CN103084181A - Copper-based composite oxide catalyst as well as preparation method and application thereof - Google Patents
Copper-based composite oxide catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a copper-based composite oxide catalyst as well as a preparation method and application thereof. The catalyst is mainly formed by adding a precipitator into a reverse phase microemulsion system consisting of an oil phase, an aqueous phase, a surfactant and a cosurfactant, and performing ageing and roasting, wherein the metal components in the catalyst comprise components with CuM; M is selected from at least one of M1 and M2; M1 comprises one or more of Fe, Co, Ni and Ru; and M2 comprises one or more of Mn, Zn, Mg, Al, Si, Ti, Zr and Pd. The catalyst is small in particle size, large in specific surface area and uniform in component distribution and can be used for the mixed alcohol reaction for producing synthesis gas; and moreover, the composition of the microemulsion system and the catalyst components and contents are adjusted, and high mixed alcohol selectivity can be obtained.
Description
Technical field
The present invention relates to a kind of catalyst and method for making thereof and application, particularly relate to a kind of copper-base composite oxidate catalyst and method for making thereof and the application in synthesis gas mixed alcohol processed.
Background technology
The energy is the essential condition that guarantees a national economy sustainable development and safety and stability, and day by day exhausted along with petroleum resources will occupy an important position in future take coal and natural gas as main energy resource structure.Coal is also the main energy sources resource of China, mainly take burning as main, along with the deterioration increasingly of environment, realizes that the clean utilization of coal is extremely urgent.Effectively utilize angle to consider from rationally reaching of resource, ICL for Indirect Coal Liquefaction is converted into the correlative study of liquid fuel and downstream chemical product, and prospect has a very wide range of applications.
Research take coal and natural gas as the primary raw material Synthesis of mixed alcohols is C
1One of important content of chemistry, its technological process and synthesizing methanol are similar.The application prospect of mixed alcohol is increasingly bright and clear, the additive that acts as a fuel, and it has good dissolubility, volatility, driver behavior and higher octane number.In addition, it can also use as raw material and the clean fuel of some chemical products.
At present, existing a large amount of report by the co hydrogenation Synthesis of mixed alcohols wherein, is applied in the catalyst of this Synthesis of mixed alcohols reaction, and is the most representative by following four kinds:
(1) modified methanol synthetic catalyst (Cu/ZnO/Al
2O
3, ZnO/Cr
2O
3):
This catalyst is added appropriate alkali metal or Modified With Alkali-earth Compounds and is got by methanol synthesis catalyst, and more typical patent has EP0034338A2 and U.S. US4513100.Although this type of catalyst activity is higher, in product, isobutanol content is higher, but shortcoming is reaction condition harsher (pressure is 14～20MPa, and temperature is 350～450 ℃), higher alcohol is lower (being generally less than 35%) selectively, water content higher (being generally 30～50%) in product.
(2) Cu-Co catalyst:
IFP (IFP) has at first developed Cu-Co co-precipitation low-carbon alcohol catalyst, has patent US4122110,4291126 and GB2118061,2158730, and 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 gentle (similar to the low pressure methanol synthetic catalyst), but less stable.
(3) anti-sulphur MoS
2Catalyst:
The molybdenum of U.S. DOW company exploitation is sulfide catalyst (patent US4882360), and this catalyst system not only has anti-sulphur, and the product water content is few, and higher alcohol content is higher, reaches 30～70%, is mainly wherein ethanol and normal propyl alcohol.This type of catalyst Main Problems is that wherein auxiliary element very easily and form carbonyls between carbon monoxide, causes the loss of auxiliary element, affects the activity of catalyst and selective, causes catalyst stability and life-span to be restricted.
(4) Rh catalyst based (as US4014913 and 4096164):
After adding one to two kind of transition metal or metal oxide auxiliary agent in support type Rh catalyst, low-carbon alcohols is synthesized higher activity and selectivity, and special city is to C
2 +Pure is selectively higher, and product is take ethanol as main.But the Rh compound is expensive, and catalyst is easily by CO
2Poison, its activity and selectivity does not generally reach industrial requirement.
The method for preparing nanocatalyst is a lot, as sol-gel process, the precipitation method, Low Temperature Solid-Phase synthetic method, micro emulsion method etc.Wherein, the micro emulsion method is simple due to its device, processing ease, the catalyst granules of preparation evenly, and can effectively control the plurality of advantages such as granular size and extremely people's concern, and shown stronger application prospect.Transparent or semitransparent, isotropic thermodynamic stable system that microemulsion normally is comprised of surfactant, cosurfactant (alcohols), oil phase (hydrocarbon) and water (electrolyte aqueous solution).The co-continuous that different according to decentralized photo and continuous phase, the structure of microemulsion are divided into positive microemulsion (O/W), reverse micro emulsion (W/O) and intermediate state is three kinds of microemulsions mutually.Wherein, reverse micro emulsion is used comparatively general in the nanocatalyst preparation, in reverse micro emulsion, water core is surrounded by the interface that surfactant and cosurfactant formed, its size can be controlled in several or tens nanometers between, yardstick is little and separated from one another, therefore can be regarded as one " microreactor ", is the reaction medium of desirable preparation nanocatalyst.
Yet, utilize the reverse micro emulsion method, prepare the patent report that yet there are no of copper-base composite oxidate nanocatalyst.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of copper-base composite oxidate catalyst and method for making and the application in synthesis gas mixed alcohol processed.By adopting the reverse micro emulsion method, the copper-base composite oxidate catalyst for preparing has the advantages such as particle diameter is little, specific area is high, each uniform component distribution, and can be applicable in synthesis gas mixed alcohol processed.
For solving the problems of the technologies described above, copper-base composite oxidate catalyst of the present invention, mainly the Reverse Microemulsion System (W/O that is formed by oil phase, water, surfactant and cosurfactant, Water-In-Oil), after adding precipitating reagent, aging, roasting gained, wherein, the metal component in this catalyst comprises the composition with following general formula (I):
CuM?（I）
Wherein, M is selected from Fischer-Tropsch component M
1, adjuvant component M
2In at least a, M
1Comprise: one or more in Fe, Co, Ni, Ru; M
2Comprise: one or more in Mn, Zn, Mg, Al, Si, Ti, Zr, Pd.
Cu/M
1, Cu/M
2The scope of mol ratio be 10:1～1:10.
Described oil phase comprises: one or more in the oil phase alkane such as pentane, n-hexane, cyclohexane, normal heptane, normal octane.
Water is the slaine mixed aqueous solution that includes CuM; Wherein, slaine is one or more in water-soluble nitrate, sulfate, hydrochloride or acylate.Wherein, acylate comprises formates, acetylacetonate, acetate, citrate.
Surfactant comprises: one or more in anionic surfactant, cationic surface active agent, zwitterionic surfactant, nonionic surface active agent;
Wherein, anionic surfactant comprises: stearic acid, oleic acid, laurate, sulfated castor oil, lauryl sodium sulfate, sldium lauryl sulfate, dioctyl sodium sulfosuccinate, neopelex, softex kw, dodecyl sodium sulfate, sodium glycocholate.
N-dodecyl-B-alanine), quaternary ammonium salt (comprising: hexamethonium chloride), imidazoline, moroxydine class (comprising: Moroxydine Hydrochloride), triazine derivative (comprising: s-triazine, triazine etc. partially) cationic surface active agent comprises: fatty amine salt (comprising:.
Zwitterionic surfactant comprises: lecithin, amino acid pattern (comprising: alpha amino acid, beta amino acids etc.), betaine type (comprising: dodecyldimethylammonium hydroxide inner salt, myristyl dimethyl betaine etc.) etc.
Glycerin monostearate), polyalcohol (comprising: smooth, the poly-sorb fat of sucrose ester, aliphatic acid sorb etc.), polyoxyethylene-type (comprising: Nonyl pheno (10) ether, cetyl polyethylene glycol oxide ether), Pluronic F68 nonionic surface active agent comprises: fatty glyceride (comprising:.
Cosurfactant comprises: a kind of in the alcohols such as ethanol, propyl alcohol, n-butanol, isobutanol, n-amyl alcohol.
Precipitating reagent comprises: Na
2CO
3, K
2CO
3, (NH
4)
2CO
3Etc. one or more in alkaline salt solution.
Copper-base composite oxidate catalyst of the present invention is nanocatalyst, and its granular size is in 2～100nm scope.The specific area of this catalyst is through adopting the nitrogen adsorption method to measure, and its specific surface scope is at 10～300m
2/ g.
In copper-base composite oxidate catalyst of the present invention, preferred CuM
1M
2The percentage by weight that accounts for the catalyst gross mass is respectively: Cu:20%～60%; M
1: 20～60%; M
2: 0～30%.
In addition, the invention also discloses the preparation method of above-mentioned copper-base composite oxidate catalyst (nanocatalyst), namely prepare this catalyst by the reverse micro emulsion method, step comprises:
(1) add successively a certain amount of oil phase as above, surfactant and cosurfactant, magnetic agitation is to Uniform Dispersion, drip the fast slaine mixed aqueous solution that drips wherein as the certain density CuM of containing as above of water with fixing under stirring, thereby form Reverse Microemulsion System;
(2) under stirring, drip certain density precipitating reagent as above in the microemulsion system, the gained mixed solution after aging certain hour, through centrifugation, washing, oven dry and roasting, obtains powder catalyst at a certain temperature.
This powder catalyst can be used for the fixed bed reactors evaluation through after compressing tablet, fragmentation and sieving.
In described step (1), the mass ratio of oil phase and surfactant is 0.5～10, preferred 1～5; The mass ratio of surfactant and cosurfactant is 0.5～10, preferred 1～5; The mass ratio of oil phase and water (the slaine mixed aqueous solution that contains CuM) is 0.5～10, preferred 1～5.
In described step (2), precipitating reagent is 0.2～5 with the mol ratio of the slaine that contains CuM (total slaine), preferred 0.8～2; Aging temperature is 30～100 ℃, preferred 50～80 ℃; Ageing time is 0.5～12h, preferred 1～5h; Bake out temperature is 50～120 ℃, preferred 100～120 ℃; Drying time is 1～24h, preferred 10～12h; Sintering temperature is 200～800 ℃, preferred 300～400 ℃; Roasting time is 0.5～12h, preferred 2～5h.
Moreover, the copper-base composite oxidate catalyst (nanocatalyst) of the present invention's preparation, can be used in synthesis gas mixed alcohol reaction processed, reaction unit is fixed bed reactors, reaction condition is: with catalyst gradient increased temperature to 200～600 ℃ in hydrogen or synthesis gas atmosphere, preferred 300～400 ℃, activation 1～24h, preferred 6～12h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 150～350 ℃, preferred 200～300 ℃; Reaction velocity is 1000～10000h
-1, preferred 4000～6000h
-1Operating pressure is 0.1～13MPa, preferred 2～6MPa, especially preferred 6MPa; H
2The mol ratio of/CO=0.1～10, preferred 1～3.
Gained catalyst particle size of the present invention is little, specific area is high, each uniform component distribution, can be used for synthesis gas mixed alcohol reaction processed, and passes through formation and catalytic component and the content thereof of modulation microemulsion system, can obtain higher mixed alcohol selective, wherein, total alcohol selectively can reach more than 30%, C
2 +The ratio of alcohol in total alcohol can reach more than 94%.
The specific embodiment
The particle diameter of the catalyst of following examples preparations is in 2～100nm scope, and the specific area of this catalyst measures through the nitrogen adsorption method, and its specific surface scope is at 10～300m
2/ g.
Embodiment 1
Cyclohexane, softex kw and n-butanol are mixed according to mass ratio 2:1:1 and stir (total oil phase), with Cu (NO
3)
23H
2O, Co (NO
3)
26H
2O, Zn (NO
3)
26H
2O and Al (NO
3)
39H
2O Cu/Co/Zn/Al=6/4/5/5 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, the mass ratio of water and oil phase is 1:1, this mixed solution is dropped to oil phase, and fully stir the formation Reverse Microemulsion System.Under stirring, utilize peristaltic pump to drip the Na that the 100ml molar concentration is 1.35mol/L in this system
2CO
3Solution, gained mixed solution is at 70 ℃ of aging 3h, centrifugal, washing with separates after gained be deposited in 120 ℃ dry 12h after, roasting 2h in 400 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 1
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, catalyst is risen to 300 ℃ in atmosphere of hydrogen, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 240 ℃; Reaction velocity is 5000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Embodiment 2
Normal octane, dodecyl sodium sulfate and n-butanol are mixed according to mass ratio 3:1:2 and stir (total oil phase), with Cu (NO
3)
23H
2O, Co (NO
3)
26H
2O, Zn (NO
3)
26H
2O and Al (NO
3)
39H
2O Cu/Co/Zn/Al=6/4/5/5 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, the mass ratio of water and oil phase is 1:1, this mixed solution is dropped to oil phase and fully stirs form microemulsion system.Under stirring, utilize peristaltic pump to drip the K that the 100ml molar concentration is 1.35mol/L in this system
2CO
3Solution, gained mixed solution is at 60 ℃ of aging 4h, centrifugal, washing with separates after gained be deposited in 120 ℃ dry 12h after, roasting 4h in 350 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 2
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, catalyst is risen to 300 ℃ in atmosphere of hydrogen, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 260 ℃; Reaction velocity is 4000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Embodiment 3
Cyclohexane, softex kw and n-butanol are mixed according to mass ratio 2:1:1 and stir (total oil phase), with Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O Cu/Fe=3/1 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, and the mass ratio of water and oil phase is 1:1, and this mixed solution is dropped to oil phase and fully stirs the formation microemulsion system.Utilize peristaltic pump to drip the Na that the 100ml molar concentration is 1.35mol/L in this system under stirring
2CO
3Solution, gained mixed solution is at 70 ℃ of aging 3h, centrifugal, washing with separates after gained be deposited in 120 ℃ and dry after 12h roasting 2h in 400 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 3
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, and catalyst is risen to 300 ℃ in the synthesis gas atmosphere, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 220 ℃; Reaction velocity is 5000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Embodiment 4
Cyclohexane, Nonyl pheno (10) ether and n-amyl alcohol are mixed according to mass ratio 3:2:1 and stir (total oil phase), with Cu (NO
3)
23H
2O, Co (NO
3)
26H
2O, Mg (NO
3)
26H
2O and Al (NO
3)
39H
2O Cu/Co/Mg/Al=1/1/1/1 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, the mass ratio of water and oil phase is 1:1, this mixed solution is dropped to oil phase and fully stirs form microemulsion system.Utilize peristaltic pump to drip the K that the 100ml molar concentration is 1.35mol/L in this system under stirring
2CO
3Solution, gained mixed solution is at 60 ℃ of aging 2h, centrifugal, washing with separates after gained be deposited in 120 ℃ and dry after 12h roasting 4h in 400 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 4
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, catalyst is risen to 300 ℃ in atmosphere of hydrogen, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 240 ℃; Reaction velocity is 5000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Embodiment 5
Cyclohexane, cetyl polyethylene glycol oxide ether and isobutanol are mixed according to mass ratio 2:1:1 and stir (total oil phase), with Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O Cu/Fe=1/1 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, and the mass ratio of water and oil phase is 1:1, and this mixed solution is dropped to oil phase and fully stirs the formation microemulsion system.Utilize peristaltic pump to drip the Na that the 100ml molar concentration is 1.5mol/L in this system under stirring
2CO
3Solution, gained mixed solution is at 70 ℃ of aging 3h, centrifugal, washing with separates after gained be deposited in 120 ℃ dry 12h after, roasting 2h in 400 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 5
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, and catalyst is risen to 300 ℃ in the synthesis gas atmosphere, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 240 ℃; Reaction velocity is 5000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Embodiment 6
Cyclohexane, softex kw and n-butanol are mixed according to mass ratio 2:1:1 and stir (total oil phase), with Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O Cu/Fe=3/1 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, and the mass ratio of water and oil phase is 1:1, and this mixed solution is dropped to oil phase and fully stirs the formation microemulsion system.Utilize peristaltic pump to drip the Na that the 100ml molar concentration is 1.35mol/L in this system under stirring
2CO
3Solution, gained mixed solution is at 70 ℃ of aging 3h, centrifugal, washing with separates after gained be deposited in 120 ℃ dry 12h after, roasting 2h in 400 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 6
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, and catalyst is risen to 300 ℃ in the synthesis gas atmosphere, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 200 ℃; Reaction velocity is 5000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Embodiment 7
Cyclohexane, cetyl polyethylene glycol oxide ether and n-butanol are mixed according to mass ratio 2:1:2 and stir (total oil phase), with Cu (NO
3)
23H
2O, Fe (NO
3)
39H
2O and Zr (NO
3)
45H
2O Cu/Fe/Zr=3/1/1 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, and the mass ratio of water and oil phase is 1:1, and this mixed solution is dropped to oil phase and fully stirs the formation microemulsion system.Utilize peristaltic pump to drip the Na that the 100ml molar concentration is 1.32mol/L in this system under stirring
2CO
3Solution, gained mixed solution is at 70 ℃ of aging 3h, centrifugal, washing with separates after gained be deposited in 120 ℃ dry 12h after, roasting 2h in 400 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 7
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, and catalyst is risen to 300 ℃ in the synthesis gas atmosphere, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 200 ℃; Reaction velocity is 5000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Embodiment 8
Cyclohexane, softex kw and n-butanol are mixed according to mass ratio 2:1:1 and stir (total oil phase), with Cu (NO
3)
23H
2O and Co (NO
3)
26H
2O Cu/Co=1/1 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, and the mass ratio of water and oil phase is 1:1, and this mixed solution is dropped to oil phase and fully stirs the formation microemulsion system.Utilize peristaltic pump to drip the Na that the 100ml molar concentration is 1.2mol/L in this system under stirring
2CO
3Solution, gained mixed solution is at 70 ℃ of aging 3h, centrifugal, washing with separates after gained be deposited in 120 ℃ dry 12h after, roasting 2h in 400 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 8
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, catalyst is risen to 300 ℃ in atmosphere of hydrogen, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 270 ℃; Reaction velocity is 5000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Embodiment 9
Cyclohexane, softex kw and n-butanol are mixed according to mass ratio 2:1:1 and stir (total oil phase), with Cu (NO
3)
23H
2O and Co (NO
3)
26H
2O Cu/Co=1/10 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, and the mass ratio of water and oil phase is 1:1, and this mixed solution is dropped to oil phase and fully stirs the formation microemulsion system.Utilize peristaltic pump to drip the Na that the 100ml molar concentration is 1.2mol/L in this system under stirring
2CO
3Solution, gained mixed solution is at 70 ℃ of aging 3h, centrifugal, washing with separates after gained be deposited in 120 ℃ dry 12h after, roasting 2h in 400 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 9
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, catalyst is risen to 300 ℃ in atmosphere of hydrogen, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 240 ℃; Reaction velocity is 6000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Embodiment 10
Cyclohexane, softex kw and n-butanol are mixed according to mass ratio 2:1:1 and stir (total oil phase), with Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O Cu/Fe=10/1 in molar ratio is dissolved in the 100mL deionized water that to form total metal concentration be the mixed solution (water) of 1mol/L, and the mass ratio of water and oil phase is 1:1, and this mixed solution is dropped to oil phase and fully stirs the formation microemulsion system.Utilize peristaltic pump to drip the Na that the 100ml molar concentration is 1.255mol/L in this system under stirring
2CO
3Solution, gained mixed solution is at 70 ℃ of aging 3h, centrifugal, washing with separates after gained be deposited in 120 ℃ dry 12h after, roasting 2h in 400 ℃ of air atmospheres, compressing tablet also is crushed to 40～60 orders, obtains catalyst 10
#
This catalyst is for the synthesis of in gas mixed alcohol reaction processed, and reaction unit is fixed bed reactors, and catalyst is risen to 300 ℃ in the synthesis gas atmosphere, activation 8h; Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 200 ℃; Reaction velocity is 5000h
-1, operating pressure is 6.0MPa, H
2The mol ratio of/CO=2.0, reaction result sees Table 1.
Table 1 embodiment catalyst reaction result
Claims (15)
1. copper-base composite oxidate catalyst, it is characterized in that: be mainly the Reverse Microemulsion System that is formed by oil phase, water, surfactant and cosurfactant, after adding precipitating reagent, aging, roasting gained, wherein, the metal component in this catalyst comprises the composition with following general formula (I):
CuM?（I）
Wherein, M is selected from M
1, M
2In at least a; M
1Comprise: one or more in Fe, Co, Ni, Ru; M
2Comprise: one or more in Mn, Zn, Mg, Al, Si, Ti, Zr, Pd;
Cu/M
1, Cu/M
2The scope of mol ratio be 10:1～1:10.
Oil phase comprises: one or more in pentane, n-hexane, cyclohexane, normal heptane, normal octane;
Water is the slaine mixed aqueous solution that includes CuM;
Cosurfactant comprises: one or more in ethanol, propyl alcohol, n-butanol, isobutanol, n-amyl alcohol;
Precipitating reagent comprises: Na
2CO
3, K
2CO
3, (NH
4)
2CO
3In one or more.
2. catalyst as claimed in claim 1, it is characterized in that: the granular size of described catalyst is at 2～100nm; The specific surface of the catalyst through adopting the measurement of nitrogen adsorption method is 10～300m
2/ g.
3. catalyst as claimed in claim 1 is characterized in that: in described catalyst, and CuM
1M
2The percentage by weight that accounts for the catalyst gross mass is respectively: Cu:20%～60%; M
1: 20～60%; M
2: 0～30%.
4. the preparation method of catalyst as claimed in claim 1, is characterized in that, comprises step:
(1) add successively oil phase, surfactant and cosurfactant, be stirred to Uniform Dispersion, to drip the slaine mixed aqueous solution of CuM as claimed in claim 1 that contains as water, form Reverse Microemulsion System under stirring;
Wherein, oil phase comprises: one or more in pentane, n-hexane, cyclohexane, normal heptane, normal octane;
Surfactant comprises: one or more in anionic surfactant, cationic surface active agent, zwitterionic surfactant, nonionic surface active agent;
Cosurfactant comprises: one or more in ethanol, propyl alcohol, n-butanol, isobutanol, n-amyl alcohol;
(2) under stirring, drip precipitating reagent in Reverse Microemulsion System, the gained mixed solution is after aging, and separation, washing, oven dry and roasting obtain catalyst.
5. method as claimed in claim 4, it is characterized in that: in described step (1), anionic surfactant comprises: stearic acid, oleic acid, laurate, sulfated castor oil, lauryl sodium sulfate, sldium lauryl sulfate, dioctyl sodium sulfosuccinate, neopelex, softex kw, dodecyl sodium sulfate, sodium glycocholate;
Cationic surface active agent comprises: fatty amine salt, quaternary ammonium salt, imidazoline, moroxydine class, triazine derivative;
Zwitterionic surfactant comprises: lecithin, amino acid pattern, betaine type;
Nonionic surface active agent comprises: fatty glyceride, polyalcohol, polyoxyethylene-type, Pluronic F68.
6. method as claimed in claim 5, it is characterized in that: in described cationic surface active agent, the cationic surface active agent fatty amine salt comprises: N-dodecyl-B-alanine; Quaternary ammonium salt comprises: hexamethonium chloride; The moroxydine class comprises: Moroxydine Hydrochloride; Triazine derivative comprises: s-triazine, inclined to one side triazine;
In zwitterionic surfactant, amino acid pattern comprises: alpha amino acid, beta amino acids; Betaine type comprises: dodecyldimethylammonium hydroxide inner salt, myristyl dimethyl betaine;
In nonionic surface active agent, fatty glyceride comprises: glycerin monostearate; Polyalcohol comprises: sucrose ester, aliphatic acid sorb are smooth, poly-sorb fat; Polyoxyethylene-type comprises: NPE, cetyl polyethylene glycol oxide ether.
7. method as claimed in claim 4, it is characterized in that: in described step (1), the mass ratio of oil phase and surfactant is 0.5～10;
The mass ratio of surfactant and cosurfactant is 0.5～10;
Oil phase and be 0.5～10 as the mass ratio of the slaine mixed aqueous solution that contains CuM of water.
8. method as claimed in claim 7, it is characterized in that: the mass ratio of described oil phase and surfactant is 1～5;
The mass ratio of surfactant and cosurfactant is 1～5;
Oil phase and be 1～5 as the mass ratio of the slaine mixed aqueous solution that contains CuM of water.
9. method as claimed in claim 4, it is characterized in that: in described step (1), the slaine that contains CuM is one or more in water-soluble nitrate, sulfate, hydrochloride or the acylate that contains CuM.
10. method as claimed in claim 9, it is characterized in that: described acylate comprises: formates, acetylacetonate, acetate, citrate.
11. method as claimed in claim 4 is characterized in that: in described step (2), precipitating reagent is 0.2～5 with the mol ratio of total slaine;
Aging temperature is 30～100 ℃, and ageing time is 0.5～12h;
Bake out temperature is 50～120 ℃, and drying time is 1～24h;
Sintering temperature is 200～800 ℃, and roasting time is 0.5～12h.
12. method as claimed in claim 11 is characterized in that: described precipitating reagent is 0.8～2 with the mol ratio of total slaine; Aging temperature is 50～80 ℃, and ageing time is 1～5h;
Bake out temperature is 100～120 ℃, and drying time is 10～12h;
Sintering temperature is 300～400 ℃, and roasting time is 2～5h.
13. the application of catalyst as claimed in claim 1 is characterized in that: in gas mixed alcohol reaction processed, reaction unit is fixed bed reactors, and reaction condition is:
With catalyst gradient increased temperature to 200～600 ℃ in hydrogen or synthesis gas atmosphere, activation 1～24h;
Then, pass into synthesis gas after being cooled to room temperature, reaction temperature is 150～350 ℃;
Reaction velocity is 1000～10000h
-1
Operating pressure is 0.1～13MPa;
H
2The mol ratio of/CO is 0.1～10.
14. application as claimed in claim 13 is characterized in that: described reaction condition is:
With catalyst gradient increased temperature to 300～400 ℃ in hydrogen or synthesis gas atmosphere, activation 6～12h;
Then pass into synthesis gas after being cooled to room temperature, reaction temperature is 200～300 ℃;
Reaction velocity is 4000～6000h
-1
Operating pressure is 2～6MPa;
H
2The mol ratio of/CO is 1～3.
15. application as claimed in claim 14 is characterized in that: described operating pressure is 6MPa.
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