CN101185899A - Copper base catalyst for producing low carbon mixed alcohol by synthesis gas and preparation method and application - Google Patents
Copper base catalyst for producing low carbon mixed alcohol by synthesis gas and preparation method and application Download PDFInfo
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Abstract
The weight percentages of a copper-based catalyst for making low carbon mixed alcohol with synthetic gas are: Cu: 20-60%,Fe: 20-60%,Mn: 0-30% and Zn: 0-30%. The metal, in the form of nitrate, is dissolved into the distilled water to form a mixed solution, and is precipitated with alkaline solution at the temperature of 20-90 DEG C to prepare catalyst. The invention has the advantages of high activity, high selectivity and good stability.
Description
Technical field
The invention belongs to a kind of Preparation of catalysts methods and applications, relate in particular to a kind of preparation method and application thereof of catalyst for preparing low-carbon mixed alcohol by synthetic gas.
Background technology
The energy is the essential condition that guarantees a national economy sustainable development and safety and stability.Along with the exhaustion day by day of petroleum resources, the future source of energy structure will turn to based on coal and natural gas.In the recent period along with China's rapid development of economy, domestic Fuel Demand is increased fast, after the energy presented short state on a large scale, the absolute magnitude of petroleum import and relative proportion were all in continuous increase, and the Chinese government has given the attention of unprecedented height to the national energy security problem.Utilizing angle from resources effective, is the coal indirect reformer research of liquid fuel and chemicals, have a wide range of applications, and serve as that MAS (C is produced by synthesis gas in the basis with coal and natural gas
1-C
6Alcohols mixture Higher Alcohols, Mixed Alcohols) be C
1One of important content of chemistry, its technological process is similar with synthesizing methanol substantially.The additive that acts as a fuel, it has fine solubility, volatility, driver behavior and higher octane number.In addition, it can also use as the raw material and the clean fuel of some chemical products.
At present existing in a large number by the reports of co hydrogenation synthesis of low-carbon alcohol, wherein representative have four kinds of catalyst systems: (1) modified methanol synthetic catalyst (Cu/ZnO/Al
2O
3, ZnO/Cr
2O
3): this catalyst adds an amount of alkali metal or alkaline earth metal compound modification by methanol synthesis catalyst and gets, typical patent has EP-0034338-A2 people such as () C.E.Hofstadt and United States Patent (USP) 4513100 (Snam company subsidizes, and the invention people is people such as Fattore).Though this type of catalyst is active higher, isobutanol content height in the product, shortcoming is severe reaction conditions (pressure is 14-20MPa, and temperature is 350-450 ℃), higher alcohol selectivity low (being generally less than 35%), water content height (being generally 30-50%) in the product; (2) Rh catalyst based (as US 4014913 and 4096164): after adding one to two kind of transition metal or metal oxide auxiliary agent in the support type Rh catalyst, to low-carbon alcohols is synthetic higher activity and selectivity are arranged, particularly to C
2 +The selectivity of alcohol is higher, and product is based on ethanol.But the Rh compound costs an arm and a leg, and catalyst is easily by CO
2Poison, its activity and selectivity generally do not reach industrial requirement.(3) anti-sulphur MoS
2Catalyst: being worth mentioning most is that the molybdenum of U.S. DOW company exploitation is sulfide catalyst (main patent is seen people's such as Stevens US patent 4882360), this catalyst system and catalyzing not only has anti-sulphur, product is moisture few, and higher alcohol content is higher, reaching 30-70%, wherein mainly is ethanol and normal propyl alcohol.The subject matter that this catalyst exists be wherein auxiliary element very easily and form carbonyls between the carbon monoxide, cause the loss of auxiliary element, influence activity of such catalysts and selectivity, cause catalyst stability and life-span to be restricted.(4) Cu-Co catalyst: France Petroleum Institute (IFP) has at first developed Cu-Co co-precipitation low-carbon alcohol catalyst, only four catalyst patent (US Patent4122110 have just been obtained before 1985,4291126 and GB Patent 2118061,2158730), the synthetic product of this catalyst is mainly C
1-C
6The straight chain n-alkanol, accessory substance is mainly C
1-C
6Aliphatic hydrocarbon, reaction condition gentleness (similar) to the low pressure methanol synthetic catalyst.The shortcoming of this catalyst is a less stable.
Summary of the invention
Shortcomings such as purpose of the present invention is primarily aimed at that catalyst higher alcohol selectivity is low, severe reaction conditions, accessory substance are many provide a kind of have high activity and high selectivity, and have had the catalyst method for making and the application of fine stability.
The percentage by weight of catalyst of the present invention consists of: Cu:20-60%, Fe:20-60%, Mn:0-30%, Zn:0-30%.
Preparation of catalysts method provided by the invention may further comprise the steps:
Catalyst adopts the coprecipitation preparation.Form mixed solution in the middle of metal is dissolved in distilled water with the form of nitrate.20-90 ℃ with the alkaline solution co-precipitation, precipitation process needs fully to stir, and keeps pH=5-12, precipitation is washed till the neutrality through distilled water, then 60-160 ℃ dry down, 200-750 ℃ of roasting.
Aforesaid alkaline solution is sodium carbonate, ammoniacal liquor or potash etc.
Application of Catalyst condition of the present invention is: reaction temperature is 220-340 ℃, and pressure is 2.0-12.0MPa, and air speed is 500-10000h
-1, H
2/ CO=0.5-3.0.
The present invention compared with prior art has following characteristics:
(a) method for preparing catalyst of the present invention is simple, easy operating, and catalyst reaction performance repeatability is relatively good, realizes the industry amplification easily.
(b) each component distribution of catalyst of the present invention is more even, and has strong interaction between each component, and anti-agglutinatting property can be relatively good.
(c) but straight forming after the catalyst drying of the present invention, but also adding additives compressing tablet or extruded moulding.And the catalyst mechanical strength after roasting is relatively good.
(d) catalyst of the present invention does not need to add CO in reduction and course of reaction
2Gas greatly reduces operating cost.
(e) adopt catalyst of the present invention to carry out the synthetic of low-carbon alcohols, its total pure selectivity is 35-65%, and total pure space-time yield is 0.15-0.45g/h.mL.cat; Water in products content is 15-40%; Higher alcohol content is 35-60%.
The specific embodiment
Embodiment 1
With following metallic atom with the form of nitrate Cu: Fe: Mn: Zn=1.0 in molar ratio: form certain density mixed solution in the middle of being dissolved in distilled water at 1.0: 0.5: 0.2.60 ℃ down with 30% sodium carbonate liquor and flow co-precipitation, precipitation process needs fully to stir, and keeps pH=9-10.Precipitation is washed till the neutrality through distilled water.Wet cake through 120 ℃ dry after under 450 ℃ of air atmospheres roasting 6h, be crushed to the 40-60 order, obtain catalyst 1
#Each weight metal percentage composition Cu:39.73%, Fe:34.92%, Mn:17.17%, Zn:8.18%.Reaction condition is as follows: T=280 ℃, and P=4.0MPa, GHSV=8000h
-1, H
2/ CO=2.0, reaction result sees Table 1.
Embodiment 2
With following metallic atom with the form of nitrate Cu: Fe: Mn: Zn=1.0 in molar ratio: form certain density mixed solution in the middle of being dissolved in distilled water at 1.5: 0.5: 0.2.60 ℃ down with 20% ammoniacal liquor and flow co-precipitation, precipitation process needs fully to stir, and keeps pH=8-9.Precipitation is washed till the neutrality through distilled water.Wet cake through 120 ℃ dry after under 400 ℃ of air atmospheres roasting 6h, be crushed to the 40-60 order, obtain catalyst 2
#Each weight metal percentage composition Cu:33.82%, Fe:44.59%, Mn:14.63%, Zn:6.96%.Reaction condition is as follows: T=280 ℃, and P=4.0MPa, GHSV=8000h
-1, H
2/ CO=2.0, reaction result sees Table 1.
Embodiment 3
With following metallic atom with the form of nitrate Cu: Fe: Mn=1.0 in molar ratio: form certain density mixed solution in the middle of being dissolved in distilled water at 1.5: 0.5.60 ℃ down with 30% potash and flow co-precipitation, precipitation process needs fully to stir, and keeps pH=9-10.Precipitation is washed till the neutrality through distilled water.Wet cake through 120 ℃ dry after under 400 ℃ of air atmospheres roasting 6h, be crushed to the 40-60 order, obtain catalyst 3
#Each weight metal percentage composition Cu:36.35%, Fe:47.93%, Mn:15.72%.Reaction condition is as follows: T=280 ℃, and P=4.0MPa, GHSV=8000h
-1, H
2/ CO=2.0, reaction result sees Table 1.
Embodiment 4
With following metallic atom with the form of nitrate Cu: Fe: Zn=1.0 in molar ratio: form certain density mixed solution in the middle of being dissolved in distilled water at 0.5: 0.5.60 ℃ down with 30% sodium carbonate and flow co-precipitation, precipitation process needs fully to stir, and keeps pH=9-10.Precipitation is washed till the neutrality through distilled water.Wet cake through 120 ℃ dry after under 450 ℃ of air atmospheres roasting 6h, be crushed to the 40-60 order, obtain catalyst 4
#Each weight metal percentage composition Cu:51.18%, Fe:22.49%, Zn:26.33%.Reaction condition is as follows: T=280 ℃, and P=4.0MPa, GHSV=8000h
-1, H
2/ CO=2.0, reaction result sees Table 1.
Embodiment 5
With following metallic atom with the form of nitrate Cu: Zn=1.0 in molar ratio: 1.0 form certain density mixed solution in the middle of being dissolved in distilled water.60 ℃ down with 30% sodium carbonate and flow co-precipitation, precipitation process needs fully to stir, and keeps pH=9-10.With following metallic atom with the form of nitrate Fe: Mn=0.5 in molar ratio: 0.5 forms certain density mixed solution in the middle of being dissolved in distilled water.In above-mentioned thermal capacitance device, with 20% ammoniacal liquor and flow co-precipitation, keep pH=8-9.Precipitation is washed till the neutrality through distilled water.Wet cake through 120 ℃ dry after under 450 ℃ of air atmospheres roasting 6h, be crushed to the 40-60 order, obtain catalyst 5
#Each weight metal percentage composition Cu:35.39%, Fe:31.10%, Mn:15.30%, Zn:18.21%.Reaction condition is as follows: T=280 ℃, and P=4.0MPa, GHSV=8000h
-1, H
2/ CO=2.0, reaction result sees Table 1.
Embodiment 6
With following metallic atom with the form of nitrate Fe: Mn=0.5 in molar ratio: 0.5 forms certain density mixed solution in the middle of being dissolved in distilled water.60 ℃ down with 20% ammoniacal liquor and flow co-precipitation, keep pH=8-9.With following metallic atom with the form of nitrate Cu: Zn=1.0 in molar ratio: 1.0 form certain density mixed solution in the middle of being dissolved in distilled water.With 30% sodium carbonate and flow co-precipitation, precipitation process needs fully to stir in above-mentioned thermal capacitance device, and keeps pH=9-10.Precipitation is washed till the neutrality through distilled water.Wet cake through 120 ℃ dry after under 450 ℃ of air atmospheres roasting 6h, be crushed to the 40-60 order, obtain catalyst 6
#Each weight metal percentage composition Cu:35.39%, Fe:31.10%, Mn:15.30%, Zn:18.21%.Reaction condition is as follows: T=280 ℃, and P=4.0MPa, GHSV=8000h
-1, H
2/ CO=2.0, reaction result sees Table 1.
Embodiment 7
With following metallic atom with the form of nitrate Cu: Fe: Mn: Zn=1.5 in molar ratio: form certain density mixed solution in the middle of being dissolved in distilled water at 0.5: 0.5: 0.2.60 ℃ down with 30% sodium carbonate liquor and flow co-precipitation, precipitation process needs fully to stir, and keeps pH=9-10.Precipitation is washed till the neutrality through distilled water.Wet cake through 120 ℃ dry after under 450 ℃ of air atmospheres roasting 6h, be crushed to the 40-60 order, obtain catalyst 7
#Each weight metal percentage composition Cu:58.20%, Fe:17.05%, Mn:16.77%, Zn:7.98%.Reaction condition is as follows: T=240 ℃, and P=8.0MPa, GHSV=4000h
-1, H
2/ CO=2.0, reaction result sees Table 1.
Embodiment 8
With following metallic atom with the form of nitrate Cu: Fe: Mn: Zn=1.0 in molar ratio: form certain density mixed solution in the middle of being dissolved in distilled water at 1.5: 0.5: 0.1.60 ℃ down with 20% ammonia spirit and flow co-precipitation, precipitation process needs fully to stir, and keeps pH=8-9.Precipitation is washed till the neutrality through distilled water.Wet cake through 120 ℃ dry after under 450 ℃ of air atmospheres roasting 6h, be crushed to the 40-60 order, obtain catalyst 8
#Each weight metal percentage composition Cu:35.05%, Fe:46.20%, Mn:15.15%, Zn:3.60%.Reaction condition is as follows: T=240 ℃, and P=2.0MPa, GHSV=10000h
-1, H
2/ CO=2.0, reaction result sees Table 1.
The evaluating catalyst experiment:
Experiment adopts the pressurization continuous flow fixed bed reactor to investigate catalyst synthetic fuel methyl alcohol reactivity worth provided by the invention.Catalyst powder is broken to the 40-60 order, and loadings is 1.5ml.Unstripped gas makes through methanol decomposition.Gas enters reactor after purification, mass flowmenter metering.H in the unstripped gas
2Between/the CO=0.5-3.0.Before catalyst is estimated, catalyst is reduced.The reduction of catalyst adopts synthesis gas as reducing gases, and the condition of reduction is: pressure 0.1-1.0MPa, air speed is 500-5000h
-1, adopt temperature programmed reduction, be elevated to design temperature gradually from room temperature after, keep certain hour, be cooled to room temperature then after, switch to synthesis gas.Reactor outlet material is through cooling, gas-liquid separation, and tail gas is through metering emptying, regularly setting-out of liquid product.For guaranteeing the reliability of stationary state operating data, the catalyst operation began sampling after 48 hours.Representative for guaranteeing the coercibility product of being got, each stationary state operation is all greater than 12 hours.Gas and product liquid adopt the analysis of Tianjin, island GC-8A gas chromatograph.Thermal conductivity detector (TCD) (TCD) detects CO, the CO in the tail gas
2, H
2, CH
4Volume content and the H in the product liquid
2O, CH
3The percentage by weight of OH, its chromatographic column use carbon molecular sieve and the GDX401 packed column of 2m respectively, and column temperature is 110 ℃.Hydrocarbon in the gas and the mixed alcohol in the liquid then detect (FTD) by hydrogen flame ionization detector, and its chromatographic column is Chrmosorb 101 and the Porapak Q packed column of 2m, and column temperature is 110 ℃.
Gas is that intermediate carries out related normalizing calculating by methane gas, and liquid is that the related normalizing of intermediate calculates by methyl alcohol.Table 1 is embodiment catalyst reaction result.
Table 1 embodiment reaction result
| Embodiment | CO conversion ratio (%) | Alcohol productive rate (g/mL.h) | Water content (wt%) | Selectivity (wt.%) | Alcohol distribution (wt%) | |||
| ROH | HC | CO 2 | C 1 | C 2+ | ||||
| 1 # 2 # 3 # 4 # 5 # 6 # 7 # 8# | 52.00 57.38 54.15 69.68 47.52 58.32 69.11 30.18 | 0.274 0.352 0.361 0.212 0.314 0.388 0.301 0.390 | 25.87 32.27 24.19 16.54 25.87 17.87 21.32 35.66 | 43.53 38.12 55.69 50.70 40.13 61.31 36.24 63.36 | 28.19 32.52 25.44 33.92 30.01 21.84 40.29 23.82 | 28.28 29.36 18.87 15.38 29.86 16.85 23.47 12.82 | 53.48 47.62 56.20 43.57 55.32 41.67 40.81 63.74 | 46.52 52.38 43.80 50.43 44.68 58.33 59.19 36.26 |
Claims (4)
1. a copper-based catalysts that is used for preparing low-carbon mixed alcohol by synthetic gas is characterized in that the percentage by weight of catalyst consists of: Cu:20-60%, Fe:20-60%, Mn:0-30%, Zn:0-30%.
2. the preparation method that a kind of copper base that is used for preparing low-carbon mixed alcohol by synthetic gas as claimed in claim 1 is urged is characterized in that may further comprise the steps:
Form mixed solution in the middle of metal is dissolved in distilled water with the form of nitrate, 20-90 ℃ with the alkaline solution co-precipitation, precipitation process needs fully to stir, keep pH=5-12, precipitation is washed till the neutrality through distilled water, then 60-160 ℃ dry down, 200-750 ℃ of roasting.
3. the preparation method that a kind of copper base that is used for preparing low-carbon mixed alcohol by synthetic gas as claimed in claim 2 is urged is characterized in that described alkaline solution is sodium carbonate, ammoniacal liquor or potash etc.
4. the application that a kind of copper base that is used for preparing low-carbon mixed alcohol by synthetic gas as claimed in claim 1 is urged, its feature at application conditions is: reaction temperature is 220-340 ℃, and pressure is 2.0-12.0MPa, and air speed is 500-10000h
-1, H
2/ CO=0.5-3.0.
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| CN102228835A (en) * | 2011-04-21 | 2011-11-02 | 合肥天焱绿色能源开发有限公司 | Catalyst for synthesizing low-carbon mixed alcohol and preparation method of catalyst |
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| CN102407115A (en) * | 2011-09-26 | 2012-04-11 | 上海应用技术学院 | Catalyst for preparation of lower alcohols by synthetic gas, preparation method and application |
| CN102631927A (en) * | 2012-03-30 | 2012-08-15 | 中国科学院广州能源研究所 | Double-hole carrier iron/ copper low-carbon alcohol synthesis catalyst and preparation method thereof |
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| CN104693004A (en) * | 2013-12-05 | 2015-06-10 | 中国科学院上海高等研究院 | Method for effectively adjusting carbon chain length of mixed alcohol products prepared by synthetic gas |
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