be converted into take middle long chain alkane (carbonatoms is as 6～24) as main oily mater in this reaction system.Because the present invention is converted into final product in the step by glycerine, so this method for transformation of the present invention has very large advantage, is expected at and alleviates to a certain extent following energy dilemma.
Summary of the invention
The purpose of this invention is to provide a kind of by hydrogenolysis and the intermolecular condensation method that obtain the catalyzed conversion of middle long chain alkane of glycerol molecule under acidic conditions.
The method that is obtained the catalyzed conversion of middle long chain alkane by glycerine of the present invention can prepare take middle long chain alkane (carbonatoms is as 6～24) as main oily matter.Among the present invention used carrier there is not special requirement, but the larger carrier of specific surface area, and effect is often relatively good.The present invention adopts equi-volume impregnating that metal is carried out load, and used metal has Ir, Rh, Re, W, Mo.The used mineral acid of the present invention can be sulfuric acid or phosphoric acid.Described mineral acid will have certain concentration, is preferably 5～50wt% and (is preferably 25～40wt%).The used hydrogen pressure of the present invention does not have the upper limit, but is preferably 4～15MPa, more preferably 6～10MPa.The used temperature of the present invention is 120～350 ℃, is preferably 150～250 ℃.Reaction times required for the present invention is preferably 48～72 hours.The present invention has also found such rule, and the concentration of acid is higher, the transformation efficiency of glycerine higher (within the identical time), and the middle long chain alkane that obtains is in the majority take the alkane of long-chain (carbonatoms is as 16～24).
The method that is obtained the catalyzed conversion of middle long chain alkane by glycerine of the present invention is: be that (aqueous solution that is preferably 25～40wt%) mineral acid obtains mixed solution to 5～50wt%, and wherein: the molar ratio of glycerine and mineral acid is 1～2 with glycerine and concentration; Then the catalyzer that in mixed solution, adds catalytic amount, (described stirring is to utilize magnetic stirring in stirring, the rotating speed of described magnetic stirring is generally about 1000rpm/min), be that 120～350 ℃ (being preferably 150～250 ℃) and the pressure of hydrogen (are preferably 4～15MPa in temperature, more preferably react (time of reaction is preferably 48～72 hours) under 6～10MPa), obtain carbonatoms and be 6～24 middle long chain alkane.
Described catalyzer is by the Primary Catalysts metal of load on carrier and help catalytic metal to form, and wherein the charge capacity of Primary Catalysts metal is 1～3wt% of vehicle weight; The quality ratio of the material of described Primary Catalysts metal and described promoter metal is 0.5～5.
Described Primary Catalysts metal can be Ir or Rh, and described promoter metal can be selected from a kind of among Re, W, the Mo or any two kinds.
Described mineral acid is sulfuric acid or phosphoric acid.
Described catalyzer is prepared by following methods:
Precursor (H with the Primary Catalysts metal of 0.012～0.024g
2IrCl
6Or RhCl
3) and the precursor of the promoter metal of 0.01～0.036g (be selected from KReO
4, a kind of in three Ammonium paramolybdate tetrahydrates, phospho-wolframic acid or any two kinds) be dissolved in the 5ml deionized water and add carrier (the smog SiO for example of 0.4g
2Or molecular sieve ZSM-5 etc.), heated and stirred obtains catalyst precursor to carrier dried (temperature of general heating is 60 ℃), and then the gained catalyst precursor is put into baking oven further dry (generally being 60 ℃ of lower bakings 24 hours); The catalyst precursor of oven dry is put into tube furnace, is under the 2 ℃/min at temperature rise rate, and the temperature that makes tube furnace rises to 300～500 ℃ by room temperature and calcines (time of general calcining is about 3 hours); The catalyst precursor and the 5ml deionized water that obtain after the calcining are joined in the autoclave that is mounted with magnetic stirring together, stir (rotating speed of magnetic stirring is generally about 1000rpm/min); Go out air in the autoclave with hydrogen exchange, then hydrogen pressure and the temperature at 6～10MPa is to react (time of general reaction is about 6 hours) under 180～300 ℃, and cooling obtains described catalyzer.
When carrying out loaded metal, generally first carrier is carried out heat treated (being advisable about 100 ℃) to remove the water and air of carrier adsorption.The Primary Catalysts metal can be Ir or Rh, and the charge capacity of metal is at (1～3) wt%; Promoter metal can be a kind of among Re, W, the Mo or any two kinds.The precursor of Primary Catalysts metal and the precursor of promoter metal are with an amount of deionized water dissolving, the add-on of water can not be too much and the volume differences of carrier seldom just, then carrier is poured in the solution of metal ion, rapid stirring, stir until carrier dried is put in further oven dry in the baking oven (generally being 60 ℃ of lower bakings 24 hours) with the slimy material that obtains.The catalyst precursor of oven dry is placed tube furnace, make the temperature of tube furnace rise to 300～500 ℃ by room temperature and calcined 3 hours, temperature rise rate is 2 ℃/min.The catalyzer that to calcine again reduces in autoclave, and the rotating speed of magnetic stirring is about 1000rpm, and hydrogen pressure is 6～10MPa, and reduction temperature is 180～300 ℃, and the recovery time was generally about 6 hours.For the metal that prevents from reducing again be oxidized, can in autoclave, add an amount of water.The metal straight that reduction is good taps into next step transformation of glycerol reaction of row, adds an amount of glycerine mixed solution in autoclave, and wherein the glycerine mixed solution is glycerine and inorganic aqueous acid.
The present invention not only helps to solve the transition problem of the glycerine that produces in the production of biodiesel process, and a kind of effective way by the renewable raw materials synthetic engine fuel is provided.Have the following advantages:
1. method of the present invention is simple, does not have complicated process, no matter is the preparation of catalyzer, or follow-up reaction is all fairly simple, is fit to industrial needs;
The present invention obtain to synthesize the component that obtains fuel oil similar with Fischer-Tropsch take the middle long chain alkane of carbonatoms as 6～24 as main liquid fuel, what but compositional range will be narrow is many, this fuel oil product can help to alleviate present energy dilemma, and the oily matter of long chain alkane class can be used as the fuel of diesel engine;
3. reaction conditions of the present invention relatively relaxes, and the medium of transformation of glycerol is water, is not too high to the requirement of equipment, is conducive to the reduction of cost.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with specific embodiment, but the present invention should not be considered as only being confined to the following examples.
Embodiment 1
(1). the preparation of the mixed solution of glycerine and sulfuric acid
Get the triangular flask with stopper of a 500ml, the deionized water, the 100ml concentration that add successively 176ml are the H of 98wt%
2SO
4With 134ml glycerine.
(2). the preparation of catalyzer
H with 0.012g
2IrCl
6KReO with 0.018g
4Be dissolved in the 5ml deionized water and (need heat), then add the smog SiO of 0.4g
2Carrier is to be stirred to carrier dried under 60 ℃ in temperature, obtains catalyst precursor, and then the gained catalyst precursor is put into 60 ℃ further the oven dry 24 hours of baking oven; The catalyst precursor of oven dry is put into tube furnace, is under the 2 ℃/min at temperature rise rate, makes the temperature of tube furnace rise to 400 ℃ by room temperature and calcines 3 hours; In the autoclave that is mounted with magnetic stirring (being furnished with magnetic stirring) that the catalyst precursor that obtains and 5ml deionized water join 100ml together after the calcining, stir (rotating speed of magnetic stirring is about 1000rpm/min); H with 1MPa
2Air in the displacement autoclave three times, then hydrogen pressure and the temperature at 7MPa is to react under 200 ℃ 6 hours, then rapidly cooling obtains catalyzer.
(3). the autoclave reaction
The 10ml glycerine that step (1) is obtained and the mixed solution of sulfuric acid join in the autoclave of step (2), and magnetic stirring about utilizing rotating speed for 1000rpm/min stirs, and uses H
2Then air in the displacement displacement autoclave three times fills 6MPa H
2, be to react under 200 ℃ 72 hours in temperature, obtain take the middle long chain alkane of carbonatoms as 6～24 as main liquid fuel.
Product analysis
The oil reservoir carbonatoms is that 6～24 middle long chain alkane product is analyzed by GC-MS, and product is to the C that is distributed as of alkane
654.2%, C
7～C
931.7%, C
10～C
2014.1%.The glycerol conversion yield of aqueous phase is 99.5%.
Basically adopt above-mentioned identical method, just the H in the Kaolinite Preparation of Catalyst
2IrCl
6And KReO
4Content different, products therefrom adopts the method for above-mentioned product analysis, the result is as shown in table 1.
Table 1
Embodiment 2
(1) preparation of the mixed solution of glycerine and sulfuric acid
Get the triangular flask with stopper of a 500ml, the deionized water, the 100ml concentration that add successively 176ml are the H of 98wt%
2SO
4With 134ml glycerine.
(2). the preparation of catalyzer
RhCl with 0.012g
3KReO with 0.018g
4Be dissolved in the 5ml deionized water and (need heat), then add the smog SiO of 0.4g
2Carrier, rapid stirring obtain catalyst precursor to carrier dried, and then the gained catalyst precursor is put into 60 ℃ further the oven dry 24 hours of baking oven; The catalyst precursor of oven dry is put into tube furnace, is under the 2 ℃/min at temperature rise rate, makes the temperature of tube furnace rise to 400 ℃ by room temperature and calcines 3 hours; In the autoclave that is mounted with magnetic stirring (being furnished with magnetic stirring) that the catalyst precursor that obtains and 5ml deionized water join 100ml together after the calcining, stir (rotating speed of magnetic stirring is about 1000rpm/min); H with 1MPa
2Air in the displacement autoclave three times, then hydrogen pressure and the temperature at 7MPa is to react under 200 ℃ 6 hours, then rapidly cooling obtains catalyzer.
(3). the autoclave reaction
The 10ml glycerine that step (1) is obtained and the mixed solution of sulfuric acid join in the autoclave of step (2), and magnetic stirring about utilizing rotating speed for 1000rpm/min stirs, and uses H
2Then air in the displacement displacement autoclave three times fills 6MPa H
2, be to react under 200 ℃ 72 hours in temperature, obtain take the middle long chain alkane of carbonatoms as 6～24 as main liquid fuel.
Product analysis
The oil reservoir carbonatoms is that 6～24 middle long chain alkane product is analyzed by GC-MS, and product is to the C that is distributed as of alkane
650.1%, C
7～C
921.6%, C
10～C
2024.3%.The glycerol conversion yield of aqueous phase is 99.7%.
Basically adopt above-mentioned identical method, just the RhCl in the Kaolinite Preparation of Catalyst
3And KReO
4Content different, products therefrom adopts the method for above-mentioned product analysis, the result is as shown in table 2.
Table 2
Embodiment 3
(1). the preparation of the mixed solution of glycerine and sulfuric acid
Get the triangular flask with stopper of a 500ml, the deionized water, the 100ml concentration that add successively 176ml are the H of 98wt%
2SO
4With 134ml glycerine.
(2). the preparation of catalyzer
H with 0.012g
2IrCl
6Be dissolved in (need heating) in the 5ml deionized water with three Ammonium paramolybdate tetrahydrates of 0.01g, then add the smog SiO of 0.4g
2Carrier is stirred to carrier dried, obtains catalyst precursor, and then the gained catalyst precursor is put into 60 ℃ further the oven dry 24 hours of baking oven; The catalyst precursor of oven dry is put into tube furnace, is under the 2 ℃/min at temperature rise rate, makes the temperature of tube furnace rise to 400 ℃ by room temperature and calcines 3 hours; In the autoclave that is mounted with magnetic stirring (being furnished with magnetic stirring) that the catalyst precursor that obtains and 5ml deionized water join 100ml together after the calcining, stir (rotating speed of magnetic stirring is about 1000rpm/min); H with 1MPa
2Air in the displacement autoclave three times, then hydrogen pressure and the temperature at 7MPa is to react under 200 ℃ 6 hours, then rapidly cooling obtains catalyzer.
(3). the autoclave reaction
The 10ml glycerine that step (1) is obtained and the mixed solution of sulfuric acid join in the autoclave of step (2), and magnetic stirring about utilizing rotating speed for 1000rpm/min stirs, and uses H
2Then air in the displacement displacement autoclave three times fills 6MPa H
2, be to react under 200 ℃ 72 hours in temperature, obtain take the middle long chain alkane of carbonatoms as 6～24 as main liquid fuel.
Product analysis
The oil reservoir carbonatoms is that 6～24 middle long chain alkane product is analyzed by GC-MS, and product is to the C that is distributed as of alkane
624.2%, C
7～C
911.7%, C
10～C
209.0%.The glycerol conversion yield of aqueous phase is 40.5%.
Basically adopt above-mentioned identical method, just the H in the Kaolinite Preparation of Catalyst
2IrCl
6Different with the content of three Ammonium paramolybdate tetrahydrates, products therefrom adopts the method for above-mentioned product analysis, and the result is as shown in table 3.
Table 3
Embodiment 4
(1). the preparation of the mixed solution of glycerine and sulfuric acid
Get the triangular flask with stopper of a 500ml, the deionized water, the 100ml concentration that add successively 176ml are the H of 98wt%
2SO
4With 134ml glycerine.
(2). the preparation of catalyzer
H with 0.012g
2IrCl
6Be dissolved in (need heating) in the 5ml deionized water with the phospho-wolframic acid of 0.01g, then add the smog SiO of 0.4g
2Carrier is stirred to carrier dried, obtains catalyst precursor, and then the gained catalyst precursor is put into 60 ℃ further the oven dry 24 hours of baking oven; The catalyst precursor of oven dry is put into tube furnace, is under the 2 ℃/min at temperature rise rate, makes the temperature of tube furnace rise to 400 ℃ by room temperature and calcines 3 hours; In the autoclave that is mounted with magnetic stirring (being furnished with magnetic stirring) that the catalyst precursor that obtains and 5ml deionized water join 100ml together after the calcining, stir (rotating speed of magnetic stirring is about 1000rpm/min); H with 1MPa
2Air in the displacement autoclave three times, then hydrogen pressure and the temperature at 7MPa is to react under 200 ℃ 6 hours, then rapidly cooling obtains catalyzer.
(3). the autoclave reaction
The 10ml glycerine that step (1) is obtained and the mixed solution of sulfuric acid join in the autoclave of step (2), and magnetic stirring about utilizing rotating speed for 1000rpm/min stirs, and uses H
2Then air in the displacement displacement autoclave three times fills 6MPa H
2, be to react under 200 ℃ 72 hours in temperature, obtain take the middle long chain alkane of carbonatoms as 6～24 as main liquid fuel.
Product analysis
The oil reservoir carbonatoms is that 6～24 middle long chain alkane product is analyzed by GC-MS, and product is to the C that is distributed as of alkane
634.2%, C
7～C
918.9%, C
10～C
2012.0%.The glycerol conversion yield of aqueous phase is 60.5%.
Basically adopt above-mentioned identical method, just the H in the Kaolinite Preparation of Catalyst
2IrCl
6Different with the content of phospho-wolframic acid, products therefrom adopts the method for above-mentioned product analysis, and the result is as shown in table 4.
Table 4
Embodiment 5
(1). the preparation of the mixed solution of glycerine and sulfuric acid
Get the triangular flask with stopper of a 500ml, the deionized water, the 20ml concentration that add successively 84ml are the H of 98wt%
2SO
4With 45ml glycerine.
(2). the preparation of catalyzer
H with 0.012g
2IrCl
6KReO with 0.018g
4Be dissolved in the 5ml deionized water and (need heat), then add the molecular sieve ZSM-5 carrier of 0.4g, be stirred to carrier dried, obtain catalyst precursor, and then the gained catalyst precursor is put into 60 ℃ further the oven dry 24 hours of baking oven; The catalyst precursor of oven dry is put into tube furnace, is under the 2 ℃/min at temperature rise rate, makes the temperature of tube furnace rise to 400 ℃ by room temperature and calcines 3 hours; In the autoclave that is mounted with magnetic stirring (being furnished with magnetic stirring) that the catalyst precursor that obtains and 5ml deionized water join 100ml together after the calcining, stir (rotating speed of magnetic stirring is about 1000rpm/min); H with 1MPa
2Air in the displacement autoclave three times, then hydrogen pressure and the temperature at 7MPa is to react under 200 ℃ 6 hours, then rapidly cooling obtains catalyzer.
(3). the autoclave reaction
The 10ml glycerine that step (1) is obtained and the mixed solution of sulfuric acid join in the autoclave of step (2), and magnetic stirring about utilizing rotating speed for 1000rpm/min stirs, and uses H
2Then air in the displacement displacement autoclave three times fills 6MPa H
2, be to react under 200 ℃ 72 hours in temperature, obtain take the middle long chain alkane of carbonatoms as 6～24 as main liquid fuel.
Product analysis
The oil reservoir carbonatoms is that 6～24 middle long chain alkane product is analyzed by GC-MS, and product is to the C that is distributed as of alkane
634.5%, C
7～C
933.7%, C
10～C
2018.3%
Basically adopt above-mentioned identical method, just the H in the Kaolinite Preparation of Catalyst
2IrCl
6And KReO
4Content different, products therefrom adopts the method for above-mentioned product analysis, the result is as shown in table 5.
Table 5
Claims (10)
1. method that is obtained the catalyzed conversion of middle long chain alkane by glycerine is characterized in that: be that the aqueous solution of the mineral acid of 5～50wt% obtains mixed solution with glycerine and concentration, wherein: the molar ratio of glycerine and mineral acid is 1～2; Then adding the catalyzer of catalytic amount in mixed solution, stir, is to react under the pressure of 120～350 ℃ and hydrogen in temperature, obtains carbonatoms and be 6～24 middle long chain alkane;
Described catalyzer is by the Primary Catalysts metal of load on carrier and help catalytic metal to form, and wherein the charge capacity of Primary Catalysts metal is 1～3wt% of vehicle weight; The quality ratio of the material of described Primary Catalysts metal and described promoter metal is 0.5～5;
Described Primary Catalysts metal is Ir or Rh, and described promoter metal is selected from a kind of among Re, W, the Mo or any two kinds.
2. method according to claim 1, it is characterized in that: described catalyzer is prepared by following methods:
Be dissolved in the precursor of the promoter metal of the precursor of the Primary Catalysts metal of 0.012～0.024g and 0.01～0.036g in the 5ml deionized water and add the carrier of 0.4g, heated and stirred is to carrier dried, obtain catalyst precursor, and then the gained catalyst precursor is put into baking oven dry; The catalyst precursor of oven dry is put into tube furnace, is under the 2 ℃/min at temperature rise rate, makes the temperature of tube furnace rise to 300～500 ℃ by room temperature and calcines; The catalyst precursor and the 5ml deionized water that obtain after the calcining are joined in the autoclave that is mounted with magnetic stirring together, stir; Go out air in the autoclave with hydrogen exchange, then hydrogen pressure and the temperature at 6～10MPa is to react under 180～300 ℃, and cooling obtains described catalyzer;
The precursor of described Primary Catalysts metal is H
2IrCl
6Or RhCl
3The precursor of described promoter metal is selected from KReO
4, a kind of in three Ammonium paramolybdate tetrahydrates, phospho-wolframic acid or any two kinds.
3. method according to claim 1 and 2, it is characterized in that: described carrier is smog SiO
2Or molecular sieve ZSM-5.
4. method according to claim 2, it is characterized in that: the time of described calcining is 3 hours.
5. method according to claim 1, it is characterized in that: the concentration of described inorganic aqueous acid is 25～40wt%.
6. method according to claim 1 or 5, it is characterized in that: described mineral acid is sulfuric acid or phosphoric acid.
7. method according to claim 1 and 2 is characterized in that: described stirring is to utilize magnetic stirring, and the rotating speed of described magnetic stirring is 1000rpm/min.
8. method according to claim 1, it is characterized in that: described temperature is 150～250 ℃.
9. method according to claim 1, it is characterized in that: the pressure of described hydrogen is 4～15MPa.
10. method according to claim 1, it is characterized in that: the time of described reaction is 48～72 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679874A (en) * | 2007-03-08 | 2010-03-24 | 维仁特能源系统公司 | By oxygenated hydrocarbon synthetic liquid fuel and chemical |
| CN102203034A (en) * | 2008-08-27 | 2011-09-28 | 维仁特能源系统公司 | Synthesis of liquid fuels from biomass |
-
2012
- 2012-04-09 CN CN2012101025543A patent/CN103361101A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679874A (en) * | 2007-03-08 | 2010-03-24 | 维仁特能源系统公司 | By oxygenated hydrocarbon synthetic liquid fuel and chemical |
| CN102203034A (en) * | 2008-08-27 | 2011-09-28 | 维仁特能源系统公司 | Synthesis of liquid fuels from biomass |
Non-Patent Citations (1)
| Title |
|---|
| 赵骧: "《催化剂》", 30 April 2001, article "催化剂一般生产方法", pages: 129-131 * |
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