CN109499581A - A kind of preparation method preparing C3H6O3 catalyst by glycerol - Google Patents
A kind of preparation method preparing C3H6O3 catalyst by glycerol Download PDFInfo
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- 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
- B01J23/83—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 rare earths or actinides
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
Abstract
The invention discloses a kind of preparation methods that 1,3-Dihydroxyacetone catalyst is prepared by glycerol, and this method comprises the following steps: (1) preparation of ZnAl-HTLc: zinc salt, aluminium salt being dissolved in deionized water and are configured to solution A, by Na2CO3It is configured to solution B with NaOH, solution A and solution B are quickly mixed, and back flow reaction, centrifuge washing, drying, obtain ZnAl-HTLc after reaction；(2) preparation of complex carrier: the ZnAl-HTLc of preparation is added in a glucose monohydrate aqueous solution, is uniformly mixed；Then said mixture is gone in ptfe autoclave, hydro-thermal reaction, cooling later, washing and drying obtains ZnAl-HTLc/ carbon complex carrier；(3) preparation of catalyst: being configured to solution for copper nitrate, lanthanum nitrate, cobalt nitrate respectively, above-mentioned solution is added in complex carrier simultaneously, dry after dipping, roasting, Hydrogen activation obtain the catalyst.The activity of catalyst of the present invention, selectivity and stability are all preferable, have a extensive future.
Description
Technical field
The invention belongs to catalyst fields, and in particular to a kind of preparation that 1,3-Dihydroxyacetone catalyst is prepared by glycerol
Method.
Background technique
1,3-Dihydroxyacetone (dihydroxyacetone, abbreviation DHA) is simplest ketose, its soluble easily in water, second
The organic solvents such as alcohol, acetone and ether.DHA is a kind of important industrial chemicals, is widely used in fine chemistry industry, food, makeup
The industries such as product and purification of water quality；Meanwhile DHA also important organic synthesis intermediate, it can be used for aldol condensation and produce a variety of chiralitys
Compound, reduction prepares secondary alcohol with optical activation, prepare saccharide compound through Diels-Alder addition or through further anti-
Intercalation reaction occurs applied to such addition reaction, with Cabbeen, prepares lactone with the cyclopropane derivative effect of 2,2- dialkoxy
Deng.
Currently, 1,3-Dihydroxyacetone mainly passes through microbe fermentation method and the preparation of glycerol Direct Catalytic Oxidation method.Micro- life
Object fermentation method is the method that glycerol fermentation is converted into DHA using acetobacter.Since strain is severe to life condition requirement
It carves, the easy loss of activity in storage and transport process；And the high concentration accumulation of substrate and product around somatic cells can then extend hair
The ferment period (300-400 hours) simultaneously reduces yield.Therefore, the higher cost of microbe fermentation method.Glycerol Direct Catalytic Oxidation method
It is the method that dihydroxyacetone (DHA) is converted glycerol by single step reaction under the collective effect of catalyst and oxidant.
For Hiroshi Kimura etc. using Pt/C, Pt-Bi/C and Pt-Bi-Ce/C as catalyst, highest can be such that 70% glycerol occurs
Conversion, but the selectivity of DHA is too low (Appl.Catal., A, 1993,96,217-228.).102432445 A of CN is then disclosed
A method of using hydrogen peroxide selective oxidation glycerol prepare DHA, but in this method DHA selectivity it is still lower, only reach
24.2~85.7%.Hu etc., which is reported, uses fixed bed reactors to obtain under 80 DEG C and acid condition with Pt-Bi/C catalyst
48% (Ind.Eng.Chem.Res., 2010,49:10876- of glycerol conversion yield 80% and C3H6O3 selectivity
10882).Patent CN 105439831 is disclosed also has preferable secondary alcohol selectivity as carrier using ZnO in glycerol oxidation.Root
According to glycerol oxidation reaction feature, the good Au catalyst of polymolecularity, stability is the principal element for determining catalytic activity, this requirement
Au does not occur to migrate and reunite in catalyst preparation process.However, the specific surface of usually ZnO is lower, it is unfavorable for when as carrier
The dispersion of Au.Especially under high load amount, surface tension effects cause Au sintering and particle to become larger, and are easy loss and noble metal
Utilization rate is low.
However, the above-mentioned generally existing active component utilization rate of catalyst is not high, activity is insufficient, the stability of carrier components,
Dispersibility and the imperfect defect of specific surface area, cause the selectivity of 1,3-Dihydroxyacetone not good enough, it is excellent to develop a kind of activity
Different catalyst is very necessary.
Summary of the invention
It is high, selective good by glycerol system that it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of activity
The catalyst and preparation method thereof of standby C3H6O3.
To achieve the above object, the technical solution used in the present invention are as follows:
A kind of preparation method preparing 1,3-Dihydroxyacetone catalyst by glycerol, includes the following steps:
(1) preparation of ZnAl-HTLc: being dissolved in deionized water by soluble zinc salt, aluminium salt and be configured to mixed solution A,
By Na2CO3It is dissolved in deionized water with NaOH and is configured to mixed solution B, it is then under quick stirring that solution A and solution B is fast
Product centrifuge washing is obtained ZnAl- to neutral, drying after reaction by speed mixing, and the back flow reaction 8-12h at 50-70 DEG C
HTLc；
(2) 60-120mL, concentration 0.5- the preparation of complex carrier: is added in the ZnAl-HTLc of step (1) preparation
In a glucose monohydrate aqueous solution of 1mo1/L, stirred at room temperature to uniformly mixed；Then said mixture is gone to
In ptfe autoclave, 160-200 DEG C isothermal reaction 4-8 hours, be cooled to room temperature after reaction, isolate product,
Then it dries after alternately being washed with deionized water and ethyl alcohol at 80-100 DEG C to get ZnAl-HTLc/ carbon complex carrier；
(3) preparation of catalyst: respectively by Cu (NO3)2·3H2O、La(NO3)3·6H2O、 Co(NO3)2·6H2O dissolution
In deionized water, heating, stirring are made into clear solution, then configured solution is added to step (2) preparation simultaneously
In complex carrier, the drying at 80-100 DEG C after 3-5h is impregnated at 30-50 DEG C, by resulting solid product in 450-550
4-6h is roasted at DEG C, by Hydrogen activation up to the catalyst after being ground up, sieved.
Preferably, the aluminium salt in step (1) is aluminum nitrate, and zinc salt is zinc nitrate, the molar ratio of Zn/Al in mixed solution A
For 1-3, the molar ratio of sodium carbonate and aluminum nitrate is 0.2-0.5 in solution B, and cationic molar ratio is 1- in NaOH and solution A
3:1, solution A are equal with the volume of solution B.
Preferably, the additional amount of ZnAl-HTLc is 10-20g in step (2).
Preferably, Cu (NO in step (3)3)2·3H2O、La(NO3)3·6H2O、 Co(NO3)2·6H2O is dissolved in deionization
Concentration after water is 0.2-0.8mol/L, and the volume of solution is respectively 80-120ml, 50-80ml, 40-60ml.
Preferably, the additional amount of complex carrier is 8-15g in step (3).
Preferably, the process of Hydrogen activation is led in step (3) are as follows: catalyst is placed in tube furnace, by tubular type furnace temperature
Be warming up to 350 DEG C from room temperature with the speed program of 2 DEG C/min, at the same be passed through into tube furnace percent by volume 5-10% hydrogen and
Activation of catalyst 3-6h is continued same nitrogen until temperature is reduced to room temperature i.e. by the mixed gas of 90-95% nitrogen composition later
It can.
In addition, the catalyst being prepared by the method is also claimed in the present invention.
Compared with prior art, advantages of the present invention with have the beneficial effect that
Catalyst of the present invention uses a kind of homemade complex carrier, and carbon nano-particle is directly implanted to zinc by hydro-thermal method
In the layer structure of aluminum hydrotalcite, to play the structure for improving hydrotalcite, its supported active position is enriched, while increasing its surface
Then long-pending and stability, resulting complex carrier pass through infusion process and have loaded three kinds of copper, lanthanum, cobalt active metals, three kinds of active groups
Dividing very stable can be adsorbed on above-mentioned carrier, and dispersibility is very high, imitate in the reaction of synthesis 1,3-Dihydroxyacetone
Fruit is very excellent, and activity and selectivity is all preferable.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of preparation method preparing 1,3-Dihydroxyacetone catalyst, includes the following steps:
(1) preparation of ZnAl-HTLc: by soluble 0.375gAl (NO3)3·9H2O、 0.891gZn(NO3)2·6H2O
It is dissolved in the deionized water of 150ml and is configured to mixed solution A, by 0.042gNa2CO3150ml deionization is dissolved in 0.48gNaOH
It is configured to mixed solution B in water, then quickly mixes solution A and solution B under quick stirring, and flow back instead at 60 DEG C
10h is answered, product centrifuge washing is obtained into ZnAl-HTLc to neutral, drying after reaction；
(2) 80mL, concentration 0.6mo1/L the preparation of complex carrier: is added in the ZnAl-HTLc12g of step (1) preparation
A glucose monohydrate aqueous solution in, stir at room temperature to be uniformly mixed；Then said mixture is gone into polytetrafluoro
In ethylene reaction kettle, 180 DEG C isothermal reaction 6 hours, be cooled to room temperature after reaction, isolate product, then use deionization
Water and ethyl alcohol are dried after alternately washing at 90 DEG C to get ZnAl-HTLc/ carbon complex carrier；
(3) preparation of catalyst: respectively by Cu (NO3)2·3H2O、La(NO3)3·6H2O、 Co(NO3)2·6H2O dissolution
In deionized water, heating, stirring are made into concentration 0.5mol/L, and volume is respectively the clear solution of 100ml, 60ml and 50ml,
Then configured solution is added to simultaneously in the 12g complex carrier of step (2) preparation, at 90 DEG C after dipping 4h at 40 DEG C
Resulting solid product is roasted 5h at 500 DEG C, catalyst is placed in tube furnace after being ground up, sieved, by tubular type by lower drying
Furnace temperature is warming up to 350 DEG C from room temperature with the speed program of 2 DEG C/min, while 7% hydrogen of percent by volume is passed through into tube furnace
Activation of catalyst 5h is continued same nitrogen until temperature is reduced to room temperature by the mixed gas of gas and 93% nitrogen composition later.
Embodiment 2
A kind of preparation method preparing 1,3-Dihydroxyacetone catalyst, includes the following steps:
(1) preparation of ZnAl-HTLc: by soluble 0.375gAl (NO3)3·9H2O、 0.594gZn(NO3)2·6H2O
It is dissolved in the deionized water of 150ml and is configured to mixed solution A, by 0.042gNa2CO3150ml deionization is dissolved in 0.32gNaOH
It is configured to mixed solution B in water, then quickly mixes solution A and solution B under quick stirring, and flow back instead at 60 DEG C
10h is answered, product centrifuge washing is obtained into ZnAl-HTLc to neutral, drying after reaction；
(2) 80mL, concentration 0.6mo1/L the preparation of complex carrier: is added in the ZnAl-HTLc15g of step (1) preparation
A glucose monohydrate aqueous solution in, stir at room temperature to be uniformly mixed；Then said mixture is gone into polytetrafluoro
In ethylene reaction kettle, 180 DEG C isothermal reaction 6 hours, be cooled to room temperature after reaction, isolate product, then use deionization
Water and ethyl alcohol are dried after alternately washing at 90 DEG C to get ZnAl-HTLc/ carbon complex carrier；
(3) preparation of catalyst: respectively by Cu (NO3)2·3H2O、La(NO3)3·6H2O、 Co(NO3)2·6H2O dissolution
In deionized water, heating, stirring are made into concentration 0.6mol/L, and volume is respectively the clear solution of 100ml, 60ml and 50ml,
Then configured solution is added to simultaneously in the 12g complex carrier of step (2) preparation, at 90 DEG C after dipping 4h at 40 DEG C
Resulting solid product is roasted 5h at 500 DEG C, catalyst is placed in tube furnace after being ground up, sieved, by tubular type by lower drying
Furnace temperature is warming up to 350 DEG C from room temperature with the speed program of 2 DEG C/min, while 7% hydrogen of percent by volume is passed through into tube furnace
Activation of catalyst 5h is continued same nitrogen until temperature is reduced to room temperature by the mixed gas of gas and 93% nitrogen composition later.
Embodiment 3
A kind of preparation method preparing 1,3-Dihydroxyacetone catalyst, includes the following steps:
(1) preparation of ZnAl-HTLc: by soluble 0.375gAl (NO3)3·9H2O、 0.891gZn(NO3)2·6H2O
It is dissolved in the deionized water of 150ml and is configured to mixed solution A, by 0.05gNa2CO3150ml deionized water is dissolved in 0.40gNaOH
In be configured to mixed solution B, then solution A and solution B are quickly mixed under quick stirring, and the back flow reaction at 60 DEG C
Product centrifuge washing is obtained ZnAl-HTLc to neutral, drying after reaction by 10h；
(2) 100mL, concentration 0.5mo1/ the preparation of complex carrier: is added in the ZnAl-HTLc12g of step (1) preparation
In a glucose monohydrate aqueous solution of L, stirred at room temperature to uniformly mixed；Then said mixture is gone into polytetrafluoro
In ethylene reaction kettle, 180 DEG C isothermal reaction 6 hours, be cooled to room temperature after reaction, isolate product, then use deionization
Water and ethyl alcohol are dried after alternately washing at 90 DEG C to get ZnAl-HTLc/ carbon complex carrier；
(3) preparation of catalyst: respectively by Cu (NO3)2·3H2O、La(NO3)3·6H2O、 Co(NO3)2·6H2O dissolution
In deionized water, heating, stirring are made into concentration 0.8mol/L, and volume is respectively the clear solution of 100ml, 60ml and 50ml,
Then configured solution is added to simultaneously in the 15g complex carrier of step (2) preparation, at 90 DEG C after dipping 4h at 40 DEG C
Resulting solid product is roasted 5h at 500 DEG C, catalyst is placed in tube furnace after being ground up, sieved, by tubular type by lower drying
Furnace temperature is warming up to 350 DEG C from room temperature with the speed program of 2 DEG C/min, while 7% hydrogen of percent by volume is passed through into tube furnace
Activation of catalyst 5h is continued same nitrogen until temperature is reduced to room temperature by the mixed gas of gas and 93% nitrogen composition later.
Embodiment 4
A kind of preparation method preparing 1,3-Dihydroxyacetone catalyst, includes the following steps:
(1) preparation of ZnAl-HTLc: by soluble 0.375gAl (NO3)3·9H2O、 0.891gZn(NO3)2·6H2O
It is dissolved in the deionized water of 150ml and is configured to mixed solution A, by 0.048gNa2CO3150ml deionization is dissolved in 0.42gNaOH
It is configured to mixed solution B in water, then quickly mixes solution A and solution B under quick stirring, and flow back instead at 60 DEG C
10h is answered, product centrifuge washing is obtained into ZnAl-HTLc to neutral, drying after reaction；
(2) 90mL, concentration 0.7mo1/L the preparation of complex carrier: is added in the ZnAl-HTLc12g of step (1) preparation
A glucose monohydrate aqueous solution in, stir at room temperature to be uniformly mixed；Then said mixture is gone into polytetrafluoro
In ethylene reaction kettle, 180 DEG C isothermal reaction 6 hours, be cooled to room temperature after reaction, isolate product, then use deionization
Water and ethyl alcohol are dried after alternately washing at 90 DEG C to get ZnAl-HTLc/ carbon complex carrier；
(3) preparation of catalyst: respectively by Cu (NO3)2·3H2O、La(NO3)3·6H2O、 Co(NO3)2·6H2O dissolution
In deionized water, heating, stirring are made into concentration 0.5mol/L, and volume is respectively the clear solution of 100ml, 60ml and 50ml,
Then configured solution is added to simultaneously in the 10g complex carrier of step (2) preparation, at 90 DEG C after dipping 4h at 40 DEG C
Resulting solid product is roasted 5h at 500 DEG C, catalyst is placed in tube furnace after being ground up, sieved, by tubular type by lower drying
Furnace temperature is warming up to 350 DEG C from room temperature with the speed program of 2 DEG C/min, while 7% hydrogen of percent by volume is passed through into tube furnace
Activation of catalyst 5h is continued same nitrogen until temperature is reduced to room temperature by the mixed gas of gas and 93% nitrogen composition later.
Embodiment 5
A kind of preparation method preparing 1,3-Dihydroxyacetone catalyst, includes the following steps:
(1) preparation of ZnAl-HTLc: by soluble 0.375gAl (NO3)3·9H2O、 0.891gZn(NO3)2·6H2O
It is dissolved in the deionized water of 150ml and is configured to mixed solution A, by 0.042gNa2CO3150ml deionization is dissolved in 0.48gNaOH
It is configured to mixed solution B in water, then quickly mixes solution A and solution B under quick stirring, and flow back instead at 60 DEG C
10h is answered, product centrifuge washing is obtained into ZnAl-HTLc to neutral, drying after reaction；
(2) 80mL, concentration 0.6mo1/L the preparation of complex carrier: is added in the ZnAl-HTLc15g of step (1) preparation
A glucose monohydrate aqueous solution in, stir at room temperature to be uniformly mixed；Then said mixture is gone into polytetrafluoro
In ethylene reaction kettle, 180 DEG C isothermal reaction 6 hours, be cooled to room temperature after reaction, isolate product, then use deionization
Water and ethyl alcohol are dried after alternately washing at 90 DEG C to get ZnAl-HTLc/ carbon complex carrier；
(3) preparation of catalyst: respectively by Cu (NO3)2·3H2O、La(NO3)3·6H2O、 Co(NO3)2·6H2O dissolution
In deionized water, heating, stirring are made into concentration 0.5mol/L, and volume is respectively the clear solution of 110ml, 65ml and 55ml,
Then configured solution is added to simultaneously in the 12g complex carrier of step (2) preparation, at 90 DEG C after dipping 4h at 40 DEG C
Resulting solid product is roasted 5h at 500 DEG C, catalyst is placed in tube furnace after being ground up, sieved, by tubular type by lower drying
Furnace temperature is warming up to 350 DEG C from room temperature with the speed program of 2 DEG C/min, while 7% hydrogen of percent by volume is passed through into tube furnace
Activation of catalyst 5h is continued same nitrogen until temperature is reduced to room temperature by the mixed gas of gas and 93% nitrogen composition later.
Embodiment 6
A kind of preparation method preparing 1,3-Dihydroxyacetone catalyst, includes the following steps:
(1) preparation of ZnAl-HTLc: by soluble 0.325gAl (NO3)3·9H2O、 0.823gZn(NO3)2·6H2O
It is dissolved in the deionized water of 150ml and is configured to mixed solution A, by 0.042gNa2CO3150ml deionization is dissolved in 0.48gNaOH
It is configured to mixed solution B in water, then quickly mixes solution A and solution B under quick stirring, and flow back instead at 60 DEG C
10h is answered, product centrifuge washing is obtained into ZnAl-HTLc to neutral, drying after reaction；
(2) 9mL, concentration 0.6mo1/L the preparation of complex carrier: is added in the ZnAl-HTLc12g of step (1) preparation
A glucose monohydrate aqueous solution in, stir at room temperature to be uniformly mixed；Then said mixture is gone into polytetrafluoro
In ethylene reaction kettle, 180 DEG C isothermal reaction 6 hours, be cooled to room temperature after reaction, isolate product, then use deionization
Water and ethyl alcohol are dried after alternately washing at 90 DEG C to get ZnAl-HTLc/ carbon complex carrier；
(3) preparation of catalyst: respectively by Cu (NO3)2·3H2O、La(NO3)3·6H2O、 Co(NO3)2·6H2O dissolution
In deionized water, heating, stirring are made into concentration 0.6mol/L, and volume is respectively the clear solution of 100ml, 60ml and 50ml,
Then configured solution is added to simultaneously in the 12g complex carrier of step (2) preparation, at 90 DEG C after dipping 4h at 40 DEG C
Resulting solid product is roasted 5h at 500 DEG C, catalyst is placed in tube furnace after being ground up, sieved, by tubular type by lower drying
Furnace temperature is warming up to 350 DEG C from room temperature with the speed program of 2 DEG C/min, while 7% hydrogen of percent by volume is passed through into tube furnace
Activation of catalyst 5h is continued same nitrogen until temperature is reduced to room temperature by the mixed gas of gas and 93% nitrogen composition later.
Embodiment 7
Application examples:
The embodiment 1-6 catalyst prepared is used for glycerol oxidation and prepares 1,3-Dihydroxyacetone reaction, measures its catalysis
Performance.
Test method is: according to the mass ratio 50:1 of glycerol and catalyst, by 5g glycerol, 200mL deionized water and 0.1g
Catalyst be added 300mL quartz glass bottle in, it is closed completely after, utilize high-purity O2Degasification lmin is carried out, is kept in reaction process
High-purity O of 0.1MPa2, mixing speed 1000rpm is heated to 80 DEG C, reaction time 5h.After reaction, ice-water bath is used
It is cooled to room temperature, is centrifuged, filters, reaction solution carries out Shimadzu high performance liquid chromatography detection, measures the conversion ratio and 1 of glycerol, 3- bis-
The selectivity of hydroxypropanone-, the results are shown in Table 1.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (7)
1. a kind of preparation method for preparing 1,3-Dihydroxyacetone catalyst by glycerol, which comprises the steps of:
(1) preparation of ZnAl-HTLc: being dissolved in deionized water by soluble zinc salt, aluminium salt and be configured to mixed solution A, will
Na2CO3It is dissolved in deionized water with NaOH and is configured to mixed solution B, it is then under quick stirring that solution A and solution B is quick
Product centrifuge washing is obtained ZnAl- to neutral, drying after reaction by mixing, and the back flow reaction 8-12h at 50-70 DEG C
HTLc；
(2) preparation of complex carrier: 60-120mL is added in the ZnAl-HTLc of step (1) preparation, concentration is about 0.5-1mo1/L
A glucose monohydrate aqueous solution in, stir at room temperature to be uniformly mixed；Then said mixture is gone into polytetrafluoro
In ethylene reaction kettle, 160-200 DEG C isothermal reaction 4-8 hours, be cooled to room temperature after reaction, isolate product, then use
Deionized water and ethyl alcohol are dried after alternately washing at 80-100 DEG C to get ZnAl-HTLc/ carbon complex carrier；
(3) preparation of catalyst: respectively by Cu (NO3)2·3H2O、La(NO3)3·6H2O、Co(NO3)2·6H2O be dissolved in from
In sub- water, heating, stirring are made into clear solution, then configured solution are added to the compound load of step (2) preparation simultaneously
In body, the drying at 80-100 DEG C after 3-5h is impregnated at 30-50 DEG C, resulting solid product is roasted at 450-550 DEG C
4-6h, by Hydrogen activation up to the catalyst after being ground up, sieved.
2. preparation method according to claim 1, which is characterized in that the aluminium salt in step (1) is aluminum nitrate, and zinc salt is nitre
Sour zinc, the molar ratio of Zn/Al is 1-3 in mixed solution A, and the molar ratio of sodium carbonate and aluminum nitrate is 0.2-0.5 in solution B,
NaOH is 1-3:1 with molar ratio cationic in solution A, and solution A is equal with the volume of solution B.
3. preparation method according to claim 1, which is characterized in that the additional amount of ZnAl-HTLc is 10- in step (2)
20g。
4. preparation method according to claim 1, which is characterized in that Cu (NO in step (3)3)2·3H2O、La(NO3)3·
6H2O、Co(NO3)2·6H2It is 0.2-0.8mol/L that O, which is dissolved in the concentration after deionized water, and the volume of solution is respectively 80-
120ml、50-80ml、40-60ml。
5. preparation method according to claim 1, which is characterized in that the additional amount of complex carrier is 8- in step (3)
15g。
6. preparation method according to claim 1, which is characterized in that lead to the process of Hydrogen activation in step (3) are as follows: will urge
Agent is placed in tube furnace, and tubular type furnace temperature is warming up to 350 DEG C from room temperature with the speed program of 2 DEG C/min, while to tubular type
The mixed gas of percent by volume 5-10% hydrogen and 90-95% nitrogen composition is passed through in furnace, by activation of catalyst 3-6h, later
Continue with nitrogen until temperature is reduced to room temperature.
7. a kind of catalyst being prepared by any one of claim 1-6 the method.
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