CN106512986B - A kind of catalyst and preparation method and application synthesizing isobutanol by synthesis gas - Google Patents
A kind of catalyst and preparation method and application synthesizing isobutanol by synthesis gas Download PDFInfo
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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Abstract
It is a kind of by synthesis gas synthesis isobutanol catalyst be made of zinc oxide, chromium oxide, tungsten oxide, silica, potassium oxide, its weight percentage are as follows: zinc oxide 10.0-45.0%, chromium oxide 30.0-65.0%, tungsten oxide 5.0-20.0%, silica 0.1-0.4%, potassium oxide 1.0-5.0%.The present invention has CO2Selectivity is low, and total alcohol and isobutanol selectivity are high, the mild advantage of reaction condition.
Description
Technical field
The present invention relates to a kind of synthesis isobutyl alcohol catalyst and preparation methods, are synthesized more particularly to one kind by synthesis gas
The catalyst and preparation method and application of isobutanol.
Background technique
The energy resource structure in China is rich coal, oil-poor, few gas, the energy lattice within the following quite long-term, based on coal
Office will not change.Up to the present, the utilization rate of coal is low, pollutant emission is serious, wastes limited carbon resource, and make
At serious environmental pollution, therefore, exploitation green, efficient coal utilization approach are imperative.
Isobutanol is a kind of basic organic chemical industry raw material, can be used to manufacture isobutyl acetate (paint solvent), anti-oxidant
Agent 2,6-di-tert-butyl p-cresol, synthetic musk, fruit essential oil, isobutyl isobutyrate (flavorant), isobutyl lactate, butyric acid
Isobutyl ester, isobutyronitrile (fine-chemical intermediate), diisobutyl phthalate plasticizer, synthetic rubber, synthetic drug etc.,
It can be used to purify the chemical reagent of the salts such as strontium, barium, lithium and be used as advanced solvent；Isobutanol is reacted with methanol produces methyl- tert
Butyl ether (MTBE) is to obtain high-purity isobutene；Replace methyl tertiary butyl ether(MTBE) that gasoline is added to improve gasoline as oxidant
Octane number is added in diesel oil to reduce by 2.5 numerical value of PM in air.The U.S. in 2010 has been included in the addition of Environmental Protection Administration's fuel
Agent catalogue.Isobutanol produces fourth/octanol process byproduct mainly from propenecarbonyl metaplasia, and yield is difficult to meet market need
It asks, and is petroleum-based products, do not meet the energy pattern in China, the coal base isobutanol for opening up a suitable china natural resources characteristic closes
It has broad prospects at route.
Currently, the catalyst system for directly producing isobutanol by synthesis gas mainly has: based on Cu base catalyst
Low temperature modification methanol catalyst system；The Zn-Cr catalyst system of alkali metals modified；ZrO2Based catalyst system.
United States Patent (USP) (US5387570) report is modified preparation using metal Y, Ce, Nd on the basis of Cu-Mg catalyst
Cu-Mg-YOx, Cu-Mg-CeOx, Cu-Y-Ce-MgOx and Cu-Nd-Ce-MgOx catalyst, in 50~250atm, 260~420
DEG C, under GHSV=1000~5000CC (STP)/(g cath) reaction condition, for synthesis gas isobutanol, the receipts of isobutanol
Rate is 5.7~7.5g/ (kg cath).
Supercritical methanol technology prepares Zn-Cr-K catalyst, and catalyst is typically characterised by ethyl alcohol and the amount of propyl alcohol increases greatly
Add, reaction condition be 7.5Mpa, 400 DEG C, 1700h-1、H2/CO/CH4/CO2When=65.8/32.3/0.5/1.4, C2+OH/
CH3OH reaches 1.7.Selectivity of the isobutanol in alcohol phase be 26% (Fuel Processing Technology, 2001,73:
175-183).By the modified Zn-Cr catalyst of 3.0%Cs, 6.0%Pd, in 440 DEG C, 10.3MPa, H2Under conditions of/CO=1,
The space-time yield of total alcohol reaches 203g/ (kgh), CH3OH/i-C4H9The molar ratio of OH be 0.66 (CatalysisToday, 1999,
52:99-109).Using paste state bed reactor, reaction condition GHSV=5000sl/kg (cat) h, P=13.9MPa, H2/ CO rubs
Your ratio=1.0, at 375 DEG C, ethyl alcohol, normal propyl alcohol, isobutanol molar content be respectively as follows: 19,40,41 (Applied
Catalysis A:General, 247:(2003), 133-142).The utilization alkali metal that United States Patent (USP) (US4513100) is announced/
Alkali-earth metal modified Zn/Cr2O3Catalyst for methanol, at 14~25MPa, 350~450 DEG C of reaction conditions, catalyst activity compared with
Height, predominant alcohols product are methanol and isobutanol, and isobutyl alcohol content is higher, wherein water in products content reach 30~
50wt%.Chinese patent (CN103691442A) uses dipping/step impregnation method, and using aluminium oxide as carrier, ZnO is active group
Point, copper, iron, the synthesis gas isobutyl alcohol catalyst that boron doped silicon p-type semiconductor material is auxiliary agent preparation, relatively mild anti-
Isobutanol selectivity with higher under the conditions of answering.Chinese patent (CN103272609A) is disclosed by zinc oxide, copper oxide, oxygen
Change zirconium synthesis gas isobutyl alcohol catalyst as main component, and add the elements such as rare earth lanthanum, cerium, samarium, thorium, as the result is shown
CO total conversion is 59.24 (mol, %), hydro carbons, CO2, alcohols selectivity (Cmol, %) be respectively 26.35,24.22,
49.43, alcohol phase product is mainly made of methanol and isobutanol.
In reaction temperature 693K, pressure 25Mpa, air speed 20000h-1, synthesis gas composition ratio is CO:H2The reaction of=1:1
Under the conditions of, group becomes Zr (30.5wt%)；Mn (15.4wt%)；Zn (8.6wt%)；Pd (0.2wt%)；Li's (1.5wt%)
Catalyst, the selectivity of isobutanol can achieve 60wt%, yield can achieve 740g/L/h (Catalysis Letter,
3:59-64,1989).Report is mixed using the synthesis of gas produced low-carbon of coprecipitation preparation in Chinese patent (CN102029166A)
Alcohol catalyst, group become ZrO2: 54~75%, MnO2: 10~20%, RxO:0.4~1.0%, CuO:3~5%, C:4~
20%, noble metal: 0.5~1.5%, wherein R is alkali metal, and the presoma of C is starch.The catalyst is in 6.0MPa, and 340 DEG C,
GHSV=7200h-1,H2When/CO=1, C2+Selectivity >=36% of alcohol, selectivity >=25% of isobutanol.
Above studies have shown that there are severe reaction conditions, alcohol product form complexity in synthesis gas synthesis isobutanol synthesis, always
Alcohol is selectively low, CO2The problems such as selectivity is high, and the utilization rate of carbon is low, and isobutyl alcohol content is low in product.Develop suitable catalyst
The reaction can be made to carry out and obtain higher total alcohol and isobutanol yield under the conditions of relatively mild experimental technique, dropped
Low CO2Selectivity is to improve the problem that carbon resource utilization rate is still research.
Summary of the invention
Goal of the invention of the invention is to provide a kind of CO2Selectivity is low, and total alcohol and isobutanol selectivity are high, reaction condition temperature
The catalyst and preparation method and application that isobutanol is synthesized by synthesis gas of sum.
Catalyst of the invention is made of zinc oxide, chromium oxide, tungsten oxide, silica, potassium oxide, and weight percent contains
Amount are as follows: zinc oxide 10.0~45.0%, chromium oxide 30.0~65.0%, tungsten oxide 5.0~20.0%, silica 0.1~
0.4%, potassium oxide 1.0~5.0%.
For catalyst of the present invention using evaporation induction sol-gel method preparation, preparation step is as follows:
(1) soluble zinc salt: soluble chromic salts: water or alcoholic solvent=5~50g:10~80g:100~500ml is pressed, it can
Soluble zinc salt, soluble chromic salts are added in water or alcoholic solvent, and zinc chrome mixed solution is made, and are heated to 35~60 DEG C, and mechanical
Stir 1~5h；
(2) oxalic acid or citric acid: silico-tungstic acid: water or alcoholic solvent=35~50g:0.5~20g:100~500ml are pressed, it will be careless
Acid or citric acid, silico-tungstic acid are added in water or alcoholic solvent, and organic acid soln is made, is heated to 35~60 DEG C, and mechanical stirring 1
~5h；
(3) it is formed by catalyst, zinc chrome organic acid soln obtained in above-mentioned steps (2) being added drop-wise in step (1)
In mixed solution, drop rate is 5~30ml/min, obtains sol form solution；
(4) step (3) is obtained into the sealing of sol form solution, 10~48h of aged at room temperature, then machinery stirs at 50~70 DEG C
Mix 2~5h, to evaporate the further plastic of solvent, after 60~75 DEG C of dry 5~10h, be warming up to 100~150 DEG C of dryings 5~
10h is finally warming up to 400~600 DEG C of 5~10h of roasting after 200~275 DEG C of 5~10h of roasting；
(5) sylvite aqueous solution is made in soluble potassium salt, using equi-volume impregnating, sylvite aqueous solution is added to step
(4) in obtained intermediary, be placed in ultrasonator 30~240min of ultrasound, then in 100~150 DEG C dry 5~
Catalyst is made in 400~600 DEG C of dry 5~10h in 10h.
Soluble zinc salt as described above is Zn (NO3)2Or Zn (CH3COO)2；Soluble chromic salts is Cr (NO3)3Or Cr
(CH3COO)；Soluble potassium salt is KNO3、K2CO3Or K (CH3COO)。
Catalyst application of the invention is as follows:
(1) catalyst reduction: with H2The H that volume content is 1~5%2It is to go back Primordial Qi with Ar gaseous mixture, in gas space velocity 10
~100h-1, 0.2~1MPa of pressure is restored, to 25~30h of catalyst reduction under conditions of 300~360 DEG C of reduction temperature；
(2) catalyst reaction: the catalyst after reduction is passed through synthesis gas and is reacted, in H2/ CO mol ratio is 0.8~3,
8~10MPa of reaction pressure, 340~390 DEG C of reaction temperature, 2000~8000h of air speed-1Under conditions of synthesize isobutanol.
The catalyst preparation new method that the invention proposes one based on evaporating induced synthesis sol-gal process.With it is existing
There is method to compare, advantage is:
(1) catalyst composition is simple, the active component using base metal as catalyst, reduce catalyst at
This；
(2) metal oxide size is more uniform and partial size is smaller；Specific surface area of catalyst is big, activated centre high dispersive in
Catalyst surface is conducive to the progress of isobutyl alcohol synthesis reaction.
(3) catalyst can obtain the total alcohol selectivity of higher one way for synthesis gas synthesis isobutanol reaction
(Cmol, >=60%), lower CO2Selectively (Cmol ,≤10%), isobutanol distribution is higher in alcohol phase product；Make the benefit of carbon
It is greatly improved with rate, so as to avoid the waste of carbon resource.
Specific embodiment
Embodiment 1:
Weigh 20.1g Zn (NO3)2·6H2O, 50.5g Cr (NO3)3·9H2After O is mixed with 200ml deionized water, adding
Heat is to 35 DEG C, and mechanical stirring 2h is configured to mixed solution A.Take 45.2g citric acid, 8.5g silico-tungstic acid and 200ml deionized water
After mixing, 35 DEG C are heated to, and mechanical stirring 2h is configured to mixed solution B.Using peristaltic pump, drop rate 30ml/ is adjusted
Above-mentioned B solution is added drop-wise in above-mentioned solution A by min, obtains sol form solution.For 24 hours by sol form solution sealing aged at room temperature
Afterwards, mechanical stirring 2h is finally placed in baking oven after 60 DEG C of dry 5h, is warming up to evaporate the further plastic of solvent at 70 DEG C
100 DEG C of dry 5h are warming up to 400 DEG C of dry 5h, obtain pulverulent solids C in Muffle furnace after 200 DEG C of dry 5h.
Weigh 1.4g KNO3Be dissolved in wiring solution-forming in appropriate amount of deionized water, powder is added drop-wise to using equi-volume impregnating
On shape solid C, it is placed in ultrasonator ultrasonic 120min；Then, 100 DEG C of dry 5h in baking oven are placed in, are placed in Muffle furnace
400 DEG C of dry 5h, zinc oxide is made, chromium oxide, tungsten oxide, silica, potassium oxide content (wt%) are respectively as follows: 32.67,
55.62,10.01,0.21,1.51 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 4V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 80h-1, restore pressure 0.2MPa, reduction temperature
To catalyst reduction 30h under conditions of 360 DEG C of degree.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO(mol)
=2,10MPa, 360 DEG C, 3000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 21.12
(mol.%), the selectivity (Cmol.%) of total alcohols is 60.12, CO2Selectivity (Cmol.%) be 9.82, methanol in alcohol,
The distribution (wt.%) of ethyl alcohol, propyl alcohol, isobutanol and C5+ alcohol is respectively 76.03,1.80,0.87,20.67 and 0.53.
Embodiment 2:
Weigh 31.2g Zn (CH3COO)2·2H2O, 29.6g Cr (CH3COO)3It is configured to mix with 400ml deionized water
Solution A is heated to 50 DEG C, and mechanical stirring 4h.48.1g citric acid is taken, 9.2g silico-tungstic acid is configured to mix with 400ml deionized water
It closes solution B and is heated to 50 DEG C, and mechanical stirring 4h.Using peristaltic pump, drop rate 25ml/min is adjusted, above-mentioned B solution is dripped
It is added in above-mentioned solution A, obtains sol form solution.After above-mentioned solution aged at room temperature 30h, mechanical stirring 2h is at 70 DEG C to steam
The further plastic of solvent is sent out, is finally placed in baking oven after 70 DEG C of dry 10h, is warming up to 110 DEG C of dry 10h, 200 DEG C in Muffle furnace
After dry 5h, 400 DEG C of dry 5h are warming up to, pulverulent solids C is obtained.
Weigh 0.8g K2CO3Be dissolved in wiring solution-forming in appropriate amount of deionized water, powder is added drop-wise to using equi-volume impregnating
On shape solid C, it is placed in ultrasonator ultrasonic 180min；Then, 100 DEG C of dry 5h in baking oven are placed in, are placed in Muffle furnace
400 DEG C of dry 5h, zinc oxide is made, chromium oxide, tungsten oxide, silica, potassium oxide content (wt.%) are respectively as follows: 29.87,
55.50,11.30,0.23,3.10 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 5V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 100h-1, restore pressure 0.2MPa, reduction temperature
To catalyst reduction 25h under conditions of 360 DEG C of degree.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO(mol)
=1,8MPa, 370 DEG C, 5000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 25.32 (mol.%),
The selectivity (Cmol.%) of total alcohols is 67.48, CO2Selectivity (Cmol.%) be 8.94, methanol in alcohol, ethyl alcohol, propyl alcohol,
The distribution (wt.%) of isobutanol and C5+ alcohol is respectively 70.14,1.58,2.03,24.97 and 1.28.
Embodiment 3:
Weigh 22.1g Zn (NO3)2·6H2O, 54.4g Cr (NO3)3·9H2O is configured to mix with 200ml dehydrated alcohol
Solution A is heated to 45 DEG C, and mechanical stirring 2h.31.6g oxalic acid is taken, 7.4g silico-tungstic acid is configured to mix with 200ml dehydrated alcohol
Solution B is heated to 45 DEG C, and mechanical stirring 2h.Using peristaltic pump, drop rate 20ml/min is adjusted, above-mentioned B solution is added dropwise
Into above-mentioned solution A, sol form solution is obtained.After above-mentioned solution aged at room temperature 48h, mechanical stirring 2h is at 70 DEG C to evaporate
The further plastic of solvent is finally placed in baking oven after 60 DEG C of dry 5h, is warming up to 100 DEG C of dry 5h, 200 DEG C of dryings in Muffle furnace
After 5h, 400 DEG C of dry 5h are warming up to, pulverulent solids C is obtained.
Weigh 0.7g KNO3Be dissolved in wiring solution-forming in appropriate amount of deionized water, powder is added drop-wise to using equi-volume impregnating
On shape solid C, it is placed in ultrasonator ultrasonic 120min；Then, 100 DEG C of dry 5h in baking oven are placed in, are placed in Muffle furnace
400 DEG C of dry 5h, zinc oxide is made, chromium oxide, tungsten oxide, silica, potassium oxide content (wt.%) are respectively as follows: 34.02,
53.19,9.81,0.19,2.81 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 5V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 100h-1, restore pressure 0.3MPa, reduction temperature
To catalyst reduction 30h under conditions of 360 DEG C of degree.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO(mol)
=1.5,9MPa, 350 DEG C, 8000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 24.48
(mol.%), the selectivity (Cmol.%) of total alcohols is 66.51, CO2Selectivity (Cmol.%) be 7.14, methanol in alcohol,
The distribution (wt.%) of ethyl alcohol, propyl alcohol, isobutanol and C5+ alcohol is respectively 68.16,1.89,0.82,27.79 and 1.33.
Embodiment 4:
Weigh 40.6g Zn (CH3COO)2·2H2O, 46.3g Cr (NO3)3·9H2O and 500ml deionized water is configured to mix
Solution A is closed, 50 DEG C, and mechanical stirring 5h are heated to.36.41g oxalic acid is taken, 10.5g silico-tungstic acid is configured to 500ml deionized water
Mixed solution B is heated to 50 DEG C, and mechanical stirring 5h.Using peristaltic pump, drop rate 20ml/min is adjusted, by above-mentioned B solution
It is added drop-wise in above-mentioned solution A, obtains sol form solution.After above-mentioned solution aged at room temperature 36h, at 70 DEG C mechanical stirring 2h with
The further plastic of solvent is evaporated, is finally placed in baking oven after 70 DEG C of dry 5h, is warming up to 100 DEG C of dry 5h, 200 DEG C in Muffle furnace
After dry 5h, 500 DEG C of dry 5h are warming up to, pulverulent solids C is obtained.
Weigh 1.1g KNO3Be dissolved in wiring solution-forming in appropriate amount of deionized water, powder is added drop-wise to using equi-volume impregnating
On shape solid C, it is placed in ultrasonator ultrasonic 120min；Then, 100 DEG C of dry 5h in baking oven are placed in, are placed in Muffle furnace
400 DEG C of dry 5h, zinc oxide is made, chromium oxide, tungsten oxide, silica, potassium oxide content (wt.%) are respectively as follows: 35.17,
48.58,12.45,0.25,3.64 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 4V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 100h-1, restore pressure 0.2MPa, reduction temperature
To catalyst reduction 28h under conditions of 360 DEG C of degree.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO(mol)
=2,10MPa, 390 DEG C, 4000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 27.23
(mol.%), the selectivity (Cmol.%) of total alcohols is 67.31, CO2Selectivity (Cmol.%) be 6.62, methanol in alcohol,
The distribution (wt.%) of ethyl alcohol, propyl alcohol, isobutanol and C5+ alcohol is respectively 65.96,1.03,0.90,30.41 and 1.60.
Embodiment 5:
Weigh 42.8g Zn (NO3)2·6H2O, 48.0g Cr (NO3)3·9H2O and 250ml ethyl alcohol are configured to mixed solution
A is heated to 35 DEG C, and mechanical stirring 2h.48.9g citric acid is taken, 9.8g silico-tungstic acid and 250ml ethyl alcohol are configured to mixed solution B
It is heated to 35 DEG C, and mechanical stirring 2h.Using peristaltic pump, drop rate 25ml/min is adjusted, above-mentioned B solution is added drop-wise to above-mentioned
In solution A, sol form solution is obtained.By above-mentioned solution aged at room temperature for 24 hours after, at 70 DEG C mechanical stirring 2h with evaporate solvent into
One step plastic is finally placed in baking oven after 70 DEG C of dry 5h, is warming up to 100 DEG C of dry 5h, in Muffle furnace after 220 DEG C of dry 5h,
425 DEG C of dry 5h are warming up to, pulverulent solids C is obtained.
Weigh 1.4g K (CH3COO) and it is dissolved in wiring solution-forming in appropriate amount of deionized water, is added drop-wise to using equi-volume impregnating
On pulverulent solids C, it is placed in ultrasonator ultrasonic 120min；Then, 100 DEG C of dry 5h in baking oven are placed in, Muffle is placed in
400 DEG C of dry 5h in furnace are made zinc oxide, chromium oxide, tungsten oxide, silica, potassium oxide content (wt.%) and are respectively as follows:
36.92,48.94,11.15,0.24,2.42 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 5V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 100h-1, restore pressure 0.2MPa, reduction temperature
To catalyst reduction 30h under conditions of 360 DEG C of degree.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO(mol)
=3,8MPa, 340 DEG C, 2000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 26.52 (mol.%),
The selectivity (Cmol.%) of total alcohols is 68.55, CO2Selectivity (Cmol.%) be 5.52, methanol in alcohol, ethyl alcohol, propyl alcohol,
The distribution (wt.%) of isobutanol and C5+ alcohol is respectively 73.81,2.07,0.66,21.95 and 1.50.
Embodiment 6:
Weigh 7.5g Zn (NO3)2·6H2O, 57.6g Cr (NO3)3·9H2O is configured to mix molten with 200ml deionized water
Liquid A is heated to 60 DEG C, and mechanical stirring 1h.46.9g citric acid is taken, 4.6g silico-tungstic acid is configured to mix with 200ml deionized water
Solution B is heated to 60 DEG C, and mechanical stirring 1h.Using peristaltic pump, drop rate 10ml/min is adjusted, above-mentioned B solution is added dropwise
Into above-mentioned solution A, sol form solution is obtained.After above-mentioned solution aged at room temperature 10h, mechanical stirring 3h is at 70 DEG C to evaporate
The further plastic of solvent is finally placed in baking oven after 60 DEG C of dry 6h, is warming up to 150 DEG C of dry 5h, 250 DEG C of dryings in Muffle furnace
After 10h, 500 DEG C of dry 10h are warming up to, pulverulent solids C is obtained.
Weigh 4.5g KNO3Be dissolved in wiring solution-forming in appropriate amount of deionized water, powder is added drop-wise to using equi-volume impregnating
On shape solid C, it is placed in ultrasonator ultrasonic 180min；Then, 150 DEG C of dry 5h in baking oven are placed in, are placed in Muffle furnace
500 DEG C of dry 10h, zinc oxide is made, chromium oxide, tungsten oxide, silica, potassium oxide content (wt%) are respectively as follows: 12.35,
63.41,18.96,0.39,4.89 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 1.5V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 100h-1, restore pressure 0.6MPa, reduction
To catalyst reduction 30h under conditions of 300 DEG C of temperature.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO
(mol)=0.8,9MPa, 380 DEG C, 3000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 20.98
(mol.%), the selectivity (Cmol.%) of total alcohols is 63.22, CO2Selectivity (Cmol.%) be 8.64, methanol in alcohol,
The distribution (wt.%) of ethyl alcohol, propyl alcohol, isobutanol and C5+ alcohol is respectively 74.31,2.61,0.32,22.24 and 0.52.
Embodiment 7:
Weigh 40.1g Zn (CH3COO)2·2H2O, 27.9g Cr (CH3COO)3It is configured to mix with 400ml deionized water
Solution A is heated to 35 DEG C, and mechanical stirring 4h.45.6g citric acid is taken, 4.6g silico-tungstic acid is configured to mix with 400ml deionized water
It closes solution B and is heated to 35 DEG C, and mechanical stirring 4h.Using peristaltic pump, drop rate 5ml/min is adjusted, above-mentioned B solution is added dropwise
Into above-mentioned solution A, sol form solution is obtained.By above-mentioned solution aged at room temperature for 24 hours after, mechanical stirring 5h is at 70 DEG C to evaporate
The further plastic of solvent is finally placed in baking oven after 65 DEG C of dry 5h, is warming up to 150 DEG C of dry 10h, is done for 270 DEG C in Muffle furnace
After dry 10h, 600 DEG C of dry 10h are warming up to, pulverulent solids C is obtained.
Weigh 0.9g K2CO3Be dissolved in wiring solution-forming in appropriate amount of deionized water, powder is added drop-wise to using equi-volume impregnating
On shape solid C, it is placed in ultrasonator ultrasonic 240min；Then, 150 DEG C of dry 10h in baking oven are placed in, are placed in Muffle furnace
600 DEG C of dry 10h, zinc oxide is made, chromium oxide, tungsten oxide, silica, potassium oxide content (wt.%) are respectively as follows: 38.41,
52.21,5.63,0.11,3.64 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 3V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 80h-1, restore pressure 0.8MPa, reduction temperature
To catalyst reduction 25h under conditions of 350 DEG C of degree.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO(mol)
=2.5,10MPa, 370 DEG C, 5000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 25.14
(mol.%), the selectivity (Cmol.%) of total alcohols is 65.64, CO2Selectivity (Cmol.%) be 9.32, methanol in alcohol,
The distribution (wt.%) of ethyl alcohol, propyl alcohol, isobutanol and C5+ alcohol is respectively 69.42,2.03,1.97,26.27 and 0.21.
Embodiment 8:
Weigh 29.0g Zn (NO3)2·6H2O, 34.1g Cr (NO3)3·9H2O is configured to mix with 200ml dehydrated alcohol
Solution A is heated to 55 DEG C, and mechanical stirring 2h.35.2g oxalic acid is taken, 12.8g silico-tungstic acid is configured to mix with 200ml dehydrated alcohol
It closes solution B and is heated to 55 DEG C, and mechanical stirring 2h.Using peristaltic pump, drop rate 15ml/min is adjusted, above-mentioned B solution is dripped
It is added in above-mentioned solution A, obtains sol form solution.After above-mentioned solution aged at room temperature 12h, mechanical stirring 2h is at 70 DEG C to steam
The further plastic of solvent is sent out, is finally placed in baking oven after 60 DEG C of dry 8h, 120 DEG C of dry 5h are warming up to, is done for 240 DEG C in Muffle furnace
After dry 6h, 450 DEG C of dry 6h are warming up to, pulverulent solids C is obtained.
Weigh 1.1g KNO3Be dissolved in wiring solution-forming in appropriate amount of deionized water, powder is added drop-wise to using equi-volume impregnating
On shape solid C, it is placed in ultrasonator ultrasonic 120min；Then, 120 DEG C of dry 5h in baking oven are placed in, are placed in Muffle furnace
450 DEG C of dry 6h, zinc oxide is made, chromium oxide, tungsten oxide, silica, potassium oxide content (wt.%) are respectively as follows: 44.69,
33.27,17.03,0.35,4.66 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 4V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 50h-1, restore pressure 0.5MPa, reduction temperature
To catalyst reduction 30h under conditions of 300 DEG C of degree.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO(mol)
=2.3,8MPa, 360 DEG C, 4000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 20.63
(mol.%), the selectivity (Cmol.%) of total alcohols is 64.23, CO2Selectivity (Cmol.%) be 6.12, methanol in alcohol,
The distribution (wt.%) of ethyl alcohol, propyl alcohol, isobutanol and C5+ alcohol is respectively 71.92,1.42,1.67,24.60 and 0.32.
Embodiment 9:
Weigh 33.3g Zn (CH3COO)2·2H2O, 54.8g Cr (NO3)3·9H2O and 500ml deionized water is configured to mix
Solution A is closed, 45 DEG C, and mechanical stirring 3h are heated to.38.7g oxalic acid is taken, 10.4g silico-tungstic acid is configured to 500ml deionized water
Mixed solution B is heated to 45 DEG C, and mechanical stirring 3h.Using peristaltic pump, drop rate 10ml/min is adjusted, by above-mentioned B solution
It is added drop-wise in above-mentioned solution A, obtains sol form solution.After above-mentioned solution aged at room temperature 48h, at 70 DEG C mechanical stirring 5h with
The further plastic of solvent is evaporated, is finally placed in baking oven after 70 DEG C of dry 5h, is warming up to 150 DEG C of dry 8h, 275 DEG C in Muffle furnace
After dry 10h, 600 DEG C of dry 10h are warming up to, pulverulent solids C is obtained.
Weigh 0.5g KNO3Be dissolved in wiring solution-forming in appropriate amount of deionized water, powder is added drop-wise to using equi-volume impregnating
On shape solid C, it is placed in ultrasonator ultrasonic 240min；Then, 150 DEG C of dry 8h in baking oven are placed in, are placed in Muffle furnace
600 DEG C of dry 10h, zinc oxide is made, chromium oxide, tungsten oxide, silica, potassium oxide content (wt.%) are respectively as follows: 28.82,
33.27,12.35,0.24,1.13 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 3V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 60h-1, restore pressure 0.3MPa, reduction temperature
To catalyst reduction 25h under conditions of 360 DEG C of degree.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO(mol)
=2.8,9MPa, 380 DEG C, 3000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 23.65
(mol.%), the selectivity (Cmol.%) of total alcohols is 60.96, CO2Selectivity (Cmol.%) be 9.32, methanol in alcohol,
The distribution (wt.%) of ethyl alcohol, propyl alcohol, isobutanol and C5+ alcohol is respectively 68.98,1.67,2.17,26.31 and 0.72.
Embodiment 10:
Weigh 21.1g Zn (NO3)2·6H2O, 58.4g Cr (NO3)3·9H2O and 250ml ethyl alcohol are configured to mixed solution
A is heated to 40 DEG C, and mechanical stirring 3h.49.2g citric acid is taken, 15.4g silico-tungstic acid and 250ml ethyl alcohol are configured to mixed solution B
It is heated to 40 DEG C, and mechanical stirring 3h.Using peristaltic pump, drop rate 30ml/min is adjusted, above-mentioned B solution is added drop-wise to above-mentioned
In solution A, sol form solution is obtained.After above-mentioned solution aged at room temperature 30h, at 70 DEG C mechanical stirring 3h with evaporate solvent into
One step plastic is finally placed in baking oven after 65 DEG C of dry 5h, is warming up to 120 DEG C of dry 6h, in Muffle furnace after 220 DEG C of dry 8h,
500 DEG C of dry 6h are warming up to, pulverulent solids C is obtained.
Weigh 2.3g K (CH3COO) and it is dissolved in wiring solution-forming in appropriate amount of deionized water, is added drop-wise to using equi-volume impregnating
On pulverulent solids C, it is placed in ultrasonator ultrasonic 180min；Then, 120 DEG C of dry 6h in baking oven are placed in, Muffle is placed in
500 DEG C of dry 6h in furnace are made zinc oxide, chromium oxide, tungsten oxide, silica, potassium oxide content (wt.%) and are respectively as follows:
18.46,59.69,17.56,0.36,4.02 catalyst.It forms, be crushed to 30~40 mesh, it is spare.
H is diluted with 5V%2(VH2/V(H2+Ar)) it is to go back Primordial Qi, in gas space velocity 10h-1, restore pressure 1.0MPa, reduction temperature
To catalyst reduction 30h under conditions of 300 DEG C of degree.Catalyst after reduction is passed through synthesis gas and is reacted, in H2/CO(mol)
=1.8,10MPa, 390 DEG C, 6000h-1Under conditions of, carry out catalyst performance evaluation.CO conversion per pass is 22.57
(mol.%), the selectivity (Cmol.%) of total alcohols is 68.30, CO2Selectivity (Cmol.%) be 5.69, methanol in alcohol,
The distribution (wt.%) of ethyl alcohol, propyl alcohol, isobutanol and C5+ alcohol is respectively 67.03,1.73,2.51,28.21 and 0.38.
Claims (5)
1. a kind of preparation method for the catalyst for synthesizing isobutanol by synthesis gas, the catalyst is by zinc oxide, chromium oxide, oxidation
Tungsten, silica, potassium oxide composition, weight percentage are as follows: zinc oxide 10.0~45.0%, chromium oxide 30.0~65.0%,
Tungsten oxide 5.0~20.0%, silica 0.1~0.4%, potassium oxide 1.0~5.0%；It is characterized by comprising steps are as follows:
(1) soluble zinc salt: soluble chromic salts: water or alcoholic solvent=5~ml of g:100~500 of 50 g:10~80 is pressed, it will be solvable
Property zinc salt, soluble chromic salts is added in water or alcoholic solvent, zinc chrome mixed solution is made, is heated to 35~60 DEG C, and machinery stirs
Mix 1~5 h；
(2) oxalic acid or citric acid: silico-tungstic acid: water or alcoholic solvent=35~ml of g:100~500 of 50 g:0.5~20 are pressed, by oxalic acid
Or citric acid, silico-tungstic acid are added in water or alcoholic solvent, and organic acid soln is made, and are heated to 35~60 DEG C, and mechanical stirring 1
~5 h；
(3) it is formed by catalyst, organic acid soln obtained in above-mentioned steps (2) is added drop-wise to the zinc chrome in step (1) and is mixed
In solution, drop rate is 5~30 ml/min, obtains sol form solution；
(4) step (3) is obtained sol form solution to seal, 10~48 h of aged at room temperature, then the mechanical stirring at 50~70 DEG C
2~5 h after 60~75 DEG C of dry 5~10 h, are warming up to 100~150 DEG C of dryings 5 to evaporate the further plastic of solvent
~10 h are finally warming up to 400~600 DEG C of 5~10 h of roasting after 200~275 DEG C of 5~10 h of roasting；
(5) sylvite aqueous solution is made in soluble potassium salt, using equi-volume impregnating, sylvite aqueous solution is added to step (4) institute
In obtained intermediary, 30~240 min of ultrasound are placed in ultrasonator, then in 100~150 DEG C of dry 5~10 h,
In 400~600 DEG C of dry 5~10 h, catalyst is made.
2. a kind of preparation method for the catalyst for synthesizing isobutanol by synthesis gas as described in claim 1, it is characterised in that institute
The soluble zinc salt stated is Zn (NO3)2Or Zn (CH3COO)2 。
3. a kind of preparation method for the catalyst for synthesizing isobutanol by synthesis gas as described in claim 1, it is characterised in that institute
The soluble chromic salts stated is Cr (NO3)3Or Cr (CH3COO)3。
4. a kind of preparation method for the catalyst for synthesizing isobutanol by synthesis gas as described in claim 1, it is characterised in that institute
The soluble potassium salt stated is KNO3、K2CO3Or K (CH3COO)。
5. the application of the method as described in claim 1 catalyst obtained for synthesizing isobutanol by synthesis gas, it is characterised in that
Include the following steps:
(1) catalyst reduction: with H2H2 and the Ar gaseous mixture that volume content is 1~5 % be also Primordial Qi, gas space velocity 10~
100 h-1, 0.2~1 MPa of pressure is restored, to 25~30 h of catalyst reduction under conditions of 300~360 DEG C of reduction temperature；
(2) catalyst reaction: the catalyst after reduction is passed through synthesis gas and is reacted, in H2/ CO mol ratio is 0.8~3, reaction
8~10 MPa of pressure, 340~390 DEG C of reaction temperature, 2000~8000 h of air speed-1Under conditions of synthesize isobutanol.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3418258A (en) * | 1964-02-18 | 1968-12-24 | Basf Ag | Production of highly active metals of the iron group |
| CN101185895A (en) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | Catalyst for synthesizing low carbon mellow with synthesis gas and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3418258A (en) * | 1964-02-18 | 1968-12-24 | Basf Ag | Production of highly active metals of the iron group |
| CN101185895A (en) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | Catalyst for synthesizing low carbon mellow with synthesis gas and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Iso-butanol direct synthesis from syngas over the alkali metalsmodified Cr/ZnO catalysts";Li Tan等;《Applied Catalysis A: General》;20150803;第505卷;第141-149页 * |
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