CN103864576B - Method of preparing ethylene glycol by photo-catalytic formaldehyde conversion - Google Patents

Method of preparing ethylene glycol by photo-catalytic formaldehyde conversion Download PDF

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CN103864576B
CN103864576B CN201410122413.7A CN201410122413A CN103864576B CN 103864576 B CN103864576 B CN 103864576B CN 201410122413 A CN201410122413 A CN 201410122413A CN 103864576 B CN103864576 B CN 103864576B
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ethylene glycol
formaldehyde
photochemical catalysis
water
reaction
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CN103864576A (en
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王野
沈泽斌
范文青
谢顺吉
张庆红
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Xiamen University
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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
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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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

A kind of photochemical catalysis formaldehyde conversion prepares the method for ethylene glycol
Technical field
The present invention relates to ethylene glycol, especially relate to a kind of method that photochemical catalysis formaldehyde conversion prepares ethylene glycol.
Background technology
Along with the development of human society, the problem of energy and environment seems more and more outstanding, and solution energy shortage and environmental pollution are the important steps keeping social sustainable development.Photochemical catalysis synthetic technology, 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 applied in fields such as polyreaction, olefin oxidation, carbonylations.But because reaction conversion ratio is low, the reasons such as selectivity of product difference, also do not have a photochemical catalysis synthetic technology to realize industrialization so far.But, as a kind of emerging technology, photochemical catalysis synthesis has powerful vitality, has broad application prospects, is also in high speed development at present.
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 widely applied.China is the first in the world large ethylene glycol consumption big country, although the throughput of ethylene glycol improves year by year, still cannot meet the demand of social production, the import volume causing ethylene glycol annual rises year by year.Current industrial is produced 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 commercial routes 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 in the coal-ethylene glycol progress that had some important.The operational path of " coal-ethylene glycol " is on the basis of the barkite technique of beginning in 1978, adopt the technology similar with company of Ube Industries Ltd., carbon monoxide after utilizing dehydrogenation to purify, with nitrous acid ester in noble metal catalyst effect, normal pressure and about 140 DEG C 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 is complicated, still fundamentally could not reach save energy and environment amenable object.
Formaldehyde is industrially prepared by the catalyzed oxidation of methyl alcohol, has advantage cheap and easy to get, and therefore formaldehyde prepares ethylene glycol is an economically viable synthetic route.The research being prepared ethylene glycol by photochemical catalysis synthesis does not also have pertinent literature to 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 the compound that C-C coupling prepares high value, be considered to one of 21st century most potential organic synthesis approach by photocatalysis technology.
Chinese patent CN102070407A discloses a kind of method of noble metal support nano titanium dioxide photocatalysis synthesizing glycol, by P25TiO 2nano particle; Nanometer ball or nanometer rod is prepared by sol-gel method; Prepare nanotube by hydrothermal method or nanometer rod carries out calcination process, 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 under magnetic force or mechanical stirring or pass into nitrogen, after the oxygen in removing system, open ultraviolet lamp that power is 10 ~ 2000W or visible light source carries out reaction 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 conversion prepares the method for 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, after the oxygen under agitation removing system, open xenon lamp, carry out light-catalyzed reaction, by catalyzer and solution separating after reaction, 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, containing the one in Bi composite oxides, semiconductor sulfide, niobium tantalum oxysalt etc., 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 semiconductor sulfide can be selected from the one in ZnS, CdS etc., and 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 etc. of anatase octahedrite, rutile, monoclinic phase, Tetragonal or two kinds of crystalline phases; Oxygen in described under agitation removing system, can adopt the oxygen under agitation vacuumizing or pass in the method removing system of rare gas element; The power of described xenon lamp can be 50 ~ 300W; Described light-catalyzed reaction can carry out light-catalyzed reaction under UV-light or visible light conditions, and the time of reaction can be 6 ~ 60h; Described by catalyzer and solution separating by method that is centrifugal or that staticly settle by catalyzer and solution separating; Described again ethylene glycol and separation of by-products are can be passed through distillation or underpressure distillation by ethylene glycol and separation of by-products.
Described Nano semiconductor photocatalyst by mass percentage can the metal of load 0.1% ~ 10% or metal oxide, and described metal can from base metal salt MCl xor precious metal salt, described base metal salt MCl xin M be 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, achieves photochemical catalysis C-C and is coupled at the reaction that formaldehyde prepares 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 are high, low in raw material price 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, with the ramp of 5 DEG C/min, at the temperature of 180 DEG C, keep 48h, obtain the WO of Hydrothermal Synthesis 3nanometer rod.Get the WO that 20mg is obtained 3nanometer rod, joining 5ml formaldehyde mass percentage is in the solution of the Formaldehyde-water of 37%.Under agitation vacuumize or pass into rare gas element, after the oxygen in removing system, opening the xenon lamp of 200W, under visible light conditions, 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:
Cd (the NO of 5mmol is added in 80ml methanol aqueous solution 3) 24H 2(the NH of O and 10mmol 3) 2cS, transfers in the autoclave of 100ml after magnetic agitation is even, with the ramp of 5 DEG C/min, at the temperature of 120 DEG C, keeps 48h.After centrifuge washing 3 times, in 60 DEG C of baking ovens, place 12h.Namely CdS pressed powder is obtained after drying grinding.Get the CdS that 10mg is obtained, joining 5ml formaldehyde mass percentage is in the solution of the Formaldehyde-water of 20%.Under agitation vacuumize or pass into rare gas element, after the oxygen in removing system, opening the xenon lamp of 200W, under visible light conditions, 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 deionized water respectively, is mixed in the autoclave of 100ml, with the ramp of 5 DEG C/min, at the temperature of 180 DEG C, keeps 20h after magnetic agitation is even.After centrifuge washing 3 times, in 60 DEG C of baking ovens, place 12h.Namely bismuth tungstate pressed powder is obtained after drying grinding.Get the bismuth tungstate that 10mg is obtained, joining 5ml formaldehyde mass percentage is in the solution of the Formaldehyde-water of 20%.Under agitation vacuumize or pass into rare gas element, after the oxygen in removing system, opening 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 DEG C.After dried solid abrasive, with the ramp of 5 DEG C/min, at N 2under atmosphere protection, under 700 DEG C of conditions, calcine 4h, obtain the solid pucherite of monoclinic phase.Get the pucherite that 10mg is obtained, joining 5ml mass percentage is in the solution of the Formaldehyde-water of 37%.Under agitation vacuumize or pass into rare gas element, after the oxygen in removing system, opening 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 together with the KOH of 10mmol in the deionized water of 100ml, transfer in the autoclave of 100ml after magnetic agitation 30min, with the ramp of 5 DEG C/min, at the temperature of 180 DEG C, keep 60h.After centrifuge washing 3 times, in 60 DEG C of baking ovens, place 12h.Namely KNbO is obtained after drying grinding 3pressed powder.Get the potassium niobate that 10mg is obtained, joining 5ml formaldehyde mass percentage is in the solution of the Formaldehyde-water of 20%.Under agitation vacuumize or pass into rare gas element, after the oxygen in removing system, opening 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, with the ramp of 5 DEG C/min, at the temperature of 180 DEG C, keep 48h, obtain the WO of Hydrothermal Synthesis 3nanometer rod.Get the WO that 20mg is obtained 3nanometer rod, joining 5ml formaldehyde mass percentage is 37%, and methanol quality mark is in the formaldehyde-methanol-water solution of 7.5%.Then in solution, add the Platinic chloride that 75ul concentration is 5mmol/L, under agitation vacuumize or pass into rare gas element, after the oxygen in removing 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 the 2mol/L of 100ml, then be adjusted to pH with strong aqua and equal 2, now separate out precipitation.The solution obtained is loaded in autoclave together with precipitation, with the ramp of 5 DEG C/min, at the temperature of 200 DEG C, keeps 18h, obtain the monoclinic phase pucherite of Hydrothermal Synthesis.Get the monoclinic phase pucherite that 10mg is obtained, joining 5ml formaldehyde mass percentage is in the Formaldehyde-water solution of 37%, and original position adds the CoCl of 80uL0.1mol/L 2solution.Under agitation vacuumize or pass into rare gas element, after the oxygen in removing system, opening 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 conversion prepares a method for 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, after the oxygen under agitation removing system, open xenon lamp, carry out light-catalyzed reaction, by catalyzer and solution separating after reaction, then by ethylene glycol and separation of by-products, obtain ethylene glycol;
Described Nano semiconductor photocatalyst is selected from conductor oxidate, containing the one in Bi composite oxides, semiconductor sulfide, niobium tantalum oxysalt; Described conductor oxidate is selected from TiO 2, WO 3in one, be describedly selected from BiVO containing Bi composite oxides 4, Bi 2wO 6, Bi 2mo 3o 12in one, described semiconductor sulfide is selected from the one in ZnS, CdS, and described niobium tantalum oxysalt is selected from KNbO 3, NaTaO 3in one.
2. a kind of photochemical catalysis formaldehyde conversion prepares the method for 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 conversion prepares the method for ethylene glycol as claimed in claim 1, it is characterized in that the pattern of described Nano semiconductor photocatalyst is nano particle, nanometer sheet, nanometer ball or nanometer rod.
4. a kind of photochemical catalysis formaldehyde conversion prepares the method for ethylene glycol as claimed in claim 1, it is characterized in that the crystal formation of described Nano semiconductor photocatalyst is anatase octahedrite, rutile, monoclinic phase or Tetragonal.
5. a kind of photochemical catalysis formaldehyde conversion prepares the method for ethylene glycol as claimed in claim 1, the oxygen under agitation removing system described in it is characterized in that, is to adopt the oxygen under agitation vacuumizing or pass in the method removing system of rare gas element.
6. a kind of photochemical catalysis formaldehyde conversion prepares the method for ethylene glycol as claimed in claim 1, it is characterized in that the power of described xenon lamp is 50 ~ 300W; Described light-catalyzed reaction carries out light-catalyzed reaction under UV-light or visible light conditions, and the time of reaction is 6 ~ 60h.
7. a kind of photochemical catalysis formaldehyde conversion prepares the method for ethylene glycol as claimed in claim 1, it is characterized in that described is by catalyzer and solution separating by catalyzer and solution separating by method that is centrifugal or that staticly settle; Described ethylene glycol and separation of by-products being through again is distilled ethylene glycol and separation of by-products.
8. a kind of photochemical catalysis formaldehyde conversion prepares the method for ethylene glycol as claimed in claim 7, it is characterized in that described distillation adopts underpressure distillation.
9. a kind of photochemical catalysis formaldehyde conversion prepares the method for 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 conversion prepares the method for 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 one in Fe, Co, Ni, Cu, X is 2 or 3; Described precious metal salt is selected from H 2ptCl 6, HAuCl 4, PdCl 2, RuCl 3, IrCl 3in one.
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CN105536770B (en) * 2016-01-27 2017-11-24 厦门大学 A kind of pucherite based photocatalyst and preparation method and application
CN106748640B (en) * 2016-12-29 2019-10-18 厦门大学 The method that photocatalytic conversion lignin and its derivative aryl oxide prepare aromatic compound
CN106831331B (en) * 2016-12-29 2019-10-18 厦门大学 A kind of method that photocatalytic conversion methanol prepares ethylene glycol
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
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
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
CN112441884B (en) * 2020-11-30 2022-06-21 厦门大学 Method for preparing ethylene glycol through tantalum-based semiconductor photocatalytic methanol coupling
CN112538003B (en) * 2020-12-10 2022-07-01 厦门大学 Method for directly preparing ethylene glycol from sulfide semiconductor photocatalytic methanol
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CN102070407B (en) * 2011-01-25 2013-08-07 鄂尔多斯市联科清洁能源技术有限公司 Method for synthesizing ethylene glycol from noble metal load nanometer titanium dioxide through photocatalysis

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