CN105728042B - A kind of catalyst and preparation method and application by furfural production levulinate - Google Patents

A kind of catalyst and preparation method and application by furfural production levulinate Download PDF

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CN105728042B
CN105728042B CN201610128748.9A CN201610128748A CN105728042B CN 105728042 B CN105728042 B CN 105728042B CN 201610128748 A CN201610128748 A CN 201610128748A CN 105728042 B CN105728042 B CN 105728042B
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catalyst
furfural
added
alcohol
levulinate
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CN105728042A (en
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樊卫斌
朱善辉
王建国
秦张峰
岑友良
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B01J27/055—Sulfates with alkali metals, copper, gold or silver
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol

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Abstract

A kind of catalyst group by furfural production levulinate becomes the mass content 0.5%-5% of metal component, and the mass content of acid constituents is 5%-30%, remaining is carrier.The advantages of present invention has simple process, and reaction condition is mild, and low energy consumption, pollution-free and high yield.

Description

A kind of catalyst and preparation method and application by furfural production levulinate
Technical field
The invention belongs to a kind of methods for preparing levulinate, are particularly related to one kind by furfural production levulic acid The catalyst and preparation method and application of ester.
Background technique
Furfural is important biomass platform chemicals and the Essential Chemistry raw material of industry, can be by corncob, bagasse and paddy The discarded farm-forestry crop such as shell hydrolyzes in acid medium to be made.Traditionally, furfural mainly synthesizes furfuryl alcohol, 2- methyl through catalytic hydrogenation The fine chemicals such as furans and tetrahydrofuran.Now, the whole world can produce 200000 tons of furfurals every year, thus be badly in need of developing new work Skill technology converts furfural.
Levulinate is widely used, can be used as solvent, food additives and liquid fuel additive, can also be used to close At liquid fuel gamma-valerolactone.Currently, there are mainly two types of the synthetic methods of levulinate: (1) being existed by carbohydrate or cellulose Alcoholysis under strong acid condition；(2) under acid catalysis alcoholysis occurs for furfuryl alcohol.Li et al. is with (ACS Catalysis Sustainable Chemistry&Engineering, 2013,1,1593-1599) Amberlyst and Pd/Al2O3For catalyst, xylose and first Alcohol one kettle way is converted to levulinate, and the yield of levulinate is 20%.Tominaga etc. (Green Chemistry, 2011,13,810-812) with mixed acid beta-naphthalenesulfonic-acid and In (OTf)3For catalyst, using methanol as solvent, alcoholysis cellulose, second The yield of acyl propionic ester reaches 75%, if alcoholysis glucose, yield if is 58%.In addition, patent (CN104693023A) is public Cloth one kind uses magnetic basic zirconium phosphate for catalyst, reacts 3 in 190~200 DEG C of temperature of alcoholic solution using glucose as raw material ~6h obtains the method that levulinate yield is 30%~50%.The above method is using carbohydrate or cellulose as raw material, reaction Temperature is higher, and generally using liquid acid as catalyst, and yield is lower.In the second approach, furfuryl alcohol alcoholysis under acid catalysis Generate levulinate.Zhu etc. (ChemCatChem, 2014,6,3080-3083) report graphene oxide can be catalyzed at 120 DEG C Furfuryl alcohol alcoholysis generates levulinate, yield > 90%, but the stability of graphene oxide is very poor, cannot reuse.Due to Raw material furfuryl alcohol is made of furfural catalytic hydrogenation, is directly converted into levulinate using furfural as raw material and saves process flow And construction investment.Yuan etc. (ChemSusChem, 2014,7,202-209) uses Pt/ZrNbPO4Catalyst is in 5MPa H2Condition The levulinate that yield is 75.6% is made in lower coupling conversion furfural and ethyl alcohol.But the technique uses high pressure hydrogen, increases Investment and security risk.
Summary of the invention
The object of the present invention is to provide a kind of simple processes, and reaction condition is mild, and low energy consumption, pollution-free and high yield by The method of furfural production levulinate.
The response path for synthesizing levulinate by furfural and monohydric alcohol in the present invention is as follows: (1) furfural is being catalyzed first The metal component catalysis of agent is lower and monohydric alcohol occurs hydrogen transfer reaction and generates furfuryl alcohol；(2) it is catalyzed in the solid acid component of catalyst Under, furfuryl alcohol occurs alcoholysis reaction and is converted to levulinate.This two-step reaction is completed in a reactor.
The present invention is that metal-acid bifunctional catalyst is added, one is reacted in reaction kettle using furfural and monohydric alcohol as raw material After the section time, the product of generation obtains levulinate by the techniques such as separation and drying.
To achieve the above object, catalyst group of the present invention becomes the mass content 0.5%-5% of metal component, acid constituents Mass content is 5%-30%, remaining is carrier.
Catalyst metal components as described above are one or more of Pt, Pd, Ru, Au, Cu and Ni, and acid constituents is H3PW12O40、H4SiW12O40、H3PMo12O40、H2SO4And H3PO4One or more of, carrier is SiO2、ZrO2、γ-Al2O3、 C、CeO2、TiO2With the one or more of ZSM-5.
The preparation method of catalyst of the present invention includes the following steps:
Using incipient impregnation-sedimentation, active acid constituent is made into aqueous solution first, carrier needed for being added, at room temperature 5-20h, the 200-350 DEG C of roasting 2-6h in Muffle furnace are impregnated, then, the forerunner containing metal component is added in above-mentioned sample The aqueous solution that body is made into is 5-20 times of active metal by the quality of sodium borohydride, adds required sodium borohydride, stirs 0.5- 3h, is centrifugated out solid, and catalyst is made in 60-110 DEG C of dry 10-20h.
The presoma of metal component as described above is chloroplatinic acid, palladium chloride, ruthenic chloride, gold chloride, copper nitrate and nitric acid One or more of nickel.
Catalyst of the present invention includes the following steps:
(1) furfural, monohydric alcohol and catalyst are uniformly mixed by the mass ratio of 1-10:10-100:1, is made into furfural, one The mixture of the pure and mild catalyst of member, is put into reactor；
(2) configured mixture is heated to 100-200 DEG C of reaction temperature, cooling after reacting 10-30h, separation obtains To levulinate.
Monohydric alcohol as described above is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, isoamyl One or more of alcohol, n-hexyl alcohol.
The invention has the following advantages over the prior art:
(1) entire technique uses one-step method, saves project amount and simplifies experimental provision, can significantly reduce and be produced into This.
(2) it does not need to use external hydrogen, but using reactant monohydric alcohol as hydrogen source, which can recycle benefit With improving the economy and safety of entire technique；
(3) metal-acid bifunctional catalyst is used, preparation process is simple, is easy to separate with product, and the activity of catalyst is very It is high and may be reused.
(4) reaction condition is mild, and raw material furfural can convert completely, and the total recovery of levulinate is up to 90%, the party Method significantly improves the yield of levulinate.
Specific embodiment
The operating method that the technology is illustrated below with reference to specific example, the example provided are given for example only the present invention, but It is not in any way limit the scope of the present invention.
Embodiment 1
Firstly, weighing 1.0g H3PW12O40, 10mL water is added, 10g SiO is added in wiring solution-forming2, 8h is impregnated at room temperature, 250 DEG C of roasting 4h in Muffle furnace.Then, 200mL chloroplatinic acid aqueous solution is added in above-mentioned sample, adds 0.5g hydroboration Sodium stirs 1h, is centrifugated out solid, 80 DEG C of dry 20h obtain Pt-H3PW12O40/SiO2Catalyst, wherein the quality of Pt contains Amount is 1%, H3PW12O40Mass content be 10%.
2g furfural, 15g methanol and 0.5g Pt-H3PW12O40/SiO2It is added in autoclave.Reaction system plus Heat is to 160 DEG C, and continuous heating 10h, cooling reaction kettle, takes out product, centrifuge separation, with gas chromatographic analysis, furfural turns Rate is 100%, and levulinate total recovery reaches 76.4%.
Embodiment 2
Firstly, weighing 2.0g H4SiW12O40, 20mL water is added, 10g ZrO is added in wiring solution-forming2, impregnate at room temperature 10h, 200 DEG C of roasting 5h in Muffle furnace.Then, 200mL chloroplatinic acid aqueous solution is added in above-mentioned sample, adds 1.0g boron Sodium hydride stirs 0.5h, is centrifugated out solid, 100 DEG C of dry 12h obtain Pt-H4SiW12O40/ZrO2Catalyst, wherein Pt Mass content be 1%, H4SiW12O40Mass content be 20%.
2g furfural, 10g ethyl alcohol, 5g propyl alcohol and 0.5g Pt-H4SiW12O40/ZrO2It is added in autoclave.Anti- System is answered to be heated to 160 DEG C, and continuous heating 15h, cooling reaction kettle takes out product, centrifuge separation, with gas chromatographic analysis, The conversion ratio of furfural is 100%, and levulinate total recovery reaches 80.1%.
Embodiment 3
Firstly, weighing 2.0g H4SiW12O40, 20mL water is added, 10g ZrO is added in wiring solution-forming2, impregnate at room temperature 15h, 350 DEG C of roasting 2h in Muffle furnace.Then, 200mL palladium chloride aqueous solution is added in above-mentioned sample, adds 1.0g boron Sodium hydride stirs 3h, is centrifugated out solid, 110 DEG C of dry 10h obtain Pd-H4SiW12O40/ZrO2Catalyst, wherein Pd Mass content is 2%, H4SiW12O40Mass content be 20%.
3g furfural, 20g normal propyl alcohol and 0.4g Pd-H4SiW12O40/ZrO2It is added in autoclave.Reactant System is heated to 200 DEG C, and continuous heating is for 24 hours, and cooling reaction kettle takes out product, centrifuge separation, with gas chromatographic analysis, furfural Conversion ratio be 100%, levulinate total recovery reaches 78.9%.
Embodiment 4
Firstly, weighing 1.0g H3PMo12O40, 10mL water is added, 10g γ-Al is added in wiring solution-forming2O3, impregnate at room temperature 20h, 200 DEG C of roasting 6h in Muffle furnace.Then, 200mL palladium chloride aqueous solution is added in above-mentioned sample, adds 1.5g boron Sodium hydride stirs 2h, is centrifugated out solid, 60 DEG C of dry 20h obtain Pd-H3PMo12O40/γ-Al2O3Catalyst, wherein The mass content of Pd is 2%, H3PMo12O40Mass content be 10%.
2g furfural, 10g isopropanol and 0.3g Pd-H3PMo12O40/γ-Al2O3It is added in autoclave.Anti- System is answered to be heated to 190 DEG C, and continuous heating 10h, cooling reaction kettle takes out product, centrifuge separation, with gas chromatographic analysis, The conversion ratio of furfural is 100%, and levulinate total recovery reaches 85.7%.
Embodiment 5
Firstly, weighing 1.5g H3PMo12O40, 15mL water is added, wiring solution-forming is added 10g C, impregnates 15h at room temperature, 200 DEG C of roasting 3h in Muffle furnace.Then, 200mL ruthenium chloride aqueous solution is added in above-mentioned sample, adds 0.5g hydroboration Sodium stirs 1h, is centrifugated out solid, 90 DEG C of dry 15h obtain Ru-H3PMo12O40/ C catalyst, the wherein mass content of Ru For 0.5%, H3PMo12O40Mass content be 15%.
5g furfural, 80g isopropanol and 1.0g Ru-H3PMo12O40/ C is added in autoclave.Reaction system plus Heat is to 130 DEG C, and continuous heating is for 24 hours, cooling reaction kettle, takes out product, centrifuge separation, with gas chromatographic analysis, furfural turns Rate is 100%, and levulinate total recovery reaches 90.1%.
Embodiment 6
Firstly, weighing 2.5g H3PMo12O40, 25mL water is added, 10g CeO is added in wiring solution-forming2, impregnate at room temperature 18h, 250 DEG C of roasting 6h in Muffle furnace.Then, addition 200mL palladium chloride and ruthenium chloride aqueous solution in above-mentioned sample, then plus Enter 1.5g sodium borohydride, stirs 2.5h, be centrifugated out solid, 70 DEG C of dry 18h obtain PdRu-H3PMo12O40/CeO2Catalysis Agent, the mass content that wherein mass content of Pd is 0.5%, Ru is 0.5%, H3PMo12O40Mass content be 25%.
4g furfural, 30g n-butanol and 0.5g PdRu-H3PMo12O40/CeO2It is added in autoclave.Reaction System is heated to 180 DEG C, and continuous heating 30h, and cooling reaction kettle takes out product, centrifuge separation, with gas chromatographic analysis, chaff The conversion ratio of aldehyde is 100%, and levulinate total recovery reaches 78.1%.
Embodiment 7
Firstly, weighing 1.0g H3PMo12O40, 10mL water is added, 10g CeO is added in wiring solution-forming2, impregnate at room temperature 12h, 300 DEG C of roasting 3h in Muffle furnace.Then, 200mL chlorauric acid solution is added in above-mentioned sample, adds 0.5g boron hydrogen Change sodium, stirs 1.5h, be centrifugated out solid, 100 DEG C of dry 15h obtain Au-H3PMo12O40/CeO2Catalyst, wherein Au Mass content is 1.0%, H3PMo12O40Mass content be 10%.
3g furfural, 10g n-butanol and 0.4g Au-H3PMo12O40/CeO2It is added in autoclave.Reactant System is heated to 170 DEG C, and continuous heating is for 24 hours, and cooling reaction kettle takes out product, centrifuge separation, with gas chromatographic analysis, furfural Conversion ratio be 100%, levulinate total recovery reaches 82.6%.
Embodiment 8
Firstly, weighing 1.5g H2SO4, 15mL water is added, 10g CeO is added in wiring solution-forming2, 20h is impregnated at room temperature, 200 DEG C of roasting 2h in Muffle furnace.Then, 200mL gold chloride and palladium chloride solution are added in above-mentioned sample, 1.0g boron hydrogen is added Change sodium, stirs 0.5h, be centrifugated out solid, 90 DEG C of dry 16h obtain AuPd-SO3H/CeO2Catalyst, the wherein quality of Au The mass content that content is 1.0%, Pd is 1.0%, SO3The loading content of H is 15%.
3g furfural, 10g isobutanol and 0.4g AuPd-SO3H/CeO2It is added in autoclave.Reaction system plus Heat is to 170 DEG C, and continuous heating is for 24 hours, cooling reaction kettle, takes out product, centrifuge separation, with gas chromatographic analysis, furfural turns Rate is 100%, and levulinate total recovery reaches 88.1%.
Embodiment 9
Firstly, weighing 2.0g H3PO4, 20mL water is added, 10g TiO is added in wiring solution-forming2, 15h is impregnated at room temperature, 250 DEG C of roasting 5h in Muffle furnace.Then, 200mL copper nitrate solution is added in above-mentioned sample, adds 2.5g sodium borohydride, 2h is stirred, is centrifugated out solid, 90 DEG C of dry 12h obtain Cu-H3PO4/TiO2Catalyst, wherein the mass content of Cu be 5.0%, H3PO4Mass content be 20%.
2g furfural, 10g isobutanol and 0.3g Cu-H3PO4/TiO2It is added in autoclave.Reaction system plus Heat is to 200 DEG C, and continuous heating is for 24 hours, cooling reaction kettle, takes out product, centrifuge separation, with gas chromatographic analysis, furfural turns Rate is 100%, and levulinate total recovery reaches 78.9%.
Embodiment 10
Firstly, weighing 2.0g H3PO4, 20mL water is added, 10g TiO is added in wiring solution-forming2, 18h is impregnated at room temperature, 200 DEG C of roasting 3h in Muffle furnace.Then, 200mL nickel nitrate solution is added in above-mentioned sample, adds 2.5g sodium borohydride, 0.5h is stirred, is centrifugated out solid, 90 DEG C of dry 14h obtain Ni-H3PO4/TiO2Catalyst, wherein the mass content of Ni be 5.0%, H3PO4Mass content be 20%.
2g furfural, 10g n-amyl alcohol and 0.3g Ni-H3PO4/TiO2It is added in autoclave.Reaction system plus Heat is to 200 DEG C, and continuous heating is for 24 hours, cooling reaction kettle, takes out product, centrifuge separation, with gas chromatographic analysis, furfural turns Rate is 100%, and levulinate total recovery reaches 80.3%.
Embodiment 11
Firstly, weighing 1.0g H3PMo12O40, 10mL water is added, 5g TiO is added in wiring solution-forming2With 5g ZrO2, room temperature Lower dipping 15h, 250 DEG C of roasting 6h in Muffle furnace.Then, 200mL copper nitrate solution is added in above-mentioned sample, adds 2.5g sodium borohydride stirs 3h, is centrifugated out solid, 70 DEG C of dry 20h obtain Cu-H3PMo12O40/TiO2ZrO2Catalysis Agent, wherein the mass content of Cu is 5.0%, H3PMo12O40Mass content be 10%.
4g furfural, 20g n-amyl alcohol and 0.5g Cu-H3PMo12O40/TiO2ZrO2It is added in autoclave.Anti- System is answered to be heated to 200 DEG C, and continuous heating 30h, cooling reaction kettle takes out product, centrifuge separation, with gas chromatographic analysis, The conversion ratio of furfural is 100%, and levulinate total recovery reaches 89.0%.
Embodiment 12
Firstly, weighing 1.0g H3PMo12O40With 1.0g H4SiW12O40, 20mL water is added, 10g is added in wiring solution-forming TiO2, 5h is impregnated at room temperature, 200 DEG C of roasting 5h in Muffle furnace.Then, 200mL chlorauric acid solution is added in above-mentioned sample, 2.0g sodium borohydride is added, stirs 2.5h, is centrifugated out solid, 100 DEG C of dry 10h obtain Au- H3PMo12O40H4SiW12O40/TiO2Catalyst, wherein the mass content of Au is 2.0%, H3PMo12O40Mass content be 10%, H4SiW12O40Mass content be 10%.
2g furfural, 5g n-amyl alcohol, 5g isoamyl alcohol and 0.3g Au-H3PMo12O40H4SiW12O40/TiO2It is anti-to be added to high pressure It answers in kettle.Reaction system is heated to 140 DEG C, and continuous heating 20h, cooling reaction kettle takes out product, and gas is used in centrifuge separation Analysis of hplc, the conversion ratio of furfural are 100%, and levulinate total recovery reaches 93.1%.
Embodiment 13
Firstly, weighing 1.5g H4SiW12O40, 15mL water is added, wiring solution-forming is added 10g ZSM-5, impregnates at room temperature 12h, 350 DEG C of roasting 5h in Muffle furnace.Then, 200mL nickel nitrate solution is added in above-mentioned sample, adds 3.0g boron hydrogen Change sodium, stirs 1h, be centrifugated out solid, 90 DEG C of dry 14h obtain Ni-H4SiW12O40/ ZSM-5 catalyst, the wherein matter of Ni Amount content is 4.0%, H4SiW12O40Mass content be 15%.
2g furfural, 10g n-hexyl alcohol and 0.3g Ni-H4SiW12O40/ ZSM-5 is added in autoclave.Reactant System is heated to 190 DEG C, and continuous heating 30h, and cooling reaction kettle takes out product, centrifuge separation, with gas chromatographic analysis, furfural Conversion ratio be 100%, levulinate total recovery reaches 87.6%.

Claims (2)

1. a kind of application of catalyst in furfural production levulinate, which comprises the steps of:
(1) furfural, monohydric alcohol and catalyst are uniformly mixed by 1 ~ 10:10 ~ 100:1 mass ratio, is made into furfural, monohydric alcohol With the mixture of catalyst, it is put into reactor；
(2) configured mixture is heated to 100 ~ 200 DEG C of reaction temperature, cooling after reacting 10 ~ 30h, separation obtains second Acyl propionic ester；
The catalyst composition are as follows: the mass content 0.5%-5% of metal component, the mass content of acid constituents are 5%-30%, remaining For carrier；
The metal component is one or more of Pt, Pd, Ru, Au, Cu or Ni；
The acid constituents is H3PW12O40、H4SiW12O40、H3PMo12O40、H2SO4Or H3PO4；
The carrier is SiO2、ZrO2、γ-Al2O3、C、CeO2、TiO2With the one or more of ZSM-5；
The preparation method of the catalyst includes the following steps:
Using incipient impregnation-sedimentation, active acid constituent is made into aqueous solution first, carrier needed for being added impregnates 5 at room temperature Then ~ 20h, 200 ~ 350 DEG C of 2 ~ 6h of roasting in Muffle furnace are added the presoma containing metal component in above-mentioned sample and match At aqueous solution, be 5 ~ 20 times of active metal by the quality of sodium borohydride, add required sodium borohydride, stir 0.5 ~ 3h, It is centrifugated out solid, catalyst is made in 60 ~ 110 DEG C of dry 10 ~ 20h；
The presoma of the metal component is one of chloroplatinic acid, palladium chloride, ruthenic chloride, gold chloride, copper nitrate or nickel nitrate Or it is several.
2. application of the catalyst as described in claim 1 in furfural production levulinate, it is characterised in that described one First alcohol be one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol or It is a variety of.
CN201610128748.9A 2016-03-07 2016-03-07 A kind of catalyst and preparation method and application by furfural production levulinate Active CN105728042B (en)

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