CN106866372A - Recycling method of the tungsten-based catalyst in saccharide compound is catalyzed low-carbon alcohols processed - Google Patents

Recycling method of the tungsten-based catalyst in saccharide compound is catalyzed low-carbon alcohols processed Download PDF

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CN106866372A
CN106866372A CN201510918735.7A CN201510918735A CN106866372A CN 106866372 A CN106866372 A CN 106866372A CN 201510918735 A CN201510918735 A CN 201510918735A CN 106866372 A CN106866372 A CN 106866372A
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tungsten
paratungstate
catalyst
saccharide compound
reaction
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CN106866372B (en
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庞纪峰
郑明远
张涛
王爱琴
王晓东
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • 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
    • C07C29/132—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 an oxygen containing functional group
    • C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • 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
    • C07C29/132—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 an oxygen containing functional group
    • C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

In the reaction that saccharide compound catalyzed conversion prepares low-carbon alcohols, tungsten salt solution partly or entirely can be dissolved in reaction solution, cause the difficulty for reclaiming.In the present invention, it is tungsten source to use the paratungstate of low solubility, and is applied in the reaction that saccharide compound catalyzed conversion prepares propane diols, and low-carbon alcohols are prepared by a step catalytic conversion process.By being separated off solid matter, concentration separates out paratungstate to reacted solution, and filters, is recycled in reactor, realizes the whole flow process circulation of tungsten.The present invention has the tungsten-based catalyst rate of recovery high, and process is simple, and the overall process for realizing tungsten catalyst is utilized.

Description

Recycling method of the tungsten-based catalyst in saccharide compound is catalyzed low-carbon alcohols processed
Technical field
The invention belongs to the catalytic field in biomass chemical industry, more particularly to tungsten salt catalyst Recycle, the recovery application method of tungsten salt specifically in saccharide compound catalyzed conversion.
Background technology
The low-carbon alcohols such as ethylene glycol, propane diols are important energy liquid fuels, are also very heavy The polyester synthesis raw material wanted, for example, being used for PET (PET), poly- naphthalene Naphthalate (PEN), is also used as antifreezing agent, lubricant, plasticizer, table Face activating agent etc., is widely used Organic Chemicals.
At present, ethylene glycol, the production method of 1,2-PD mainly include oxirane, epoxy Propane direct hydration method, indirect hydration method.Although various method technologies all comparative maturities, but still There are many weak points.Such as these methods have environmental pollution and are seriously asked with costly Topic, it is difficult to mass produce.Simultaneously as the fossil class cost of material such as ethene, propylene is fast Speed goes up, the cost of above-mentioned production technology also more and more higher.Therefore, research and develop low cost, Efficiently, environmentally friendly biomass catalyzing Hydrogenation has important showing for the method for low-carbon alcohols Sincere justice.
With agrotechnical development, saccharide compound yield is growing.Development is with carbohydrate Compound prepares propane diols, not only can to a certain extent reduce the dependence to petroleum resources, together When, help to realize deep processing of farm products high valuable chemicals.At present, with carbohydrate chemical combination Technology (the document 1 of thing polyalcohol：A kind of new technology for producing ethylene glycol, CN200610068869.5 documents 2：It is a kind of that dihydroxylic alcohols and polyalcohol are produced by cracking sorbierite Method, CN200510008652.0) there is technology path complexity, high energy consumption, selectivity of product The shortcomings of difference, have a strong impact on the economy of process.
At present, obtained to ethylene glycol method by catalytic hydroconversion carbohydrate under hydrothermal condition To broad development, and show catalytic selectivity (document 3 higher：CN 101735014A, A kind of method of carbohydrate preparing ethylene glycol；Document 4：CN 102190562A, a kind of carbon The method of hydrate preparing ethylene glycol).The method is constituted with tungsten-based catalyst and hydrogenation catalyst Mixed catalyst catalyzed conversion is carried out to cellulose so that obtain 60-75% ethylene glycol and Propane diols.Similarly, the dual-component catalyst for being constituted using tungsten and hydrogenation metal, in hydro-thermal plus Also can realize that the high selectivities containing sugar compounds such as cellulose, starch prepare second two under conditions of hydrogen Alcohol, propane diols (document 5：A kind of method of preparing ethanediol from polyhydroxy compounds WO2011113281A)。
However, during the course of the reaction, tungsten can partly or entirely dissolve in the solution, by rectifying After process, high boiling polyol dissolves together with tungsten salt, and both are difficult to separate.Industrial one As organic matter is removed by burning, obtain tungsten oxide, then use alkali soluble solution, ammonification is reclaimed, mistake Journey is extremely complex, the relatively low (document 6 of organic efficiency of product：Grinding for tungsten is extracted in tungsten waste Study carefully, Chinese Mining Industry, 2008,17:77-81).In addition, the presence of tungsten salt can make rectifying substrate difficult To utilize, the economy of whole process is influenceed.
It is anti-that the tungsten-based catalyst that the present invention is provided prepares low-carbon alcohols in saccharide compound catalyzed conversion Should in recycling method, have the advantages that it is simple to operate, easily utilize.The tungsten base of selection Catalyst shows higher urging in saccharide compound catalyzed conversion prepares the reaction of low-carbon alcohols Change activity, and subsequent catalyst is easily reclaimed, recycled.In addition, whole course of reaction Middle tungsten catalyst has that organic efficiency is high, be easy to industrialized advantage.
The content of the invention
It is an object of the invention to provide a kind of tungsten-based catalyst in saccharide compound catalyzed conversion Prepare the recycling method in low-carbon alcohols reaction.
To achieve the above object, the technical scheme taken of the present invention is：
A kind of tungsten-based catalyst following in saccharide compound catalyzed conversion prepares low-carbon alcohols reaction Ring application method, it is characterised in that：
With saccharide compound as reaction raw materials, urged in water on reactor or fixed bed Change hydrogenation reaction, the catalyst for being used is composite catalyst, including catalyst A is Ru/C Or skeleton Ni is solid catalyst, catalyst B is paratungstate, and hydrogen is filled in reaction, Pressure is 3-15Mpa, 120-310 DEG C of reaction temperature, and the mass concentration of saccharide compound is 1-60%, mass space velocity is 0.1-10h-1；
Product is separated by filtration and obtains product liquid, by concentration, separates out para-tungstic acid Salt, again isolated liquid product rectification；
Paratungstate is separated out after concentration, and thickening temperature is 30-120 DEG C, solution reclaimed water after concentration Content is less than 10%, and -10-50 DEG C of crystallization temperature, crystallization time is 0.5-24h.
Saccharide compound be starch, cellulose, hemicellulose, sucrose, glucose, fructose, One or two or more kinds in levulan, xylose, soluble oligomeric xylose.
Reaction condition is：Reaction temperature is 180-300 DEG C, and pressure is 3-12Mpa, carbohydrate The mass concentration of compound is 10-50%, and mass space velocity is 1-8h-1, or, in reactor The quality of saccharide compound is 1-50 with the ratio of catalyst gross mass.
It is ethylene glycol, propane diols, fourth two that product is separated by filtration the main matter after concentration Alcohol, glycerine, mannitol, sorbierite, anhydro sorbitol, the polyalcohol of C6-C18, secondary tungsten The mass concentration of hydrochlorate is 1-50%.
Micro ammonium paratungstate can be added in crystallization process as Nucleating Agent, addition is less than liquid The 0.01% of tungsten salt quality in body product.
It is preferred that crystallization condition：Crystallization temperature is -10-30 DEG C, and water content is 0.1-3%, crystallization Time is 0.5-10h.
The tungsten salt ratio that single is reclaimed is more than 90%, and purity is higher than 95%, the tungsten salt of recovery Reactivity is constant in saccharide compound conversion, and can repeatedly circulate.
Paratungstate eduction rate is more than 93%；Paratungstate after recovery can be recycled 10 More than secondary.
The invention has the advantages that：
1. tungsten catalyst can be recycled directly without complex process operation.
2. with the saccharide compound in biomass as raw material, there is recyclability, accord with Close the requirement of sustainable development.
3. the economy of whole process is improve, with good industrial applications prospect.
Below by specific embodiment, the present invention is described in detail, but these embodiments are not Present disclosure is construed as limiting.
Specific embodiment
Embodiment 1
Reaction experiment：1.0gRu/C catalyst and 50ml water are added to 300ml reactors In, after being passed through three gases of nitrogen displacement, temperature programming to 220 DEG C, at this moment by 40wt%'s The ammonium paratungstate of saccharide compound and 1wt% is driven into reactor by pump, while liquid is taken, Mass space velocity is 2.In course of reaction, product is taken out, handed in high performance liquid chromatography calcium type ion Change on post and separated and detected with differential refractive index detector.In product yield to propane diols, The product such as ethylene glycol and glycerine is calculated.This reaction can be carried out in fixed bed, operate class Seemingly, sugared solution, air speed and reaction temperature are adjustable.
Operating condition and amount of substrate can be adjusted as needed.
Embodiment 2
Catalyst reclaims cyclic test：
The reaction solution of embodiment 1 is separated by filtration with solid catalyst, obtains containing ammonium paratungstate Polyhydric alcohol solutions, concentrate at 80 DEG C, when water content is less than 5%, crystallization, crystallization Temperature is 0 DEG C, adds 0.01g ammonium paratungstate crystal seeds, and crystallization time is 3h, separates out para-tungstic acid Ammonium salt, filtering.
Embodiment 3
After product filtering and concentrating, the organic efficiency situation of tungsten-based catalyst under the conditions of different water cut As shown in Table 1., with embodiment 1, recovering condition is with embodiment 2 for reaction condition.
The tungsten salt rate of recovery (reaction condition under the different water cut of table one：220 DEG C, mass space velocity is 1, Sugared concentration is 10%, and tungsten salt is ammonium paratungstate；Concentrated at 80 DEG C, crystallization temperature is 0 DEG C, is added Plus 0.1g ammonium paratungstate crystal seeds, crystallization time is 3h)
As shown in Table 1, precipitation influence of the moisture content on tungsten salt is very big.Wherein, it is low in moisture content The rate of recovery of tungsten salt alreadys exceed 96% when 3%.
Embodiment 4
Catalyst under different crystallization conditions reclaims result, and reaction condition is with embodiment 1 (table two).
Under the different crystallization conditions of table two, the catalyst that glucose catalyzed conversion prepares low-carbon alcohols is reclaimed As a result (reaction condition：220 DEG C, mass space velocity is 1, and sugared concentration is 10%, and tungsten salt is secondary tungsten Sour ammonium, moisture content 3%)
As shown in Table 2, reaction condition also can significantly change the organic efficiency of catalyst, excellent Change reaction condition to 0 DEG C of crystallization, it is secondary when adding crystal seed 0.02g and crystallization 24 hours The ammonium tungstate rate of recovery reaches 99%.
Embodiment 5
The circulation of ammonium paratungstate after crystallization regeneration, reaction condition is with embodiment 1 (table three), circulation During, fresh ammonium paratungstate is added every time, additional amount is the 2% of initial catalyst dosage.
Table three reclaims circulation of the ammonium paratungstate in glucose catalyzed conversion prepares low-carbon alcohols reaction As a result (reaction condition：220 DEG C, mass space velocity is 1, and sugared concentration is 10%, and catalyst is Ru/C+ reclaims ammonium paratungstate)
As shown in Table 3, the ammonium paratungstate after recovery still has identical catalysis activity, even if following Ring 20 times, the yield of ethylene glycol still reaches 60%.
Comparative example
Institute of the invention is compared using method with other method, and reaction condition is with embodiment 1
Four catalyst of table compare with the circulating effect of other catalyst
As shown in Table 4, the round-robin method of tungsten catalyst of the invention and other tungsten catalysts Reclaim round-robin method compared to have tungsten recovery rate is high, catalyst usage amount is low, catalysis activity is high, Catalyst recycle process is simple, the advantages of do not sacrifice high boiling alcohol, with application value very high.

Claims (9)

1. recycling method of the tungsten-based catalyst in saccharide compound is catalyzed low-carbon alcohols processed, It is characterized in that：
With saccharide compound as reaction raw materials, urged in water on reactor or fixed bed Change hydrogenation reaction, the catalyst for being used is composite catalyst, including catalyst A is Ru/C Or skeleton Ni is the one kind in solid catalyst or two kinds, catalyst B is paratungstate, instead Middle hydrogen should be filled, pressure is 3-15Mpa, 120-310 DEG C of reaction temperature, saccharide compound Mass concentration be 1-60%, mass space velocity is 0.1-10h-1；
Product is separated by filtration and obtains product liquid, by condensing crystallizing, separates out secondary Tungstates, thickening temperature is 30-120 DEG C, and water content is less than 10%, crystalline substance in solution after concentration Change -10-50 DEG C of temperature, crystallization time is 0.5-24h, and the paratungstate after recovery can be recycled；
Isolated pure paratungstate and polyhydric alcohol solutions again.
2. in accordance with the method for claim 1, it is characterised in that：
Saccharide compound be starch, cellulose, hemicellulose, sucrose, glucose, fructose, One or two or more kinds in levulan, xylose, soluble oligomeric xylose.
3. in accordance with the method for claim 1, it is characterised in that：
The paratungstate be ammonium paratungstate, sodium paratungstate, paratungstate potassium one or two More than.
4. in accordance with the method for claim 1, it is characterised in that：
Reaction condition is：Reaction temperature is 180-300 DEG C, and pressure is 3-12Mpa, carbohydrate The mass concentration of compound is 10-50%, and mass space velocity is 1-8h-1, or, in reactor The quality of saccharide compound is 1-50 with the ratio of catalyst gross mass.
5. in accordance with the method for claim 1, it is characterised in that：
It is ethylene glycol, propane diols, fourth two that product is separated by filtration the main matter after concentration Alcohol, glycerine, mannitol, sorbierite, anhydro sorbitol, the polyalcohol of C6-C18, secondary tungsten The mass concentration of hydrochlorate is 1-50%.
6. in accordance with the method for claim 1, it is characterised in that：
Micro ammonium paratungstate can be added in product crystallization process as Nucleating Agent, addition 0.1% of amount less than tungsten salt quality in product liquid.
7. in accordance with the method for claim 1, it is characterised in that：
It is preferred that crystallization condition：Crystallization temperature is -10-30 DEG C, and water content is 0.1-3%, crystallization Time is 0.5-10h.
8. in accordance with the method for claim 1, it is characterised in that：
The tungsten salt ratio that single is reclaimed is more than 90%, and purity is higher than 95%, the tungsten salt of recovery Reactivity is constant in saccharide compound conversion, and can repeatedly circulate.
9. according to the method described in claim 1 or 8, it is characterised in that：Para-tungstic acid is saltoutd Extracting rate is more than 93%；Paratungstate after recovery can be recycled more than 10 times.
CN201510918735.7A 2015-12-12 2015-12-12 Recycling method of tungsten-based catalyst in preparation of low-carbon alcohol by catalysis of carbohydrate Active CN106866372B (en)

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WO2022064039A1 (en) * 2020-09-28 2022-03-31 Avantium Knowledge Centre B.V. Process for recovering and regenerating a catalyst from ash

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US20230331648A1 (en) * 2020-09-28 2023-10-19 Avantium Knowledge Centre B.V. Process for producing glycols from carbohydrates and burning waste

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Publication number Priority date Publication date Assignee Title
WO2022064039A1 (en) * 2020-09-28 2022-03-31 Avantium Knowledge Centre B.V. Process for recovering and regenerating a catalyst from ash

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