CN105903472A - Equally distributed CoCu catalyst for preparing ethyl alcohol and higher alcohol through synthesis gas - Google Patents

Equally distributed CoCu catalyst for preparing ethyl alcohol and higher alcohol through synthesis gas Download PDF

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CN105903472A
CN105903472A CN201610346469.XA CN201610346469A CN105903472A CN 105903472 A CN105903472 A CN 105903472A CN 201610346469 A CN201610346469 A CN 201610346469A CN 105903472 A CN105903472 A CN 105903472A
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cocu
catalyst
ldhs
alcohol
equally distributed
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CN105903472B (en
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何静
宁珣
安哲
刘阳
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • 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
    • C07C29/153—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 characterised by the catalyst used
    • C07C29/156—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 characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof

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  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to an equally distributed CoCu catalyst, belonging to the technical field of a catalyst. The catalyst comprises a CoCu metal center and a carrier, wherein the CoCu metal center is shown as CoCu (enriching) or CoCu (non-enriching); CoCu (enriching) indicates that the Cu center has a certain surface enriching behavior; the CoCu (non-enriching) indicates that the Cu center has no surface enriching behavior; the carrier is an ZnAl compound oxide carrier prepared according to a hydrotalcite precursor method. According to the equally distributed CoCu catalyst provided by the invention, Cu and Co interact with each other at atom level; the catalyst is used for catalyzing the conversion of the synthesis gas under a mild reaction condition; the reachable optimal catalytic property is as follows: CO conversion rate can reach 31.8%, the total alcohol selectivity can reach 48.8%, about 94.4% of alcohol product is ethyl alcohol and higher alcohol and about 30.8% of alcohol product is above C5 long-chain alcohol. The equally distributed CoCu catalyst provided by the invention can ensure that the alcohol product converted from the synthesis gas under the catalytic effect of the CuCo catalyst is not limited to low carbon alcohol any more and more above C5 long-chain alcohol can be generated.

Description

A kind of synthesis gas ethanol and the equally distributed CoCu catalyst of higher alcohol
Technical field
The invention belongs to catalyst technical field, be specifically related to uniform point of a kind of synthesis gas ethanol and higher alcohol The CoCu catalyst of cloth
Background technology
Catalyze and synthesize gas conversion and prepare ethanol and higher alcohol is paid close attention to the most widely.Owing to fossil resource is short Lacking, synthesis gas can convert via Renewable resource-biomass efficient and prepare, and ethanol and higher alcohol can conducts Clean gasoline additive, liquid fuel, chemicals and industrial chemicals have the highest Economic Application and are worth.
According to reaction mechanism, alcohol premise is prepared in synthesis gas conversion to be needed to exist CO molecular dissociation simultaneously and non-dissociates Secondly center, the speeds match of carbochain propagation process and CO insertion process is more to obtain ethanol and higher alcohol Key factor.This just requires in catalyst difunctional active center to reach to be uniformly distributed thus promotes concerted catalysis Effect.Co and Cu/ZnO (catalyst for methanol) was combined first by IFP (IFP) in 1975, First invented CoCu catalyst, 220～350 DEG C and 50～150atm reaction condition under, in product C2+The selectivity of oxide reaches 80%.Due to CoCu catalyst table in alcohol reaction is prepared in synthesis gas conversion Having revealed the biggest potentiality, therefore in follow-up research, researchers are devoted in CoCu bimetallic system This two classes active component is optimized combination to realize C2+The high selectivity of alcohol.
But, tradition infusion process (> 10% relatively big for preparation load capacity) bimetallic catalyst be difficult to accomplish all Even dispersion, the CoCu/Al obtained2O3Catalyze and synthesize methanol in gas product the most.Wei Feng is prepared for many The CoCu/SiO that wall carbon nano tube MWNTs promotes2Catalyst, research shows that the addition of MWNTs makes catalysis Agent precursor generates more CoxCu3-xO4Composite oxides, illustrate the dispersion of Co and Cu evenly, Interact higher.Being applied in CO hydrogenation reaction, CO conversion ratio has 31.6% to rise to 37.1%, C2+ Alcohol selectivity is risen to 61.7% by 57%.On the other hand use there is the catalyst precarsor of unique texture also can one Determine in degree, to promote that Co's and Cu is dispersed.N.Tien-Thao et al. utilizes perovskite structure compound Construction features, with LaCo1-xCuxO3-δBe prepared for the CoCu catalyst of support type for precursor, research finds altogether With Cu and the Co ion being present in perovskite crystalline lattice at H2Under atmosphere, reduction is easier to obtain the double gold of CoCu Genus center, is more likely to generate product alcohol, and the selectivity of alcohol product is 40-45wt%.But owing to Cu has more High surface energy, easy surface aggregation, L.H.Zhang et al. thinks perovskite structure compound LaFe0.7Cu0.3O3 For carrier impregnation Co salt, obtain catalyst Cu-Co/LaFeO through roasting reduction3, analyze in reduction process profit Preferentially reduce at the adnexa of Cu with the hydrogen overflow Co on Cu surface, thus define the double gold of more CoCu Genus center, makes the selectivity of the alcohol in product be up to 69.6%, and catalyst shows good stability, But the selectivity of its Higher Alcohols is not the highest, nearly 50wt%.As can be seen here, the major part that presently, there are CoCu base catalyst synthesis gas converts, and the alcohol product mainly generated is the mixing low-carbon alcohols of C1-C5, and And the selectivity of alcohol product is the highest.
Therefore this just requires that we are by designing equally distributed CoCu catalyst so that it is can be more selective Catalyze and synthesize gas conversion and prepare ethanol and higher alcohol, and more generate the long-chain alcohol of more than C5.
Summary of the invention
It is an object of the invention to provide a kind of equally distributed CoCu catalyst, described catalyst can high select Property the gas that catalyzes and synthesizes be converted into ethanol and higher alcohol (the more long-chain alcohol generating more than C5).
To achieve these goals, the present invention is by the following technical solutions:
A kind of equally distributed CoCu catalyst, described catalyst includes CoCu metal center and carrier；Institute Stating CoCu metal center and be expressed as CoCu (enrichment) or CoCu (not being enriched with), wherein CoCu (enrichment) represents Cu Center has the behavior of certain surface enrichment, CoCu (not being enriched with) Cu center to there is not the behavior of surface enrichment； Described carrier is the ZnAl composite oxide carrier that hydrotalcite precursor method prepares.CoCu (enrichment) or CoCu is (no Enrichment) correspond to CoCu (layered) or CoCu (intercalated) the most respectively.
First optimal technical scheme of described CoCu catalyst, the Co of the described catalyst of described catalyst Load capacity is 10%～22%, and Cu load capacity is 5%～22%.
Second optimal technical scheme of described CoCu catalyst, the Co load capacity of described catalyst is 10%～15%, Cu load capacity is 10%～15%.
3rd optimal technical scheme of described CoCu catalyst, described metal center Co and Cu is uniform It is distributed on described composite oxide carrier.
4th optimal technical scheme of described CoCu catalyst, the particle diameter of described metal center is 4～10nm.
5th optimal technical scheme of described CoCu catalyst, the amount of Zn material is the 1-4 of the amount of Co material Times, further preferred 2-3 times.
The preparation method of a kind of described CoCu catalyst, said method comprising the steps of:
1) CoCu based hydrotalcite precursor is prepared:
Method one: constant pH coprecipitation method prepares CoCuZnAl-CO3-LDHs；
Method two: prepare CoZnAl-NO initially with nucleation crystallization isolation method3-LDHs, then use ion to hand over The method of changing prepares CoZnAl-Cu (C2O4)2-LDHs。
2) catalyst is prepared: by step 1) gained hydrotalcite precursor is at H2In atmosphere, at 500 DEG C～700 DEG C Reductase 12 h～4h, i.e. obtains CoCu (enrichment)-ZnAl2O4With CoCu (not being enriched with)-ZnAl2O4Catalyst.
Method one: constant pH coprecipitation method prepares CoCuZnAl-CO3-LDHs is preferred: will Cu(NO3)2·3H2O、Co(NO3)2·6H2O、Zn(NO3)2·6H2O and Al (NO3)3·9H2O is dissolved in deionization In water, it is made into mixed nitrate solution stirring and is completely dissolved purple clear solution；Weigh the Na of certain mass2CO3 It is dissolved in deionized water with NaOH, is made into concentration [NaOH]=1.8 ([M2+]+[M3+]), [Na2CO3]=2 [M3+] mixed ammonium/alkali solutions, be added dropwise in mixed nitrate solution, pH controls as between 9-10. After titration, crystallization temperature controls at 65-80 DEG C, crystallization time 18-24h；Crystallization terminate after reduce pressure sucking filtration, Deionized water wash, is dried, grinds to obtain Co2Cu1Zn4Al3-CO3-LDHs brucite powder.
Method two: prepare CoZnAl-NO initially with nucleation crystallization isolation method3-LDHs, then use ion to hand over The method of changing prepares CoZnAl-Cu (C2O4)2-LDHs, preferably:
Weigh certain mass Co (NO3)2·6H2O、Zn(NO3)2·6H2O and Al (NO3)3·9H2O be dissolved in from Sub-water, is made into mixed nitrate solution, separately weighs certain NaOH and is dissolved in deionized water, makes concentration [NaOH]=2 ([M2+]+[M3+]) aqueous slkali；Two kinds of solution are poured in churned mechanically reactor simultaneously, complete Continuing stirring a period of time after Biing, 100 DEG C of crystallization overnight, keep in building-up process being passed through N2；Crystallization terminates Rear deionized water filtering and washing, by sample drying, grinds to obtain CoZnAl-NO3-LDHs powder, synthesizes and washes CO it is used in the process of washing2Deionized water；Weigh and a certain amount of above-mentioned prepare gained CoZnAl-NO3-LDHs, weighs the Na of respective amount according to certain Co/Cu ratio2Cu(C2O4)2·2H2O It is made into aqueous solution, adds the CoZnAl-NO weighed up3-LDHs, stirs 6-10h, after filtering and washing under room temperature Vacuum drying, grinds to obtain CoZnAl-Cu (C2O4)2-LDHs；It is CO used by synthesis and washing process2 Deionized water.
Described CoCu catalyst is applied to synthesis gas conversion and prepares ethanol and the application of more than C5 higher alcohol. Reaction condition is as follows: weigh the catalyst of certain mass, in place of loading thermocouple reaction tube in one's power, and remainder Fill with quartz sand.First by online for catalyst prereduction, it is passed through reducing gases H2, volume space velocity is set to 2000-4000h-1, heating rate is preferably 5 DEG C/min and rises to 400 DEG C of holdings 1 hour.After by H2Switching For N2, question response device temperature is down to 50 DEG C, by N2Changing reaction gas into, volume space velocity is 2000h-1, to rise Temperature speed is that after 2 DEG C/min rises to reaction temperature, pressure rises to 3MPa, carries out catalytic reaction evaluation.Catalysis Range of reaction temperature is 240 DEG C-300 DEG C, reacts 24h.
With immediate prior art ratio, there is advantages that
1) the equally distributed CoCu catalyst of the present invention is present in the Co base neatly of brucite laminate with Cu Stone is precursor, utilize brucite laminate metal with atomic level high degree of dispersion, in the transition process of roasting topology in situ Controlling being uniformly distributed of CoCu, brucite laminate metal ratio has adjustability simultaneously, makes activity in catalyst The content of center Co and Cu is the most adjustable.CoCu of the present invention (layered) catalyst is applied to synthesis gas and converts Preparing ethanol and higher alcohol, can obtain the alcohol product of nearly 60% under the CO conversion ratio of 21.5%, wherein alcohol produces Thing be mainly C1-C10 mixed alcohol (the alcohol scope that the catalyst of COCu (enrichment) obtains is C1-C6, The alcohol scope that the catalyst of COCu (not being enriched with) obtains is C1-C10, and conventional method one correspondence is COCu The catalyst of (enrichment), what method two correspondence obtained is the catalyst of COCu (not being enriched with)), ethanol and The selectivity of higher alcohol, up to 80%, generates；
2) the equally distributed CoCu catalyst of the present invention is present in the Co base neatly of hydrotalcite layers with Cu Stone is precursor, utilizes brucite layer interlayer anion certain way ordered arrangement, and roasting topology in position changed Journey inhibits the Hydrogen spillover phenomenon on Cu surface, makes Cu be not easy to be enriched in the surface of metallic particles, control CoCu is uniformly distributed, and hydrotalcite layers anion has adjustability simultaneously, makes active center Co in catalyst The most adjustable with the content of Cu.CoCu (intercalated) catalyst prepared by the present invention can be at the CO of 31.8% Obtaining the alcohol product of nearly 50% under conversion ratio, wherein alcohol product is mainly the mixed alcohol of C1-C10, ethanol and height The selectivity of level alcohol is up to 95%, and C5 and above alcohol product account for 30%.
3) catalyst of the present invention can realize the Efficient Conversion of synthesis gas under the conditions of relatively mild, the most instead Answering temperature is 260 DEG C, and reaction pressure is 3MPa, and mass space velocity is 2000h-1。
Accompanying drawing explanation
Hydrotalcite precursor Co in Fig. 1: embodiment 22Cu2Zn4Al3-CO3The XRD curve of-LDHs；
Fig. 2: embodiment 2 catalyst Co1Cu1(layered)-ZnAl2O4XRD curve；
Hydrotalcite precursor CoZnAl-NO in Fig. 3: embodiment 23CoZnAl-after-LDHs and ion exchange Cu(C2O4)2-LDHs (Co/Cu=1/1) XRD curve.
Fig. 4: embodiment 2 catalyst Co1Cu1(intercalated)-ZnAl2O4XRD curve.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but the present invention is not limited to following example.
The catalytic performance test of the CoCu catalyst of load is carried out, instead on miniature tubular type catalyst test apparatus Should pipe specification d=10mm and l=600mm.Reaction unit comprises three gas circuits, each leads into as H2, reaction Gas and N2, wherein the reaction gas i.e. volume of synthesis gas consists of H2/ CO=2/1.Between reaction in High Temperature High Pressure Under carry out, and reaction gas is inflammable and explosive and poisonous, it is therefore necessary to be passed through inert N before reaction each time2 Carry out the process that builds the pressure, it is ensured that device is air tight.
Embodiment 1
Step A: weigh the Cu (NO of certain mass3)2·3H2O、Co(NO3)2·6H2O、Zn(NO3)2·6H2O With Al (NO3)3·9H2O is dissolved in 300mL deionized water, be made into concentration respectively 0.01mol/L, 0.02mol/L, The mixed nitrate solution stirring of 0.04mol/L and 0.03mol/L is completely dissolved purple clear solution；Weigh one Determine the Na of quality2CO3It is dissolved in 300mL deionized water with NaOH, is made into concentration [NaOH]=1.8 ([M2+]+[M3+]), [Na2CO3]=2 [M3+] mixed ammonium/alkali solutions.It is stirred vigorously at 25 DEG C In the lower four-hole boiling flask of instillation simultaneously, pH controls as between 9-10.After titration, crystallization temperature controls 65-80 DEG C, crystallization time 18-24h.Crystallization terminate after reduce pressure sucking filtration, deionized water wash, sample is placed in 60 DEG C of oven dried overnight, grind to obtain Co2Cu1Zn4Al3-CO3-LDHs brucite powder, kept dry.
Step B: take the catalyst precarsor Co of certain mass2Cu1Zn4Al3-CO3-LDHs is placed in type porcelain boat, Porcelain boat puts into the quartz ampoule central authorities of tube furnace, is passed through reducibility gas H with after vacuum pump evacuation2Put normal pressure, Heating schedule is set as: start to be raised to 600 DEG C with 5 DEG C/min heating rate from room temperature, the coldest after keeping 3h But it is down to room temperature, obtains sample Co2Cu1(layered)-ZnAl2O4, ICP records the negative of catalyst Co and Cu Carrying capacity is 11% and 6%.
Step C: by fine catalyst Co2Cu1(layered)-ZnAl2O4Granulating and forming is 20-40 mesh, catalysis Performance evaluation is carried out on miniature tubular type catalyst test apparatus.Weigh the catalyst of certain mass Co2Cu1(layered)-ZnAl2O4, in place of loading thermocouple reaction tube in one's power, remainder quartz sand is filled. First by online for catalyst prereduction, it is passed through reducing gases H2, volume space velocity is set to 2000h-1, heating rate It is that 5 DEG C/min rises to 350 DEG C of holdings 1 hour.After by H2Switch to N2, question response device temperature is down to room Temperature, by N2Changing reaction gas into, volume space velocity is 2000h-1, it is that 5 DEG C/min rises to reaction with heating rate After temperature, pressure rises to 3Mpa, carries out the catalytic reaction of 24h.Catalysate use gas chromatogram online and Off-line analysis, recording conversion ratio under stable reaction state is 13.3%, and alcohol products distribution is C1-C6, and total alcohol selects Selecting property is 36.7%, and the selectivity of ethanol and higher alcohol is 87.5%, and C5 and above alcohol are 2.8%.
Embodiment 2
Step A: weigh the Cu (NO of certain mass3)2·3H2O、Co(NO3)2·6H2O、Zn(NO3)2·6H2O With Al (NO3)3·9H2O is dissolved in 300mL deionized water, be made into concentration respectively 0.02mol/L, 0.02mol/L, The mixed nitrate solution stirring of 0.04mol/L and 0.03mol/L is completely dissolved purple clear solution；Weigh one Determine the Na of quality2CO3It is dissolved in 300mL deionized water with NaOH, is made into concentration [NaOH]=1.8 ([M2+]+[M3+]), [Na2CO3]=2 [M3+] mixed ammonium/alkali solutions.It is stirred vigorously at 25 DEG C In the lower four-hole boiling flask of instillation simultaneously, pH controls as between 9-10.After titration, crystallization temperature controls 65-80 DEG C, crystallization time 18-24h.Crystallization terminate after reduce pressure sucking filtration, deionized water wash, sample is placed in 60 DEG C of oven dried overnight, grind to obtain Co2Cu2Zn4Al3-CO3-LDHs brucite powder, kept dry.
Step B: take the catalyst precarsor Co of certain mass2Cu2Zn4Al3-CO3-LDHs is placed in type porcelain boat, Porcelain boat puts into the quartz ampoule central authorities of tube furnace, is passed through reducibility gas H with after vacuum pump evacuation2Put normal pressure, Heating schedule is set as: start to be raised to 600 DEG C with 5 DEG C/min heating rate from room temperature, the coldest after keeping 3h But it is down to room temperature, obtains sample Co1Cu1(layered)-ZnAl2O4, ICP records the negative of catalyst Co and Cu Carrying capacity is 11% and 12%.
Step C: by fine catalyst Co1Cu1(layered)-ZnAl2O4Granulating and forming is 20-40 mesh, catalysis Performance evaluation is carried out on miniature tubular type catalyst test apparatus.Weigh the catalyst of certain mass Co1Cu1(layered)-ZnAl2O4, in place of loading thermocouple reaction tube in one's power, remainder quartz sand is filled. First by online for catalyst prereduction, it is passed through reducing gases H2, volume space velocity is set to 2000h-1, heating rate It is that 5 DEG C/min rises to 350 DEG C of holdings 1 hour.After by H2Switch to N2, question response device temperature is down to room Temperature, by N2Changing reaction gas into, volume space velocity is 2000h-1, it is that 5 DEG C/min rises to reaction with heating rate After temperature, pressure rises to 3Mpa, carries out the catalytic reaction of 24h.Catalysate use gas chromatogram online and Off-line analysis, recording conversion ratio under stable reaction state is 21.4%, and alcohol products distribution is C1-C6, and total alcohol selects Selecting property is 56.6%, and the selectivity of ethanol and higher alcohol is 79.5%, and C5 and above alcohol are 3.6%.
Embodiment 3
Step A: weigh the Cu (NO of certain mass3)2·3H2O、Co(NO3)2·6H2O、Zn(NO3)2·6H2O With Al (NO3)3·9H2O is dissolved in 300mL deionized water, be made into concentration respectively 0.04mol/L, 0.02mol/L, The mixed nitrate solution stirring of 0.04mol/L and 0.03mol/L is completely dissolved purple clear solution；Weigh one Determine the Na of quality2CO3It is dissolved in 300mL deionized water with NaOH, is made into concentration [NaOH]=1.8 ([M2+]+[M3+]), [Na2CO3]=2 [M3+] mixed ammonium/alkali solutions.It is stirred vigorously at 25 DEG C In the lower four-hole boiling flask of instillation simultaneously, pH controls as between 9-10.After titration, crystallization temperature controls 65-80 DEG C, crystallization time 18-24h.Crystallization terminate after reduce pressure sucking filtration, deionized water wash, sample is placed in 60 DEG C of oven dried overnight, grind to obtain Co2Cu4Zn4Al3-CO3-LDHs brucite powder, kept dry.
Step B: take the catalyst precarsor Co of certain mass2Cu4Zn4Al3-CO3-LDHs is placed in type porcelain boat, Porcelain boat puts into the quartz ampoule central authorities of tube furnace, is passed through reducibility gas H with after vacuum pump evacuation2Put normal pressure, Heating schedule is set as: start to be raised to 600 DEG C with 5 DEG C/min heating rate from room temperature, the coldest after keeping 3h But it is down to room temperature, obtains sample Co1Cu2(layered)-ZnAl2O4, ICP records the negative of catalyst Co and Cu Carrying capacity is 11% and 23%.
Step C: by fine catalyst Co1Cu2(layered)-ZnAl2O4Granulating and forming is 20-40 mesh, catalysis Performance evaluation is carried out on miniature tubular type catalyst test apparatus.Weigh the catalyst of certain mass Co1Cu2(layered)-ZnAl2O4, in place of loading thermocouple reaction tube in one's power, remainder quartz sand is filled. First by online for catalyst prereduction, it is passed through reducing gases H2, volume space velocity is set to 2000h-1, heating rate It is that 5 DEG C/min rises to 350 DEG C of holdings 1 hour.After by H2Switch to N2, question response device temperature is down to room Temperature, by N2Changing reaction gas into, volume space velocity is 2000h-1, it is that 5 DEG C/min rises to reaction with heating rate After temperature, pressure rises to 3Mpa, carries out the catalytic reaction of 24h.Catalysate use gas chromatogram online and Off-line analysis, recording conversion ratio under stable reaction state is 8.0%, and alcohol products distribution is C1-C6, and total alcohol selects Selecting property is 48.7%, and the selectivity of ethanol and higher alcohol is 73.2%, and C5 and above alcohol are 2.2%.
Embodiment 4
Step A: weigh certain mass Co (NO3)2·6H2O、Zn(NO3)2·6H2O and Al (NO3)3·9H2O It is dissolved in 200ml deionized water, is made into concentration and is respectively the mixed of 0.02mol/L, 0.04mol/L and 0.03mol/L Close nitrate solution, separately weigh certain NaOH and be dissolved in 200ml deionized water, make concentration [NaOH]=2 ([M2+]+[M3+]) aqueous slkali.Two kinds of solution are poured slowly into simultaneously that mechanical agitation is violent three mouthfuls In Ping, after continue to be stirred vigorously 5min, 100 DEG C of crystallization overnight, in building-up process keep be passed through N2。 Crystallization terminates rear deionized water filtering and washing, sample is placed in 60 DEG C of vacuum drying ovens and is dried overnight, grind CoZnAl-NO3-LDHs powder, is CO used by synthesis and washing process2Deionized water.
Step B: weigh and a certain amount of above-mentioned prepare gained CoZnAl-NO3-LDHs, according to certain Co/Cu ratio Example is 2/1 Na weighing respective amount2Cu(C2O4)2·2H2O (M=322) is made into aqueous solution, adds the water weighed up Talcum powder, stirs 6-10h under room temperature, the rearmounted 60 DEG C of vacuum drying 12h of filtering and washing, grinds to obtain CoZnAl- Cu(C2O4)2-LDHs (Co/Cu=2/1).It is CO used by synthesis and washing process2Deionized water.
Step C: take the catalyst precarsor CoZnAl-Cu (C of certain mass2O4)2-LDHs (Co/Cu=2/1) puts In type porcelain boat, porcelain boat puts into the quartz ampoule central authorities of tube furnace, is passed through reducibility gas after vacuum pump evacuation H2Putting normal pressure, heating schedule is set as: start to be raised to 600 DEG C with 5 DEG C/min heating rate from room temperature, keeps After 3h, natural cooling is down to room temperature, obtains sample Co2Cu1(intercalated)-ZnAl2O4, ICP records catalysis The load capacity of agent Co and Cu is 10.5% and 5.8%.
Step D: by fine catalyst Co2Cu1(intercalated)-ZnAl2O4Granulating and forming is 20-40 mesh, Catalytic performance test is carried out on miniature tubular type catalyst test apparatus.Weigh the catalyst of certain mass Co2Cu1(intercalated)-ZnAl2O4, in place of loading thermocouple reaction tube in one's power, remainder quartz sand Fill.First by online for catalyst prereduction, it is passed through reducing gases H2, volume space velocity is set to 2000h-1, rise Temperature speed is that 5 DEG C/min rises to 350 DEG C of holdings 1 hour.After by H2Switch to N2, question response device temperature It is down to room temperature, by N2Changing reaction gas into, volume space velocity is 2000h-1, it is 5 DEG C/min liter with heating rate To reaction temperature, pressure rises to 3Mpa, carries out the catalytic reaction of 24h.Catalysate uses gas chromatogram Online and off-line analysis, recording conversion ratio under stable reaction state is 29.1%, and alcohol products distribution is C1-C10, Total alcohol selectivity is 37.7%, and the selectivity of ethanol and higher alcohol is 89.8%, and the alcohol product of more than C5 accounts for 16.8%.
Embodiment 5
Step A: weigh certain mass Co (NO3)2·6H2O、Zn(NO3)2·6H2O and Al (NO3)3·9H2O It is dissolved in 200ml deionized water, is made into concentration and is respectively the mixed of 0.02mol/L, 0.04mol/L and 0.03mol/L Close nitrate solution, separately weigh certain NaOH and be dissolved in 200ml deionized water, make concentration [NaOH]=2 ([M2+]+[M3+]) aqueous slkali.Two kinds of solution are poured slowly into simultaneously that mechanical agitation is violent three mouthfuls In Ping, after continue to be stirred vigorously 5min, 100 DEG C of crystallization overnight, in building-up process keep be passed through N2。 Crystallization terminates rear deionized water filtering and washing, sample is placed in 60 DEG C of vacuum drying ovens and is dried overnight, grind CoZnAl-NO3-LDHs powder, is CO used by synthesis and washing process2Deionized water.
Step B: weigh and a certain amount of above-mentioned prepare gained CoZnAl-NO3-LDHs, according to certain Co/Cu ratio Example is 1/1 Na weighing respective amount2Cu(C2O4)2·2H2O (M=322) is made into aqueous solution, adds the water weighed up Talcum powder, stirs 6-10h under room temperature, the rearmounted 60 DEG C of vacuum drying 12h of filtering and washing, grinds to obtain CoZnAl- Cu(C2O4)2-LDHs (Co/Cu=1/1).It is CO used by synthesis and washing process2Deionized water.
Step C: take the catalyst precarsor CoZnAl-Cu (C of certain mass2O4)2-LDHs (Co/Cu=1/1) puts In type porcelain boat, porcelain boat puts into the quartz ampoule central authorities of tube furnace, is passed through reducibility gas after vacuum pump evacuation H2Putting normal pressure, heating schedule is set as: start to be raised to 600 DEG C with 5 DEG C/min heating rate from room temperature, protects After holding 3h, natural cooling is down to room temperature, obtains sample Co1Cu1(intercalated)-ZnAl2O4, ICP records and urges The load capacity of agent Co and Cu is 10.6% and 11.4%.
Step D: by fine catalyst Co1Cu1(intercalated)-ZnAl2O4Granulating and forming is 20-40 mesh, Catalytic performance test is carried out on miniature tubular type catalyst test apparatus.Weigh the catalyst of certain mass Co1Cu1(intercalated)-ZnAl2O4, in place of loading thermocouple reaction tube in one's power, remainder quartz sand Fill.First by online for catalyst prereduction, it is passed through reducing gases H2, volume space velocity is set to 2000h-1, rise Temperature speed is that 5 DEG C/min rises to 350 DEG C of holdings 1 hour.After by H2Switch to N2, question response device temperature It is down to room temperature, by N2Changing reaction gas into, volume space velocity is 2000h-1, it is 5 DEG C/min liter with heating rate To reaction temperature, pressure rises to 3Mpa, carries out the catalytic reaction of 24h.Catalysate uses gas chromatogram Online and off-line analysis, recording conversion ratio under stable reaction state is 31.8%, and alcohol products distribution is C1-C10, Total alcohol selectivity is 48.8%, and the selectivity of ethanol and higher alcohol is 94.4%, and the alcohol product of more than C5 accounts for 30.8%.
Embodiment 6
Step A: weigh certain mass Co (NO3)2·6H2O、Zn(NO3)2·6H2O and Al (NO3)3·9H2O It is dissolved in 200ml deionized water, is made into concentration and is respectively the mixed of 0.02mol/L, 0.04mol/L and 0.03mol/L Close nitrate solution, separately weigh certain NaOH and be dissolved in 200ml deionized water, make concentration [NaOH]=2 ([M2+]+[M3+]) aqueous slkali.Two kinds of solution are poured slowly into simultaneously that mechanical agitation is violent three mouthfuls In Ping, after continue to be stirred vigorously 5min, 100 DEG C of crystallization overnight, in building-up process keep be passed through N2。 Crystallization terminates rear deionized water filtering and washing, sample is placed in 60 DEG C of vacuum drying ovens and is dried overnight, grind CoZnAl-NO3-LDHs powder, is CO used by synthesis and washing process2Deionized water.
Step B: weigh and a certain amount of above-mentioned prepare gained CoZnAl-NO3-LDHs, according to certain Co/Cu ratio Example is 1/2 Na weighing respective amount2Cu(C2O4)2·2H2O (M=322) is made into aqueous solution, adds the water weighed up Talcum powder, stirs 6-10h under room temperature, the rearmounted 60 DEG C of vacuum drying 12h of filtering and washing, grinds to obtain CoZnAl- Cu(C2O4)2-LDHs (Co/Cu=1/2).It is CO used by synthesis and washing process2Deionized water.
Step C: take the catalyst precarsor CoZnAl-Cu (C of certain mass2O4)2-LDHs (Co/Cu=1/2) puts In type porcelain boat, porcelain boat puts into the quartz ampoule central authorities of tube furnace, is passed through reducibility gas after vacuum pump evacuation H2Putting normal pressure, heating schedule is set as: start to be raised to 600 DEG C with 5 DEG C/min heating rate from room temperature, protects After holding 3h, natural cooling is down to room temperature, obtains sample Co1Cu2(intercalated)-ZnAl2O4, ICP records and urges The load capacity of agent Co and Cu is 10.5% and 21.9%.
Step D: by fine catalyst Co1Cu2(intercalated)-ZnAl2O4Granulating and forming is 20-40 mesh, Catalytic performance test is carried out on miniature tubular type catalyst test apparatus.Weigh the catalyst of certain mass Co1Cu2(intercalated)-ZnAl2O4, in place of loading thermocouple reaction tube in one's power, remainder quartz sand Fill.First by online for catalyst prereduction, it is passed through reducing gases H2, volume space velocity is set to 2000h-1, rise Temperature speed is that 5 DEG C/min rises to 350 DEG C of holdings 1 hour.After by H2Switch to N2, question response device temperature It is down to room temperature, by N2Changing reaction gas into, volume space velocity is 2000h-1, it is 5 DEG C/min liter with heating rate To reaction temperature, pressure rises to 3Mpa, carries out the catalytic reaction of 24h.Catalysate uses gas chromatogram Online and off-line analysis, recording conversion ratio under stable reaction state is 28.6%, and alcohol products distribution is C1-C10, Total alcohol selectivity is 38.8%, and the selectivity of ethanol and higher alcohol is 70.8%, and the alcohol product of more than C5 accounts for 15.0%.
Above example only in order to illustrate that technical scheme is not intended to limit, the common skill of art Art personnel should be appreciated that the detailed description of the invention of the present invention can be modified with reference to above-described embodiment or etc. With replacing, these all await the reply in application without departing from any amendment of spirit and scope of the invention or equivalent Within claims.

Claims (10)

1. an equally distributed CoCu catalyst, it is characterised in that described catalyst includes CoCu metal center and carrier；Described carrier is the ZnAl composite oxide carrier that hydrotalcite precursor method prepares.
2. according to the equally distributed CoCu catalyst of the one described in claim 1, it is characterized in that, CoCu metal center is expressed as CoCu (enrichment) or CoCu (not being enriched with), wherein CoCu (enrichment) represents that there is the behavior of certain surface enrichment at Cu center, and CoCu (not being enriched with) represents that Cu center does not exist the behavior of surface enrichment.
3., according to the equally distributed CoCu catalyst of the one described in claim 1, it is characterised in that Co load capacity is 10wt%～22wt%, Cu load capacity is 5wt%～22wt%.
4., according to the equally distributed CoCu catalyst of the one described in claim 1, it is characterised in that Co load capacity is 10wt%～15wt%, Cu load capacity is 10wt%～15%.
5. according to the equally distributed CoCu catalyst of the one described in claim 1, it is characterised in that metal center Co and Cu is distributed on ZnAl composite oxide carrier uniformly.
6. according to the equally distributed CoCu catalyst of the one described in claim 1, it is characterised in that the particle diameter of metal center is 4～10nm.
7. according to the equally distributed CoCu catalyst of the one described in claim 1, it is characterised in that the amount of Zn material is 1-4 times of the amount of Co material, preferably 2-3 times.
8. the method for the equally distributed CoCu catalyst prepared described in claim 1, it is characterised in that comprise the following steps:
1) CoCu based hydrotalcite precursor is prepared:
Method one: constant pH coprecipitation method prepares CoCuZnAl-CO3-LDHs；
Method two: prepare CoZnAl-NO initially with nucleation crystallization isolation method3-LDHs, then use ion exchange to prepare CoZnAl-Cu (C2O4)2-LDHs。
2) catalyst is prepared: by step 1) gained hydrotalcite precursor is at H2Reductase 12 h～4h in atmosphere, at 500 DEG C～700 DEG C, i.e. obtains CoCu (layered)-ZnAl2O4Or CoCu (intercalated)-ZnAl2O4Catalyst.
9. according to the method for claim 8, it is characterised in that
Method one: constant pH coprecipitation method prepares CoCuZnAl-CO3-LDHs: by Cu (NO3)2·3H2O、Co(NO3)2·6H2O、Zn(NO3)2·6H2O and Al (NO3)3·9H2O is dissolved in deionized water, is made into mixed nitrate solution stirring and is completely dissolved purple clear solution；Weigh the Na of certain mass2CO3It is dissolved in deionized water with NaOH, is made into concentration [NaOH]=1.8 ([M2+]+[M3+]), [Na2CO3]=2 [M3+] mixed ammonium/alkali solutions, be added dropwise in mixed nitrate solution, pH controls as between 9-10.After titration, crystallization temperature controls at 65-80 DEG C, crystallization time 18-24h；Crystallization terminate after reduce pressure sucking filtration, deionized water wash, be dried, grind to obtain Co2Cu1Zn4Al3-CO3-LDHs brucite powder；
Method two: prepare CoZnAl-NO initially with nucleation crystallization isolation method3-LDHs, then use ion exchange to prepare CoZnAl-Cu (C2O4)2-LDHs:
Weigh certain mass Co (NO3)2·6H2O、Zn(NO3)2·6H2O and Al (NO3)3·9H2O is dissolved in deionized water, is made into mixed nitrate solution, separately weighs certain NaOH and is dissolved in deionized water, makes concentration [NaOH]=2 ([M2+]+[M3+]) aqueous slkali；Two kinds of solution are poured in churned mechanically reactor simultaneously, after continue stirring a period of time, 100 DEG C of crystallization overnight, in building-up process keep be passed through N2；Crystallization terminates rear deionized water filtering and washing, by sample drying, grinds to obtain CoZnAl-NO3-LDHs powder, is CO used by synthesis and washing process2Deionized water；Weigh and a certain amount of above-mentioned prepare gained CoZnAl-NO3-LDHs, weighs the Na of respective amount according to certain Co/Cu ratio2Cu(C2O4)2·2H2O is made into aqueous solution, adds the CoZnAl-NO weighed up3-LDHs, stirs 6-10h under room temperature, filtering and washing final vacuum is dried, and grinds to obtain CoZnAl-Cu (C2O4)2-LDHs；It is CO used by synthesis and washing process2Deionized water.
10. the equally distributed CoCu catalyst described in any one of claim 1-7 is for catalyzing and synthesizing the application of ethanol and higher alcohol.
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CN108568313A (en) * 2017-03-07 2018-09-25 中国科学院大连化学物理研究所 A kind of method that catalyst and co hydrogenation directly convert producing light olefins
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CN112495385A (en) * 2020-11-26 2021-03-16 中国科学院山西煤炭化学研究所 CuCo-based composite catalyst for preparing higher alcohol from synthesis gas and preparation method and application thereof
CN112495385B (en) * 2020-11-26 2022-02-11 中国科学院山西煤炭化学研究所 CuCo-based composite catalyst for preparing higher alcohol from synthesis gas and preparation method and application thereof
CN116474803A (en) * 2023-04-19 2023-07-25 北京化工大学 CoMo composite material and preparation method and application thereof
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CN116474781A (en) * 2023-04-24 2023-07-25 北京化工大学 CuCo catalyst for preparing low-carbon alcohol from synthesis gas, preparation method and application

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