CN103864576A - Method of preparing ethylene glycol by photo-catalytic formaldehyde conversion - Google Patents
Method of preparing ethylene glycol by photo-catalytic formaldehyde conversion Download PDFInfo
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- CN103864576A CN103864576A CN201410122413.7A CN201410122413A CN103864576A CN 103864576 A CN103864576 A CN 103864576A CN 201410122413 A CN201410122413 A CN 201410122413A CN 103864576 A CN103864576 A CN 103864576A
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- ethylene glycol
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- 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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a method of preparing ethylene glycol by photo-catalytic formaldehyde conversion and relates to ethylene glycol. The method is stable in performance, low in cost and environment-friendly. The method comprises the following steps: adding a nano semiconductor photocatalyst into a formaldehyde-water or formaldehyde-methanol-water solution; after removing oxygen out of the system under stirring, turning on a xenon lamp for light-catalyzed reaction; after reaction, separating a catalyst from the solution; and then separating ethylene glycol from a byproduct to obtain ethylene glycol. By using the light-catalyzed method, the formaldehyde solution is irradiated by ultraviolet light or visible light to photo-catalytically reduce formaldehyde to ethylene glycol in one step, so that photo-catalytic C-C coupling is used in reaction for preparing ethylene glycol by using formaldehyde. The method has the advantages that technical process is simple, reaction conditions are mild, the performance of the catalyst is stable, the reaction activity is high, raw materials are low in price, and environment friendliness is achieved.
Description
Technical field
The present invention relates to ethylene glycol, especially relate to a kind of photochemical catalysis formaldehyde and transform the method for preparing ethylene glycol.
Background technology
Along with the development of human society, the problem of energy and environment seems more and more outstanding, and solving energy shortage and environmental pollution is the important step that keeps social sustainable development.The synthetic technology of photochemical catalysis, as a kind of new synthetic technology, has environmental protection, can utilize the advantages such as renewable energy source, simultaneously also for organic synthesis provides new thinking.At present, photochemical catalysis, in organic reaction, is mainly in field application such as polyreaction, olefin oxidation, carbonylations.But because reaction conversion ratio is low, the reason such as selectivity of product is poor, does not also have the synthetic technology of a photochemical catalysis to realize industrialization so far.But, as a kind of emerging technology, photochemical catalysis is synthetic has powerful vitality, has broad application prospects, at present also in high speed development.
Ethylene glycol, as a kind of important basic chemical industry raw material, is the second largest class alcohol after methyl alcohol, mainly for the production of polyster fibre, coating and wrapping material vibrin in the alcohols material of widely applying.China is the large ethylene glycol consumption of the first in the world big country, although the throughput of ethylene glycol improves year by year, still cannot meet the demand of social production, causes the annual import volume of ethylene glycol to rise year by year.In current industrial, produce ethylene glycol and mainly adopt petroleum path, obtain oxyethane by ethene through gaseous oxidation, then through liquid-phase catalysis hydration preparing ethylene glycol.But due to China's oil inadequate resource, the industrial route of seeking other effective synthesizing glycol is necessary.The R and D of the new synthetic technology of ethylene glycol are also obtaining continuous progress always.Recently, domestic research aspect coal-ethylene glycol has had some important progress.The operational path of " coal-ethylene glycol " is on the basis of the barkite technique of beginning in 1978, adopt and the similar technology of company of Ube Industries Ltd., utilize the carbon monoxide after dehydrogenation purifies, with nitrous acid ester in noble metal catalyst effect, normal pressure and 140 ℃ of left and right gas-solid catalysis synthesis of oxalate, further hydrogenation synthesizing of ethylene glycol.Producing ethylene glycol from oil or coal is all multi-step process, and manufacture method compared complexity, still could not fundamentally reach save energy and environment amenable object.
Formaldehyde industrial be to be prepared by the catalyzed oxidation of methyl alcohol, have advantages of cheap and easy to getly, therefore to prepare ethylene glycol be an economically viable synthetic route to formaldehyde.Synthesizing by photochemical catalysis the research of preparing ethylene glycol does not also have pertinent literature report at present, and ethylene glycol is prepared in the C-C coupling that we utilize Nano semiconductor photocatalyst to realize formaldehyde.C-C linked reaction is the core content of organic synthesis, realizes by photocatalysis technology the compound that high value is prepared in C-C coupling, is considered to one of most potential organic synthesis approach of 21st century.
Chinese patent CN102070407A discloses a kind of method of noble metal support nano titanium dioxide photocatalysis synthesizing glycol, by P25TiO
2nano particle; Prepare nanometer ball or nanometer rod by sol-gel method; Prepare nanotube or nanometer rod is carried out calcination process by hydrothermal method, obtain pure anatase octahedrite, pure rutile, or the TiO of the mixed crystal type nanometer structure of anatase octahedrite and rutile different ratios composition
2; By the nano-TiO of preparation
2add in methanol-water reaction solution, add noble metal source solution simultaneously, vacuumize or pass into nitrogen under magnetic force or mechanical stirring, remove after the oxygen in system, ultraviolet lamp or visible light source that unlatching power is 10~2000W react 10~240h.
Summary of the invention
The object of this invention is to provide stable performance, cost is low, and environment amenable a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol.
Synthetic route of the present invention is as follows:
Concrete steps of the present invention are as follows:
Nano semiconductor photocatalyst is joined in the solution of Formaldehyde-water or formaldehyde-methanol-water, under agitation remove after the oxygen in system, open xenon lamp, carry out light-catalyzed reaction, after reaction, by catalyzer and solution separating, then by ethylene glycol and separation of by-products, obtain ethylene glycol.
The proportioning of described Nano semiconductor photocatalyst and Formaldehyde-water or formaldehyde-methanol-water can be (10~100) mg: (5~10) ml, and wherein, Nano semiconductor photocatalyst is calculated in mass, and Formaldehyde-water or formaldehyde-methanol-water are calculated by volume; Described Nano semiconductor photocatalyst can be selected from conductor oxidate, contain the one in Bi composite oxides, chalcogenide semiconductor compound, niobium tantalum oxysalt etc., and described conductor oxidate can be selected from TiO
2, WO
3deng in one, describedly can be selected from BiVO containing Bi composite oxides
4, Bi
2wO
6, Bi
2mo
3o
12deng in one, described chalcogenide semiconductor compound can be selected from the one in ZnS, CdS etc., described niobium tantalum oxysalt can be selected from KNbO
3, NaTaO
3deng in one; The pattern of described Nano semiconductor photocatalyst can be nano particle, nanometer sheet, nanometer ball or nanometer rod etc.; The crystal formation of described Nano semiconductor photocatalyst can be the mixed crystal of anatase octahedrite, rutile, monoclinic phase, Tetragonal or two kinds of crystalline phases etc.; The described oxygen of under agitation removing in system, can adopt the method that under agitation vacuumizes or pass into rare gas element to remove the oxygen in system; The power of described xenon lamp can be 50~300W; Described light-catalyzed reaction can be carried out light-catalyzed reaction under UV-light or visible ray condition, and the time of reaction can be 6~60h; Described can be by method centrifugal or that staticly settle by catalyzer and solution separating by catalyzer and solution separating; Described again can be through distillation or underpressure distillation by ethylene glycol and separation of by-products by ethylene glycol and separation of by-products.
Described Nano semiconductor photocatalyst by mass percentage can load 0.1%~10% metal or metal oxide, described metal can be from base metal salt MCl
xor precious metal salt, described base metal salt MCl
xin M be the one in Fe, Co, Ni, Cu etc., X is 2 or 3; Described precious metal salt can be selected from H
2ptCl
6, HAuCl
4, PdCl
2, RuCl
3, IrCl
3deng in one.
The present invention utilizes light-catalysed method, with UV-light or radiation of visible light formalin, by formaldehyde one step photo catalytic reduction synthesizing glycol, has realized photochemical catalysis C-C and has been coupled at the reaction that formaldehyde is prepared ethylene glycol.The present invention has compared with existing synthesis technique that technological process is simple, reaction conditions is gentle, catalyst performance stabilised, reactive behavior is high, cost of material is cheap and advantages of environment protection.
Accompanying drawing explanation
Fig. 1 is the liquid chromatogram of glycol product.
Embodiment
Embodiment 1:
By the Na of 5mmol
2wO
42H
2the K of O and 1mmol
2sO
4be dissolved in 80ml distilled water.Drip appropriate concentrated hydrochloric acid, until the pH value of solution approximates 2.Solution is transferred in 100ml autoclave, heated up with the speed of 5 ℃/min, at the temperature of 180 ℃, keep 48h, obtain the WO of Hydrothermal Synthesis
3nanometer rod.Get the WO that 20mg makes
3nanometer rod, joins in the solution of the Formaldehyde-water that 5ml formaldehyde quality percentage composition is 37%.Under agitation vacuumize or pass into rare gas element, remove after the oxygen in system, open the xenon lamp of 200W, under visible ray condition, carry out light-catalyzed reaction 48h.After reacting liquid filtering, liquid-phase chromatographic analysis shows that the transformation efficiency of formaldehyde is 2.37%, and the selectivity of ethylene glycol is 39.2%, and the productive rate of ethylene glycol is 0.93%.
Embodiment 2:
In 80ml methanol aqueous solution, add the Cd (NO of 5mmol
3)
24H
2(the NH of O and 10mmol
3)
2cS, transfers in the autoclave of 100ml after magnetic agitation is even, heats up with the speed of 5 ℃/min, at the temperature of 120 ℃, keeps 48h.After centrifuge washing 3 times, in 60 ℃ of baking ovens, place 12h.After drying grinding, obtain CdS pressed powder.Get the CdS that 10mg makes, join in the solution of the Formaldehyde-water that 5ml formaldehyde quality percentage composition is 20%.Under agitation vacuumize or pass into rare gas element, remove after the oxygen in system, open the xenon lamp of 200W, under visible ray condition, carry out light-catalyzed reaction 24h.After reacting liquid filtering, liquid-phase chromatographic analysis shows that the transformation efficiency of formaldehyde is 2.51%, and the selectivity of ethylene glycol is 51.9%, and the productive rate of ethylene glycol is 1.30%.
Embodiment 3:
By the Bi (NO of 5mmol
3)
25H
2(the NH of O and 0.21mmol
4)
10w
12o
415H
2o is dissolved in respectively in deionized water, after magnetic agitation is even, is mixed in the autoclave of 100ml, heats up with the speed of 5 ℃/min, at the temperature of 180 ℃, keeps 20h.After centrifuge washing 3 times, in 60 ℃ of baking ovens, place 12h.After drying grinding, obtain bismuth tungstate pressed powder.Get the bismuth tungstate that 10mg makes, join in the solution of the Formaldehyde-water that 5ml formaldehyde quality percentage composition is 20%.Under agitation vacuumize or pass into rare gas element, remove after the oxygen in system, open the xenon lamp of 300W, under ultraviolet light conditions, carry out light-catalyzed reaction 12h.After reacting liquid filtering, liquid-phase chromatographic analysis shows that the transformation efficiency of formaldehyde is 4.21%, and the selectivity of ethylene glycol is 51.7%, and the productive rate of ethylene glycol is 2.18%.
Embodiment 4:
By the Bi (NO of 10mmol
3)
25H
2the NH of O and 10mmol
4vO
3join together in the deionized water of 200ml, magnetic agitation 3h makes precipitation evenly.Centrifugal and with after distilled water wash 3 times, dry 12h in the baking oven of 60 ℃.After dried solid abrasive, heat up with the speed of 5 ℃/min, at N
2under atmosphere protection, under 700 ℃ of conditions, calcine 4h, obtain the solid pucherite of monoclinic phase.Get the pucherite that 10mg makes, join in the solution of the Formaldehyde-water that 5ml quality percentage composition is 37%.Under agitation vacuumize or pass into rare gas element, remove after the oxygen in system, open the xenon lamp of 300W, under ultraviolet light conditions, carry out light-catalyzed reaction 6h.After reacting liquid filtering, liquid-phase chromatographic analysis shows that the transformation efficiency of formaldehyde is 10.7%, and the selectivity of ethylene glycol is 35.2%, and the productive rate of ethylene glycol is 3.78%.
Embodiment 5:
By the Nb of 5mmol
2o
5join in the deionized water of 100ml with together with the KOH of 10mmol, after magnetic agitation 30min, transfer in the autoclave of 100ml, heat up with the speed of 5 ℃/min, at the temperature of 180 ℃, keep 60h.After centrifuge washing 3 times, in 60 ℃ of baking ovens, place 12h.After drying grinding, obtain KNbO
3pressed powder.Get the potassium niobate that 10mg makes, join in the solution of the Formaldehyde-water that 5ml formaldehyde quality percentage composition is 20%.Under agitation vacuumize or pass into rare gas element, remove after the oxygen in system, open the xenon lamp of 300W, under ultraviolet light conditions, carry out light-catalyzed reaction 48h.After reacting liquid filtering, liquid-phase chromatographic analysis shows that the transformation efficiency of formaldehyde is 5.59%, and the selectivity of ethylene glycol is 37.9%, and the productive rate of ethylene glycol is 2.12%.
Embodiment 6:
By the Na of 5mmol
2wO
42H
2the K of O and 1mmol
2sO
4be dissolved in 80ml distilled water.Drip appropriate concentrated hydrochloric acid, until the pH value of solution approximates 2.Solution is transferred in 100ml autoclave, heated up with the speed of 5 ℃/min, at the temperature of 180 ℃, keep 48h, obtain the WO of Hydrothermal Synthesis
3nanometer rod.Get the WO that 20mg makes
3nanometer rod, joining 5ml formaldehyde quality percentage composition is 37%, in formaldehyde-methanol-water solution that methanol quality mark is 7.5%.Then be the Platinic chloride of 5mmol/L toward adding 75ul concentration in solution, under agitation vacuumize or pass into rare gas element, remove after the oxygen in system, open the xenon lamp of 300W, under ultraviolet light conditions, carry out light-catalyzed reaction 12h.After reacting liquid filtering, liquid-phase chromatographic analysis shows that the transformation efficiency of formaldehyde is 2.04%, and the selectivity of ethylene glycol is 49.8%, and the productive rate of ethylene glycol is 1.02%.
Embodiment 7:
By the Bi (NO of 10mmol
3)
25H
2the NH of O and 10mmol
4vO
3be dissolved in the salpeter solution of 2mol/L of 100ml, then be adjusted to pH with strong aqua and equal 2, now separate out precipitation.The solution obtaining is packed in autoclave together with precipitation, heat up with the speed of 5 ℃/min, at the temperature of 200 ℃, keep 18h, obtain the monoclinic phase pucherite of Hydrothermal Synthesis.Get the monoclinic phase pucherite that 10mg makes, join in the Formaldehyde-water solution that 5ml formaldehyde quality percentage composition is 37%, and original position adds the CoCl of 80uL0.1mol/L
2solution.Under agitation vacuumize or pass into rare gas element, remove after the oxygen in system, open the xenon lamp of 300W, under ultraviolet light conditions, carry out light-catalyzed reaction 60h.After reacting liquid filtering, liquid-phase chromatographic analysis shows that the transformation efficiency of formaldehyde is 29.2%, and the selectivity of ethylene glycol is 39.1%, and the yield of ethylene glycol is 11.4%.
Claims (10)
1. photochemical catalysis formaldehyde transforms a method of preparing ethylene glycol, it is characterized in that its concrete steps are as follows:
Nano semiconductor photocatalyst is joined in the solution of Formaldehyde-water or formaldehyde-methanol-water, under agitation remove after the oxygen in system, open xenon lamp, carry out light-catalyzed reaction, after reaction, by catalyzer and solution separating, then by ethylene glycol and separation of by-products, obtain ethylene glycol.
2. a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol as claimed in claim 1, the proportioning that it is characterized in that described Nano semiconductor photocatalyst and Formaldehyde-water or formaldehyde-methanol-water is (10~100) mg: (5~10) ml, wherein, Nano semiconductor photocatalyst is calculated in mass, and Formaldehyde-water or formaldehyde-methanol-water are calculated by volume.
3. a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol as claimed in claim 1, it is characterized in that described Nano semiconductor photocatalyst is selected from conductor oxidate, contains the one in Bi composite oxides, chalcogenide semiconductor compound, niobium tantalum oxysalt; Described conductor oxidate can be selected from TiO
2, WO
3in one, describedly can be selected from BiVO containing Bi composite oxides
4, Bi
2wO
6, Bi
2mo
3o
12in one, described chalcogenide semiconductor compound can be selected from the one in ZnS, CdS, described niobium tantalum oxysalt can be selected from KNbO
3, NaTaO
3in one.
4. a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol as claimed in claim 1, and the pattern that it is characterized in that described Nano semiconductor photocatalyst is nano particle, nanometer sheet, nanometer ball or nanometer rod.
5. a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol as claimed in claim 1, and the crystal formation that it is characterized in that described Nano semiconductor photocatalyst is the mixed crystal of anatase octahedrite, rutile, monoclinic phase, Tetragonal or two kinds of crystalline phases.
6. a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol as claimed in claim 1, under agitation removes the oxygen in system described in it is characterized in that, is to adopt the method that under agitation vacuumizes or pass into rare gas element to remove the oxygen in system.
7. a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol as claimed in claim 1, and the power that it is characterized in that described xenon lamp is 50~300W; Described light-catalyzed reaction is to carry out light-catalyzed reaction under UV-light or visible ray condition, and the time of reaction is 6~60h.
8. a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol as claimed in claim 1, it is characterized in that described is by catalyzer and solution separating by method centrifugal or that staticly settle by catalyzer and solution separating; Described is by ethylene glycol and separation of by-products again by ethylene glycol and separation of by-products through distillation or underpressure distillation.
9. a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol as claimed in claim 1, it is characterized in that metal or the metal oxide of described Nano semiconductor photocatalyst load by mass percentage 0.1%~10%.
10. a kind of photochemical catalysis formaldehyde transforms the method for preparing ethylene glycol as claimed in claim 9, it is characterized in that described metal is from base metal salt MCl
xor precious metal salt, described base metal salt MCl
xin M be the one in Fe, Co, Ni, Cu, X is 2 or 3; Described precious metal salt can be selected from H
2ptCl
6, HAuCl
4, PdCl
2, RuCl
3, IrCl
3in one.
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105536770A (en) * | 2016-01-27 | 2016-05-04 | 厦门大学 | Pucherite-based photocatalyst and preparation method and application thereof |
CN106748640A (en) * | 2016-12-29 | 2017-05-31 | 厦门大学 | The method that photocatalytic conversion lignin and its derivative aryl oxide prepare aromatic compound |
CN106831331A (en) * | 2016-12-29 | 2017-06-13 | 厦门大学 | A kind of method that photocatalytic conversion methyl alcohol prepares ethylene glycol |
CN106955705A (en) * | 2017-03-30 | 2017-07-18 | 内蒙古大学 | A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the copper catalyst of a variety of ester type compounds |
CN107739302A (en) * | 2017-11-07 | 2018-02-27 | 中国科学院山西煤炭化学研究所 | A kind of method of photocatalysis methanol Synthesis dimethoxym ethane and ethylene glycol |
CN108456133A (en) * | 2017-02-16 | 2018-08-28 | 中国科学院大连化学物理研究所 | A kind of method of photocatalytic cleavage lignin |
CN112441884A (en) * | 2020-11-30 | 2021-03-05 | 厦门大学 | Method for preparing ethylene glycol through tantalum-based semiconductor photocatalytic methanol coupling |
CN112538003A (en) * | 2020-12-10 | 2021-03-23 | 厦门大学 | Method for directly preparing ethylene glycol from sulfide semiconductor photocatalytic methanol |
CN113024352A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol by photocatalytic methanol conversion |
CN113559855A (en) * | 2021-07-26 | 2021-10-29 | 中国科学院过程工程研究所 | Broad-spectrum absorption catalytic fiber and preparation method and application thereof |
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CN105536770A (en) * | 2016-01-27 | 2016-05-04 | 厦门大学 | Pucherite-based photocatalyst and preparation method and application thereof |
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CN106748640A (en) * | 2016-12-29 | 2017-05-31 | 厦门大学 | The method that photocatalytic conversion lignin and its derivative aryl oxide prepare aromatic compound |
CN106831331A (en) * | 2016-12-29 | 2017-06-13 | 厦门大学 | A kind of method that photocatalytic conversion methyl alcohol prepares ethylene glycol |
CN106831331B (en) * | 2016-12-29 | 2019-10-18 | 厦门大学 | A kind of method that photocatalytic conversion methanol prepares ethylene glycol |
WO2018121402A1 (en) * | 2016-12-29 | 2018-07-05 | 厦门大学 | Method for preparing ethylene glycol by photocatalytic conversion of methanol |
CN108456133B (en) * | 2017-02-16 | 2021-09-21 | 中国科学院大连化学物理研究所 | Method for photocatalytic cracking of lignin |
CN108456133A (en) * | 2017-02-16 | 2018-08-28 | 中国科学院大连化学物理研究所 | A kind of method of photocatalytic cleavage lignin |
CN106955705A (en) * | 2017-03-30 | 2017-07-18 | 内蒙古大学 | A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the copper catalyst of a variety of ester type compounds |
CN107739302A (en) * | 2017-11-07 | 2018-02-27 | 中国科学院山西煤炭化学研究所 | A kind of method of photocatalysis methanol Synthesis dimethoxym ethane and ethylene glycol |
CN113024352A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol by photocatalytic methanol conversion |
CN113024352B (en) * | 2019-12-09 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol by photocatalytic methanol conversion |
CN112441884A (en) * | 2020-11-30 | 2021-03-05 | 厦门大学 | Method for preparing ethylene glycol through tantalum-based semiconductor photocatalytic methanol coupling |
CN112441884B (en) * | 2020-11-30 | 2022-06-21 | 厦门大学 | Method for preparing ethylene glycol through tantalum-based semiconductor photocatalytic methanol coupling |
CN112538003A (en) * | 2020-12-10 | 2021-03-23 | 厦门大学 | Method for directly preparing ethylene glycol from sulfide semiconductor photocatalytic methanol |
CN113559855A (en) * | 2021-07-26 | 2021-10-29 | 中国科学院过程工程研究所 | Broad-spectrum absorption catalytic fiber and preparation method and application thereof |
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