CN106868305B - The method of tungsten-based catalyst is recycled in a kind of complex reaction substrate - Google Patents
The method of tungsten-based catalyst is recycled in a kind of complex reaction substrate Download PDFInfo
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- CN106868305B CN106868305B CN201510918759.2A CN201510918759A CN106868305B CN 106868305 B CN106868305 B CN 106868305B CN 201510918759 A CN201510918759 A CN 201510918759A CN 106868305 B CN106868305 B CN 106868305B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
In the reaction of saccharide compound catalyzed conversion preparation low-carbon alcohols, tungsten-based catalyst can be completely or partially dissolved in reaction substrate, it is difficult to be recycled, be increased the cost of catalyst.The present invention provides a kind of methods that tungsten-based catalyst is recycled in complex reaction substrate, complex reaction substrate is rectifying residue after saccharide compound catalyzed conversion, reaction product is after rectifying separation ethylene glycol, propylene glycol, obtain bottom resultant product, bottom resultant product boiling point >=200 DEG C, wherein containing tungsten salt；Tungsten salt is precipitated and is recycled by the way that organic solvent is added into bottom resultant product, and obtains higher boiling fusel, tungsten salt mass recovery >=90%.Method provided by the invention, catalyst recovery process is simple, catalyst recovery efficiency is high, and the circulation superior activity of catalyst.In addition, overall process is convenient for industrialized production convenient for operation.
Description
Technical field
The invention belongs to the catalytic fields in biomass chemical industry, the in particular to recycling of tungsten salt catalyst, specifically
Tungsten salt recovery method in saccharide compound catalyzed conversion after product rectification.
Background technique
The low-carbon alcohols such as ethylene glycol, propylene glycol are important energy liquid fuel, are also very important polyester synthesis raw material,
For example, being used for polyethylene terephthalate (PET), polyethylene naphthalate (PEN) is also used as antifreezing agent, profit
Lubrication prescription, plasticizer, surfactant etc. are widely used Organic Chemicals.
Currently, the production method of ethylene glycol, 1,2-PD mainly include ethylene oxide, propylene oxide direct hydration method,
Indirect hydration method.Although various method technologies all comparative maturities, there are still many shortcomings.As there is rings for these methods
The problems such as border is seriously polluted and expensive, it is difficult to be mass produced.Simultaneously as the fossils class cost of material such as ethylene, propylene
Quick rise, the cost of above-mentioned production technology is also higher and higher.Therefore, it researchs and develops inexpensive, efficient, environmentally friendly
Biomass catalyzing adds the method for hydrogen preparation low-carbon alcohols to have important practical significance.
With agrotechnical development, saccharide compound yield is growing.Development prepares propylene glycol with saccharide compound,
The dependence to petroleum resources can be not only reduced to a certain extent, meanwhile, it is additional to help to realize deep processing of farm products height
It is worth chemicals.Currently, with the technology of saccharide compound polyalcohol (document 1: a kind of new process producing ethylene glycol,
CN200610068869.5 document 2: a method of dihydric alcohol and polyalcohol are produced by cracking sorbierite,
CN200510008652.0) there are technology paths it is complicated, energy consumption is high, selectivity of product is poor the disadvantages of, seriously affect the warp of process
Ji property.
Currently, broad development is obtained to ethylene glycol method by catalytic hydroconversion carbohydrate under hydrothermal condition, and
Show higher catalytic selectivity (document 3:CN 101735014A, a kind of method of carbohydrate preparing ethylene glycol；Document
4:CN 102190562A, a kind of method of carbohydrate preparing ethylene glycol).This method is with tungsten-based catalyst and hydrogenation catalyst
The mixed catalyst of composition carries out catalyzed conversion to cellulose, to obtain the ethylene glycol and propylene glycol of 60-75%.Similarly,
The dual-component catalyst constituted using tungsten and hydrogenation metal, also can be realized cellulose, starch etc. under conditions of hydro-thermal plus hydrogen
Ethylene glycol, a kind of propylene glycol (document 5: method of preparing ethanediol from polyhydroxy compounds are prepared containing sugar compounds are highly selective
WO2011113281A)。
During the reaction, tungsten can partly or entirely dissolve in the solution, and after distillation process, high boiling polyol is same
Tungsten salt dissolves together, and the two is difficult to separate.It is industrial generally to be removed organic matter by burning, tungsten oxide is obtained, then use alkali
Dissolution, ammonification recycling, process is extremely complex, the recovery efficiency of product it is lower (document 6: in tungsten waste extract tungsten research, in
State's mining industry, 2008,17:77-81).
Catalyst recovery method provided by the invention, have many advantages, such as it is easy to operate, be easily worked, urged in saccharide compound
Change in the reaction subsequent catalyst recycling of conversion preparation low-carbon alcohols and shows very high selectivity.In addition, this reaction process exists
Catalyst recovery efficiency is high, is easy to industrialized advantage.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that tungsten-based catalyst is recycled in complex reaction substrate.I.e. using organic
The method that tungsten salt is precipitated in solvent realizes the tungsten recycling dissolved after saccharide compound is selectively converted to low-carbon alcohols in the solution.
To achieve the above object, the technical scheme adopted by the invention is as follows:
Complex reaction substrate is rectifying residue after saccharide compound catalyzed conversion, specific to react are as follows: with saccharide compound
For reaction raw materials, catalytic hydrogenation reaction is carried out in water on reaction kettle or fixed bed, used catalyst is composite catalyzing
Agent, including catalyst A is Ru/C or skeleton Ni is solid catalyst, catalyst B is the carbonization of tungsten, the nitride of tungsten, tungsten
Object, the phosphide of tungsten, the oxide of tungsten, the sulfide of tungsten, the chloride of tungsten, the hydroxide of tungsten, tungsten bronze, wolframic acid, wolframic acid
One or both of salt, metatungstic acid, ammonium metatungstate, para-tungstic acid, paratungstate, peroxide wolframic acid, peroxotungstate, heteropoly tungstic acid
More than, hydrogen is filled in reaction, pressure 3-15Mpa, 120-310 DEG C of reaction temperature, the mass concentration of saccharide compound is 1-
60%, mass space velocity 0.1-10h-1；
Reaction product obtains bottom resultant product, the boiling of bottom resultant product after rectifying separation ethylene glycol, propylene glycol
Point is higher than 200 DEG C, wherein containing tungsten salt；
Tungsten salt is precipitated and is received by the way that organic solvent is added into bottom resultant product, and obtains higher boiling fusel, it is organic
The temperature that solvent handles kettle base solution is -10-100 DEG C, and organic solvent is 100:1-1:10 with substrate mass ratio, and the tungsten salt rate of recovery is super
Cross 90%.
Saccharide compound is starch, cellulose, hemicellulose, sucrose, glucose, fructose, levulan, xylose, solubility
One of xylo-oligosaccharide or two kinds or more.
Reaction condition are as follows: reaction temperature is 180-300 DEG C, and the mass concentration of pressure 3-12Mpa, saccharide compound are
10-50%, mass space velocity 1-8h-1, alternatively, the ratio of the quality of saccharide compound and catalyst gross mass is 1- in reactor
50。
Bottom resultant product is glycerol, mannitol, sorbierite, anhydro sorbitol, fourth after rectifying separates ethylene glycol, propylene glycol
The polyalcohol of glycol, C6-C18, the mass concentration of tungsten salt are 1-50%.
By the way that organic solvent is added into bottom resultant product, the method that tungsten salt is precipitated and is received, the organic solvent of use
For one or more of methanol, ethyl alcohol, propyl alcohol, butanol, tetrahydrofuran, hexamethylene, Ethyl formate, methyl acetate.
The preferred condition that is precipitated: temperature is 0-80 DEG C, and organic solvent is 10:1-1:1 with substrate mass ratio, and the processing time is
0.5-5h is more than 200rpm by centrifuge separation revolving speed.
It is preferred that reaction dissolvent can be one or more of methanol, ethyl alcohol, propyl alcohol, wherein in solvent water content
Lower than 2%.
The tungsten salt ratio of recycling is more than 90%, and the tungsten salt of recycling reactivity in saccharide compound conversion is constant.
Tungsten salt mass content≤0.005% in the higher boiling fusel of recycling.
The present invention has the advantage that
1. catalyst recovery process is simple, convenient for the raising of whole process economy.
2. having the advantages that reproducibility using the saccharide compound in biomass as raw material, meet wanting for sustainable development
It asks.
3. the recovery efficiency of catalyst is high, low energy consumption and does not lose the yield of high boiling alcohol.
Below by specific embodiment, the present invention is described in detail, but these embodiments are not to the contents of the present invention
It is construed as limiting.
Specific embodiment
Embodiment 1
Catalyzed conversion containing sugar compounds prepares low-carbon alcohols:
1.0g catalyst Ru/C and 50ml water is added in 300ml reaction kettle, is passed through nitrogen displacement three times after gas, journey
Sequence is warming up to 220 DEG C, is at this moment driven into the glucose of 40wt% and ammonium metatungstate in reactor by pump, while taking liquid,
Mass space velocity is 2.In reaction process, product is taken out, separation is carried out on high performance liquid chromatography calcium type ion exchange column and with poor
Show that refraction detector is detected.The products such as propylene glycol, ethylene glycol and glycerol are calculated in product yield.This reaction can be with
It is carried out in fixed bed again, it is adjustable to operate similar, sugared solution, air speed and reaction temperature.
According to the difference of tungsten species, tungsten catalyst can also be placed in reaction vessel in advance.
Embodiment 2
Obtain complex substrate:
Solution filters after reaction, removes solid matter, and distillation water removal, rectifying obtain ethylene glycol and propylene glycol under reduced pressure,
The mixture of high boiling alcohol and tungsten salt is remained afterwards.
Embodiment 3
Experiment is precipitated:
Bottom product after rectifying is mixed with ethyl alcohol, temperature is 10 DEG C, and the two mass ratio is 1:5, and is quickly stirred, and is stirred
Rate is 600rpm, keeps bottom product after rectifying evenly dispersed, stands 12 hours.It is then centrifuged for filtering, speed 1000rpm,
It is washed 3 times with ethanol solution, is dried to obtain solid powder.
The same ethyl alcohol of bottom product, hexamethylene after rectifying are mixed, rectification substrate is 5:1 with the weight ratio of solvent, and ethyl alcohol is same
The volume ratio of hexamethylene is 1:1, and is quickly stirred, stirring rate 600rpm, keeps bottom product after rectifying evenly dispersed, is stood
12 small layereds.It is then centrifuged for filtering, speed 1000rpm, is washed 3 times with ethanol solution, be dried to obtain solid powder.
Response parameter can be changed according to different experiments to obtain the high tungsten salt rate of recovery.
Filtered filtrate decompression distillation, carries out solvent recovery, obtains higher boiling fusel.
Embodiment 4
The recovery efficiency of tungsten-based catalyst under different solvents, reaction condition with embodiment 1,2 (reaction condition: 220 DEG C, matter
Measuring air speed is 1, and sugared concentration is 10%, and tungsten salt is ammonium metatungstate；Rectifying condition: rectification under vacuum, pressure are less than 1kPa, temperature 200
DEG C), condition is precipitated with embodiment 3 (table one).
Under one different solvents of table, and the tungsten salt rate of recovery (precipitation process: 10 DEG C of temperature, organic solvent is with substrate ratios 10:1, and 3
Hour)
As shown in Table 1, ethanol solution shows good selectivity, and other solvents will affect the precipitation effect of its tungsten salt.
Wherein, the rate of recovery of low concentration ammonium metatungstate reaches 95% under ethyl alcohol+cyclohexane solvent.
Embodiment 5
Under different condition tungsten salt recycling as a result, reaction condition with embodiment 1,2 (reaction condition: 220 DEG C, mass space velocity
It is 1, sugared concentration is 10%, and tungsten salt is ammonium metatungstate；Rectifying condition: rectification under vacuum, pressure are less than 1kPa, 200 DEG C of temperature), analysis
Condition is the same as embodiment 3 (table two) out.
Under the conditions of the different precipitations of table two, the recycling result that glucose catalyzed conversion prepares the tungsten catalyst of low-carbon alcohols is (organic
Solvent is ethyl alcohol)
As shown in Table 2, reaction condition also can significantly change the recovery efficiency of catalyst, optimization reaction condition to 25
DEG C solvent, substrate ratio are 3, the time is 1 hour, and the ammonium metatungstate rate of recovery reaches 97%, and tungsten weight content in organic high boiling alcohol
Lower than 0.0032%.
Embodiment 6
There is the influence (table three) recycled to tungsten-based catalyst in impurity, reaction condition is the same as 1,2 (reaction condition: 220 of embodiment
DEG C, mass space velocity 1, sugared concentration is 10%, and tungsten salt is ammonium metatungstate；Rectifying condition: rectification under vacuum, pressure are less than 1kPa, temperature
200 DEG C of degree), condition is precipitated with embodiment 3 (table three).
The influence that three different impurities of table recycle ammonium metatungstate in complex system after saccharide compound catalyzed conversion is (organic molten
Agent is ethyl alcohol, 10 DEG C of temperature, and solvent is with substrate ratios 10:1,3 hours)
As shown in Table 3, the presence of partial impurities can reduce the rate of recovery of tungsten in sugar, but it is still close to 90%.
Comparative example
Recovery method according to the present invention (reaction condition embodiment compared with the result of catalyst recovery method in document
1,2)。
The Comparative result of table four present invention and open source literature catalyst
Compared with the recycling of tungsten salt in document, the catalyst recovery method in the present invention is simpler and the rate of recovery is high.
Therefore, the catalyst recovery method involved in the present invention, catalyst recovery efficiency is high, it is more environmentally-friendly, be convenient for industrialized production.
Claims (5)
1. recycling the method for tungsten-based catalyst in a kind of complex reaction substrate, it is characterised in that:
Complex reaction substrate is rectifying residue after saccharide compound catalyzed conversion, specific to react are as follows: with saccharide compound is anti-
Raw material is answered, carries out catalytic hydrogenation reaction in water on reaction kettle or fixed bed, used catalyst is composite catalyst, packet
Include that catalyst A is Ru/C or skeleton Ni is solid catalyst, catalyst B is tungsten, the nitride of tungsten, the carbide of tungsten, tungsten
Phosphide, the oxide of tungsten, the sulfide of tungsten, the chloride of tungsten, the hydroxide of tungsten, tungsten bronze, wolframic acid, tungstates, partially
One or more of wolframic acid, ammonium metatungstate, para-tungstic acid, paratungstate, peroxide wolframic acid, peroxotungstate, heteropoly tungstic acid,
Hydrogen is filled in reaction, pressure is 3-15 Mpa, reaction temperature 120-310oC, the mass concentration of saccharide compound are 1-60%,
Mass space velocity is 0.1-10h-1；
Reaction product obtains bottom resultant product after rectifying separation ethylene glycol, propylene glycol, and bottom resultant product boiling point is high
In 200oC, wherein containing tungsten salt；Bottom resultant product is glycerol, mannitol, sorbierite, anhydro sorbitol, tungsten salt after rectifying
Mass concentration be 1-50%；
Tungsten salt is precipitated and is recycled by the way that organic solvent is added into bottom resultant product, and obtains higher boiling fusel, You Jirong
Agent is one or more of methanol, propyl alcohol, butanol, tetrahydrofuran, hexamethylene, Ethyl formate, methyl acetate；It is organic molten
The temperature that agent handles kettle base solution is -10-200oC, organic solvent are 100:1-1:10, the tungsten salt rate of recovery with the mass ratio of substrate
More than 90%.
2. according to the method for claim 1, it is characterised in that:
Saccharide compound is starch, cellulose, hemicellulose, sucrose, glucose, fructose, levulan, xylose, soluble oligomeric
One of xylose or two kinds or more.
3. according to the method for claim 1, it is characterised in that:
Reaction condition are as follows: reaction temperature is 180-300 DEG C, and pressure is 3-12 MPa, and the mass concentration of saccharide compound is 10-
50%, mass space velocity is 1-8 h-1。
4. according to the method for claim 1, it is characterised in that:
Precipitation condition: treatment temperature 0-80oC, organic solvent are 10:1-1:1 with substrate mass ratio, and the processing time is 0.5-5h.
5. according to the method for claim 1, it is characterised in that:
Reaction dissolvent is propyl alcohol, and wherein the content of water is lower than 2% in solvent.
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| PL3765432T3 (en) * | 2018-03-14 | 2023-01-02 | Avantium Knowledge Centre B.V. | Process for the production of ethylene glycol |
| US11008269B2 (en) | 2018-03-14 | 2021-05-18 | Avantium Knowledge Centre B.V. | Process for the production of ethylene glycol |
| CN111868019B (en) * | 2018-03-14 | 2023-06-30 | 阿凡田知识中心有限公司 | Continuous or semi-continuous process for the preparation of ethylene glycol and catalyst system for use therein |
| CN108623436B (en) * | 2018-04-08 | 2021-02-19 | 华东师范大学 | Method for converting cellulose into bioethanol by one-pot method |
Citations (2)
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| CN102643165A (en) * | 2011-06-28 | 2012-08-22 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars |
| CN102643164A (en) * | 2011-06-28 | 2012-08-22 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol by continuously hydrocracking cellulose |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643165A (en) * | 2011-06-28 | 2012-08-22 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars |
| CN102643164A (en) * | 2011-06-28 | 2012-08-22 | 中国科学院大连化学物理研究所 | Method for producing ethylene glycol and 1,2-propylene glycol by continuously hydrocracking cellulose |
Non-Patent Citations (1)
| Title |
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| 从钨酸钠溶液制备焦绿石型氧化钨的研究;吴旭;《中国优秀硕士学位论文全文数据库》;20130215(第2期);18-20 * |
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