CN106868305A - A kind of method that tungsten-based catalyst is reclaimed in complex reaction substrate - Google Patents
A kind of method that tungsten-based catalyst is reclaimed in complex reaction substrate Download PDFInfo
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- CN106868305A CN106868305A CN201510918759.2A CN201510918759A CN106868305A CN 106868305 A CN106868305 A CN 106868305A CN 201510918759 A CN201510918759 A CN 201510918759A CN 106868305 A CN106868305 A CN 106868305A
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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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- Y02P10/20—Recycling
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Abstract
In the reaction that saccharide compound catalyzed conversion prepares low-carbon alcohols, tungsten-based catalyst all or part of can be dissolved in reaction substrate, it is difficult to is reclaimed, be increased the cost of catalyst.A kind of method the invention provides tungsten-based catalyst is reclaimed in complex reaction substrate, complex reaction substrate is rectifying residue after saccharide compound catalyzed conversion, product is separated after ethylene glycol, propane diols by rectifying, obtain bottom resultant product, bottom resultant product boiling point >=200 DEG C, wherein containing tungsten salt；Tungsten salt is separated out and reclaimed by addition organic solvent in the resultant product of bottom, and obtains higher boiling fusel, tungsten salt mass recovery >=90%.The method that the present invention is provided, catalyst recovery process is simple, catalyst organic efficiency is high, and catalyst circulation superior activity.Additionally, overall process is easy to operation, it is easy to industrialized production.
Description
Technical field
The invention belongs to the catalytic field in biomass chemical industry, more particularly to tungsten salt catalyst
Reclaim, specifically the tungsten salt recovery method in saccharide compound catalyzed conversion after product rectification.
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)。
During the course of the reaction, tungsten can partly or entirely dissolve in the solution, by after distillation process,
High boiling polyol dissolves together with tungsten salt, and both are difficult to separate.It is industrial general by burning
Burning removes organic matter, obtains tungsten oxide, then uses alkali soluble solution, and ammonification is reclaimed, and process is extremely multiple
It is miscellaneous, the relatively low (document 6 of organic efficiency of product：The research of tungsten, China are extracted in tungsten waste
Mining industry, 2008,17:77-81).
The present invention provide catalyst recovery method, have the advantages that it is simple to operate, be easily worked,
Shown in the reaction subsequent catalyst that saccharide compound catalyzed conversion prepares low-carbon alcohols is reclaimed
Selectivity very high.In addition, this course of reaction is present, catalyst organic efficiency is high, be easy to industry
The advantage of change.
The content of the invention
It is an object of the invention to provide recovery tungsten-based catalyst in a kind of complex reaction substrate
Method.The method that tungsten salt is separated out using organic solvent, realizes saccharide compound selective conversion
For the tungsten for being dissolved after low-carbon alcohols in the solution is reclaimed.
To achieve the above object, the technical scheme taken of the present invention is：
Complex reaction substrate is rectifying residue after saccharide compound catalyzed conversion, specific reaction
For：With saccharide compound as reaction raw materials, it is catalyzed in water on reactor or fixed bed
Hydrogenation reaction, the catalyst for being used is composite catalyst, including catalyst A be Ru/C or
Skeleton Ni is solid catalyst, and catalyst B is tungsten, the nitride of tungsten, the carbonization of tungsten
Thing, the phosphide of tungsten, the oxide of tungsten, the sulfide of tungsten, the chloride of tungsten, the hydrogen-oxygen of tungsten
Compound, tungsten bronze, wolframic acid, tungstates, metatungstic acid, ammonium metatungstate, para-tungstic acid, para-tungstic acid
One or more in salt, peroxide wolframic acid, peroxotungstate, heteropoly tungstic acid, in reaction
Filling hydrogen, pressure is 3-15Mpa, 120-310 DEG C of reaction temperature, the matter of saccharide compound
Amount concentration is 1-60%, and mass space velocity is 0.1-10h-1；
Product obtains bottom resultant product after separating ethylene glycol, propane diols by rectifying,
Bottom resultant product boiling point is higher than 200 DEG C, wherein containing tungsten salt；
Tungsten salt is separated out and received by addition organic solvent in the resultant product of bottom, and is obtained
Higher boiling fusel, the temperature of organic solvent treatment kettle base solution is -10-100 DEG C, and organic solvent is same
Substrate mass ratio is 100:1-1:10, the tungsten salt rate of recovery is more than 90%.
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.
Bottom resultant product is glycerine, mannitol, mountain after rectifying separates ethylene glycol, propane diols
Pears alcohol, anhydro sorbitol, butanediol, the polyalcohol of C6-C18, the mass concentration of tungsten salt is
1-50%.
By to adding organic solvent in the resultant product of bottom, the method that tungsten salt is separated out and received,
The organic solvent for using is methyl alcohol, ethanol, propyl alcohol, butanol, tetrahydrofuran, hexamethylene, first
One or more in acetoacetic ester, methyl acetate.
It is preferred to separate out condition：Temperature is 0-80 DEG C, and organic solvent is with substrate mass ratio
10:1-1:1, process time is 0.5-5h, by centrifugation rotating speed more than 200rpm.
It is preferred that reaction dissolvent can be methyl alcohol, ethanol, propyl alcohol in one or more,
Wherein the content of solvent reclaimed water is less than 2%.
The tungsten salt ratio of recovery is more than 90%, and the tungsten salt of recovery is anti-in saccharide compound conversion
Should be active constant.
Tungsten salt mass content≤0.005% in the higher boiling fusel of recovery.
The invention has the advantages that：
1. catalyst recovery process is simple, is easy to the raising of whole process economy.
2. with the saccharide compound in biomass as raw material, there is recyclability, accord with
Close the requirement of sustainable development.
3. the organic efficiency of catalyst is high, and energy consumption is low 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
Present disclosure 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 reactors, nitrogen is passed through
Gas replace three gases after, temperature programming to 220 DEG C, at this moment by the glucose of 40wt% and partially
Ammonium tungstate is driven into reactor by pump, while taking liquid, mass space velocity is 2.Reacted
Cheng Zhong, takes out product, is separated on high performance liquid chromatography calcium type ion exchange column and with poor
Show that refraction detector is detected.To products such as propane diols, ethylene glycol and glycerine in product yield
Calculated.This reaction can be carried out in fixed bed again, and operation is similar, solution, the air speed of sugar
It is adjustable with reaction temperature.
According to the difference of tungsten species, it is also possible to which tungsten catalyst is positioned in reaction vessel in advance.
Embodiment 2
Obtain complex substrate：
Solution filtering after reaction, removes solid matter, under reduced pressure distillation water removal, and rectifying is obtained
Ethylene glycol and propane diols, remain the mixture of high boiling alcohol and tungsten salt afterwards.
Embodiment 3
Separate out experiment：
Bottom product after rectifying is mixed with ethanol, temperature is 10 DEG C, both mass ratioes are 1:5,
And quickly stir, stir speed (S.S.) is 600rpm, and bottom product is dispersed after making rectifying, quiet
Put 12 hours.Filtering is then centrifuged for, speed is 1000rpm, is washed with ethanol solution 3 times,
It is dried to obtain solid powder.
Product same ethanol in bottom after rectifying, hexamethylene are mixed, rectifying substrate with solvent weight
Than being 5:1, ethanol is 1 with the volume ratio of hexamethylene:1, and quickly stir, stir speed (S.S.) is
600rpm, bottom product is dispersed after making rectifying, stands 12 small layereds.It is then centrifuged for
Filtering, speed is 1000rpm, is washed with ethanol solution 3 times, is dried to obtain solid powder.
Can change response parameter to obtain the tungsten salt rate of recovery high according to different experiments.
Filtrate decompression distillation after filtering, carries out solvent recovery, obtains higher boiling fusel.
Embodiment 4
The organic efficiency of tungsten-based catalyst under different solvents, reaction condition is (anti-with embodiment 1,2
Answer condition：220 DEG C, mass space velocity is 1, and sugared concentration is 10%, and tungsten salt is ammonium metatungstate；Essence
Evaporate condition：Rectification under vacuum, pressure is less than 1kPa, 200 DEG C of temperature), condition is separated out with implementation
Example 3 (table one).
Under the different solvents of table one, the tungsten salt rate of recovery (precipitation process：10 DEG C of temperature, organic solvent
With substrate ratios 10:1,3 hour)
As shown in Table 1, ethanol solution shows good selectivity, and other solvents can influence it
The precipitation effect of tungsten salt.Wherein, under ethanol+cyclohexane solvent low concentration ammonium metatungstate return
Yield reaches 95%.
Embodiment 5
Tungsten salt under different condition reclaims result, and reaction condition is with (the reaction condition of embodiment 1,2：
220 DEG C, mass space velocity is 1, and sugared concentration is 10%, and tungsten salt is ammonium metatungstate；Rectifying condition：
Rectification under vacuum, pressure is less than 1kPa, 200 DEG C of temperature), condition is separated out with (the table of embodiment 3
Two).
Under the conditions of the different precipitations of table two, glucose catalyzed conversion prepares the tungsten catalyst of low-carbon alcohols
Reclaim result (organic solvent is ethanol)
As shown in Table 2, reaction condition also can significantly change the organic efficiency of catalyst, excellent
Change reaction condition to be to 25 DEG C of solvents, substrate ratio is 1 hour 3, time, and ammonium metatungstate is returned
Tungsten weight content is less than 0.0032% during yield reaches 97%, and organic high boiling alcohol.
Embodiment 6
Impurity exist to tungsten-based catalyst reclaim influence (table three), reaction condition with embodiment 1,
2 (reaction conditions：220 DEG C, mass space velocity is 1, and sugared concentration is 10%, and tungsten salt is ammonium metatungstate；
Rectifying condition：Rectification under vacuum, pressure is less than 1kPa, 200 DEG C of temperature), condition is separated out with real
Apply example 3 (table three).
The different impurities of table three are returned to ammonium metatungstate in complex system after saccharide compound catalyzed conversion
(organic solvent is ethanol, 10 DEG C of temperature, and solvent is with substrate ratios 10 for the influence of receipts:1,3 is small
When)
As shown in Table 3, the presence of partial impurities can reduce the rate of recovery of tungsten in sugar, but its
Still close to 90%.
Comparative example
Recovery method involved in the present invention (reacts with the results contrast of catalyst recovery method in document
Condition Example 1,2).
The Comparative result of the present invention of table four and open source literature catalyst
Compared with the recovery of tungsten salt in document, the present invention in catalyst recovery method it is simpler,
And the rate of recovery is high.Therefore, the catalyst recovery method being related in the present invention, catalyst is reclaimed
Efficiency high, it is more environmentally-friendly, be easy to industrialized production.
Claims (9)
1. a kind of method that tungsten-based catalyst is reclaimed in complex reaction substrate, it is characterised in that：
Complex reaction substrate is rectifying residue after saccharide compound catalyzed conversion, specific reaction
For：With saccharide compound as reaction raw materials, it is catalyzed in water on reactor or fixed bed
Hydrogenation reaction, the catalyst for being used is composite catalyst, including catalyst A be Ru/C or
Skeleton Ni is solid catalyst, and catalyst B is tungsten, the nitride of tungsten, the carbonization of tungsten
Thing, the phosphide of tungsten, the oxide of tungsten, the sulfide of tungsten, the chloride of tungsten, the hydrogen-oxygen of tungsten
Compound, tungsten bronze, wolframic acid, tungstates, metatungstic acid, ammonium metatungstate, para-tungstic acid, para-tungstic acid
One or more in salt, peroxide wolframic acid, peroxotungstate, heteropoly tungstic acid, in reaction
Filling hydrogen, pressure is 3-15Mpa, 120-310 DEG C of reaction temperature, the matter of saccharide compound
Amount concentration is 1-60%, and mass space velocity is 0.1-10h-1；
Product is separated after ethylene glycol, propane diols by rectifying, obtains the remaining product in bottom
Thing, bottom resultant product boiling point >=200 DEG C, wherein containing tungsten salt；
Tungsten salt is separated out and reclaimed by addition organic solvent in the resultant product of bottom, and
To higher boiling fusel, the temperature of organic solvent treatment kettle base solution is -10-200 DEG C, organic solvent
It is 100 with the mass ratio of substrate:1-1:10, tungsten salt mass recovery >=90%.
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：
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.
4. in accordance with the method for claim 1, it is characterised in that：
The higher boiling fusel of bottom resultant product is mainly glycerine, mannitol, sorb after rectifying
One or more in alcohol, anhydro sorbitol, butanediol, the polyalcohol of C6-C18,
The mass concentration of tungsten salt is 1-50%.
5. in accordance with the method for claim 1, it is characterised in that：
Tungsten salt is set to separate out and reclaim by way of adding organic solvent in bottom resultant product,
Organic solvent be methyl alcohol, ethanol, propyl alcohol, butanol, tetrahydrofuran, hexamethylene, Ethyl formate,
One or more in methyl acetate.
6. in accordance with the method for claim 1, it is characterised in that：
It is preferred that separating out condition：Treatment temperature is 0-80 DEG C, and organic solvent is with substrate mass ratio
10:1-1:1, process time is 0.5-5h.
7. in accordance with the method for claim 1, it is characterised in that：
It is preferred that reaction dissolvent can be methyl alcohol, ethanol, propyl alcohol in one or more,
Wherein the content of solvent reclaimed water is less than 2%.
8. in accordance with the method for claim 1, it is characterised in that：
The tungsten salt ratio of recovery exceedes >=90%, and the tungsten salt of recovery is in saccharide compound conversion
Reactivity is constant.
9. in accordance with the method for claim 1, it is characterised in that：The higher boiling of recovery is miscellaneous
Tungsten salt mass content≤0.005% in alcohol.
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Cited By (4)
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| CN108623436A (en) * | 2018-04-08 | 2018-10-09 | 华东师范大学 | A kind of one kettle way conversion cellulose is the method for bio-ethanol |
| WO2019175369A1 (en) * | 2018-03-14 | 2019-09-19 | Avantium Knowledge Centre B.V. | Process for the production of ethylene glycol |
| CN111868019A (en) * | 2018-03-14 | 2020-10-30 | 阿凡田知识中心有限公司 | Continuous or semi-continuous process for the production of ethylene glycol and catalyst system for use therein |
| CN111868017A (en) * | 2018-03-14 | 2020-10-30 | 阿凡田知识中心有限公司 | Process and heterogeneous catalyst composition for the production of ethylene glycol |
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| 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 |
| 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 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019175369A1 (en) * | 2018-03-14 | 2019-09-19 | Avantium Knowledge Centre B.V. | Process for the production of ethylene glycol |
| CN111868018A (en) * | 2018-03-14 | 2020-10-30 | 阿凡田知识中心有限公司 | Process for the production of ethylene glycol |
| CN111868019A (en) * | 2018-03-14 | 2020-10-30 | 阿凡田知识中心有限公司 | Continuous or semi-continuous process for the production of ethylene glycol and catalyst system for use therein |
| CN111868017A (en) * | 2018-03-14 | 2020-10-30 | 阿凡田知识中心有限公司 | Process and heterogeneous catalyst composition 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 |
| CN111868017B (en) * | 2018-03-14 | 2023-05-26 | 阿凡田知识中心有限公司 | Process and heterogeneous catalyst composition 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 |
| CN111868018B (en) * | 2018-03-14 | 2023-08-04 | 阿凡田知识中心有限公司 | Process for producing ethylene glycol |
| CN108623436A (en) * | 2018-04-08 | 2018-10-09 | 华东师范大学 | A kind of one kettle way conversion cellulose is the method for bio-ethanol |
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