CN107243345A - A kind of O composite metallic oxide catalyst that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction - Google Patents
A kind of O composite metallic oxide catalyst that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction Download PDFInfo
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a kind of O composite metallic oxide catalyst that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction, including active component and auxiliary agent, according to catalyst metals proportion of composing, the nitrate solution corresponding with metallic element in active component transition metal and auxiliary agent metal oxides is prepared；Corresponding nitrate solution and alkali lye are prepared into catalyst using coprecipitation, pH value, aged at room temperature is adjusted, filtering, washing, are dried, roasting, the amount that the consumption of each component makes final active component molar percentage account for catalyst is 40 85%, and the amount that auxiliary agent molar percentage accounts for catalyst is 15 60%.O composite metallic oxide catalyst is prepared using coprecipitation progress, preparation process is simple, and catalyst cost is relatively low, environment friendly and pollution-free, solid catalyst is easily separated with product, and the reaction condition using normal pressure, low temperature, short reaction time is gentle, catalytic activity is high, and prospects for commercial application is preferable.
Description
Technical field
The invention belongs to technical field of chemical engineering catalysts, and in particular to a kind of solid catalyst for ester exchange reaction,
Relate more specifically to a kind of ethylene carbonate and methanol ester exchange synthesizing glycol and the metal composite oxide of dimethyl carbonate
Catalyst and its preparation method and application.
Background technology
Ethylene glycol is a kind of important basic chemical industry raw material, mainly for the production of polyester.China's ethylene glycol market is not for should
Ask, be global ethylene glycol main body entrance market.The industrial product route of ethylene glycol mainly has two major classes：Oil or natural gas base second
Alkene route, coal base oxalic acid ester through hydrogenation route.Oil or natural gas base ethene route have the shortcomings that water consume is big, high energy consumption, by
Eastern cheap products impact, domestic ethene route preparing ethylene glycol is lacked competitiveness.Coal base hydrogenation of oxalate for preparing ethylene glycol route has
Resource and cost advantage, but unstable product quality, it is impossible to fully meet the demand of downstream polyester enterprise user.Therefore, open
The ethylene glycol production line tool for sending out new has very important significance.
Dimethyl carbonate is a kind of very important organic chemicals, can substitute the chloromethanes, phosgene, sulfuric acid two of severe toxicity
The reactions such as the reagents such as methyl esters are methylated, methoxylation, carbonylation, it is wide to prepare a variety of high added value fine chemicals
It is general to be applied to the fields such as medicine, synthetic material, coating, makrolon.At present, China's dimethyl carbonate is main by propene carbonate
It is made with methanol ester exchange reaction, the production method is influenceed larger by accessory substance propane diols quality and market situation.At present I
State's propane diols production capacity is seriously superfluous, in addition the petroleum base propylene feedstocks of high price so that dimethyl carbonate industry development faces larger
Pressure.It would therefore be highly desirable to develop more economical technology path.
Ester exchange reaction is carried out using ethylene carbonate and methanol as raw material, ethylene glycol and carbonic acid diformazan can be produced simultaneously
Ester, the technology path has the advantages that energy consumption is low, product purity is high, added value is high, good economy performance.Moreover, the reaction is atom
Economy is reacted, and atom utilization reaches 100%, belongs to the process for cleanly preparing of " zero-emission ", meets contemporary Green Chemistry
Development trend.
The core of ethylene carbonate and methanol ester exchange reaction is high performance catalyst, and it is broadly divided into homogeneous and non-equal
The class of phase two.Homogeneous catalyst mainly has sodium methoxide, alkali metal hydroxide, alkali carbonate, alkali ionic liquid etc..Such
Catalyst typically has preferable catalytic activity, but there is many deficiencies in separation and service life, adds production cost,
Micro or trace catalyst residual may cause large effect to product quality.Heterogeneous catalysis mainly have it is single or
Metal composite oxide, load metal oxide, molecular sieve, ion exchange resin etc..Such catalyst and homogeneous catalyst
Compared to generally existing catalytic activity and the not high defect of selectivity, but catalyst service life is longer, is easily separated with product, production
Product purity is high.Therefore, the main goal in research that efficient heterogeneous catalysis is ester exchange reaction is developed.
Patent CN 201010135117.2, patent CN 201510700289.2 report a kind of flower-like micro/nano structure respectively
Magnesia catalyst, a kind of graphene oxide-loaded magnesia catalyst, both catalyst show preferable ester and handed over
Activity is changed, in ethylene carbonate and methanol ester exchange reaction, under conditions of reaction temperature is 140 DEG C, pressurizeed, carbonic acid diformazan
Ester yield reaches 90%, but flower-like micro/nano structure magnesia catalyst preparation process is relative complex and needs to use template,
The processing such as graphene oxide carrier needs to aoxidize graphene, pickling, preparation flow is long, and both catalyst costs are relative
It is higher, be not suitable for commercial Application, and also reaction condition is relatively harsh.Patent CN 201410125570.3 reports a kind of total silicon
Beta molecular sieve catalysts, catalysis methanol and propene carbonate ester exchange reaction, are 100 DEG C, under pressurized conditions in reaction temperature,
Dimethyl carbonate yield reaches 71%.Patent CN 201410355429.2 reports a kind of highly basic Nano composite quaternary phosphonium salt resin
The ester exchange reaction of catalyst, catalysis ethylene carbonate and methanol, dimethyl carbonate yield is 60.2%.Similarly, it is above-mentioned
Molecular sieve and resinae catalyst preparation long flow path, and exist and need to use that high price template, crystallization time be longer, You Jirong
The problems such as agent consumption is big, causes catalyst preparation cost high.Patent CN 201610365870.8 reports a kind of composite solid
Base catalyst Ca-Al-O-X (X=CO3 2-、NO3 -、F-、Cl-、Br-Deng), for the ester exchange reaction of propene carbonate and methanol,
Dimethyl carbonate yield is up to about 55%, and catalyst is containing the stronger halide ion that is corrosive, to consersion unit and point
It is higher from equipment requirement.As can be seen here, cheap, efficient, environmental protection, the exploitation of the simple heterogeneous catalysis of preparation process are handed over ester
Changing reaction just has actual industrial application value.
The content of the invention
It is an object of the invention to provide a kind of environment-friendly, Cheap highly effective, preparation process is simple and has preferably industry
The metal composite oxide ester exchange catalyst of application prospect, the ester exchange reaction for methanol and ethylene carbonate.
The present invention is realized by following technical proposals.
A kind of composition metal oxidation that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction that the present invention is provided
Thing catalyst, the catalyst contains the component of following molar percentages：Active component 40-85%；Auxiliary agent 15-60%；
The active component is a kind of oxide in transition metal Mn, Fe, Co, Ni, Cu, Zn；
The auxiliary agent is MgO, Y2O3、ZrO2、La2O3、CeO2、Al2O3One or more in metal oxide.
Correspondingly, the present invention and then the O composite metallic oxide catalyst for preparing ethylene glycol co-producing dimethyl carbonate is given
Preparation method, comprise the following steps：
1) according to catalyst metals proportion of composing, prepared and active component transition metal and auxiliary agent according to molar percentage
The corresponding nitrate solution of metallic element in metal oxide；
2) it is at ambient temperature, 2 by corresponding nitrate solution and mol ratio：1 NaOH and Na2CO3Alkali lye is using altogether
The precipitation method prepare catalyst, and precipitation process is sufficiently stirred for, and are adjusted to pH value for 9-12, keep aged at room temperature, filter, wash,
Dry, roasting, the amount that the consumption of each component makes final active component molar percentage account for catalyst is 40-85%, and auxiliary agent rubs
The amount that your percentage accounts for catalyst is 15-60%.
Further, the step 1) in, corresponding nitrate is dissolved in deionized water, concentration is formed for 0.5-
2mol/L mixed solution.
Further, the step 2) in, keep aged at room temperature 3-12h, filtering, washing, 110-120 DEG C of dry 10h, 300-
900 DEG C of roasting 5h.
The present invention gives a kind of application of O composite metallic oxide catalyst in ethylene glycol co-producing dimethyl carbonate,
According to mol ratio it is 1 by ethylene carbonate and methanol：(2-10) ratio is mixed, and O composite metallic oxide catalyst is being carried out into ester
The 1-8wt.% that molar percentage is ethylene carbonate amount is added during exchange reaction, reaction temperature is 30-70 DEG C, and reaction pressure is
Normal pressure, the reaction time is 0.5-6h.
Through using after O composite metallic oxide catalyst of the present invention so that the ethylene in ethylene glycol co-producing dimethyl carbonate
Alkene ester conversion rate is not less than 60.2%, and dimethyl carbonate yield is not less than 47.1%, and ethylene glycol yield is not less than 45.1%.
Compared with prior art, the beneficial effects of the present invention are：Composition metal oxidation is prepared using coprecipitation progress
Thing catalyst, preparation process is simple, and catalyst cost is relatively low, environment friendly and pollution-free, and solid catalyst is easily separated with product, reacts bar
Part is gentle (normal pressure, low temperature, short reaction time), and catalytic activity is high, and prospects for commercial application is preferable.
Embodiment
With reference to embodiment, the invention will be described in further detail, but be not intended as to invention do any limitation according to
According to.
A kind of preparation for O composite metallic oxide catalyst for preparing ethylene glycol co-producing dimethyl carbonate that the present invention is provided
Method, comprises the following steps：
1) according to catalyst metals proportion of composing, prepared and active component transition metal and auxiliary agent according to molar percentage
The corresponding nitrate solution of metal oxide metal element, corresponding nitrate is dissolved in deionized water, forms concentration
For 0.5-2mol/L mixed solution.
2) it is at ambient temperature, 2 by corresponding nitrate solution and mol ratio：1 NaOH and Na2CO3Alkali lye is using altogether
The precipitation method prepare catalyst, and precipitation process is sufficiently stirred for, and are adjusted to pH value for 9-12, keep aged at room temperature 3-12h, filter,
Washing, 110-120 DEG C of dry 10h, 300-900 DEG C of roasting 5h, the consumption of each component makes final active component molar percentage
The amount for accounting for catalyst is 40-85%, and the amount that auxiliary agent molar percentage accounts for catalyst is 15-60%.
Wherein, active component is a kind of oxide in transition metal Mn, Fe, Co, Ni, Cu, Zn；
Auxiliary agent is MgO, Y2O3、ZrO2、La2O3、CeO2、Al2O3One or more in metal oxide.
Application process of the O composite metallic oxide catalyst of the present invention in ethylene glycol co-producing dimethyl carbonate, by ethylene
Alkene ester and methanol are 1 according to mol ratio：(2-10) ratio is mixed, and O composite metallic oxide catalyst is being carried out into ester exchange reaction
When add molar percentage be ethylene carbonate amount 1-8wt.%, reaction temperature be 30-70 DEG C, reaction pressure is normal pressure, instead
It is 0.5-6h between seasonable.
Specific embodiment is given below to further illustrate the present invention.
Embodiment 1
It is Fe67Al33 according to catalyst mole composition, corresponding nitrate is dissolved into deionized water, is configured as
0.5mol/L mixed solution, is at room temperature 2 with mol ratio：1 NaOH and Na2CO3Alkali lye is catalyzed using coprecipitation
It is prepared by agent.Precipitation process is sufficiently stirred for, and it is 10 to be adjusted to pH value, keeps aged at room temperature 10h, filtering, washing, 110 DEG C of dryings
10h, 300 DEG C of roasting 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：6, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 4wt.% of ethylene carbonate, and reaction temperature is 70 DEG C, and reaction pressure is normal pressure, and the reaction time is
3h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
60.2%, dimethyl carbonate yield is 58.3%, and ethylene glycol yield is 57.5%.
Embodiment 2
Catalyst mole composition is Zn60Zr40, and corresponding nitrate is dissolved into deionized water, 1mol/ is configured as
L mixed solution, is at room temperature 2 with mol ratio：1 NaOH and Na2CO3Alkali lye carries out catalyst preparation using coprecipitation.
Precipitation process is sufficiently stirred for, and it is 9 to be adjusted to pH value, keeps aged at room temperature 5h, filtering, washing, 110 DEG C of dry 10h, 500 DEG C
It is calcined 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：2, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 6wt.% of ethylene carbonate, and reaction temperature is 50 DEG C, and reaction pressure is normal pressure, and the reaction time is
5h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
78.3%, dimethyl carbonate yield is 77.6%, and ethylene glycol yield is 77.3%.
Embodiment 3
Catalyst mole composition is Cu70La30, and corresponding nitrate is dissolved into deionized water, is configured as
1.5mol/L mixed solution, is at room temperature 2 with mol ratio：1 NaOH and Na2CO3Alkali lye is catalyzed using coprecipitation
It is prepared by agent.Precipitation process is sufficiently stirred for, and it is 11 to be adjusted to pH value, keeps aged at room temperature 3h, filtering, washing, 110 DEG C of dryings
10h, 500 DEG C of roasting 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：10, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 8wt.% of ethylene carbonate, and reaction temperature is 45 DEG C, and reaction pressure is normal pressure, and the reaction time is
2h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
67.4%, dimethyl carbonate yield is 65.8%, and ethylene glycol yield is 63.6%.
Embodiment 4
Catalyst mole composition is Mn85Y15, and corresponding nitrate is dissolved into deionized water, 2mol/L is configured as
Mixed solution, at room temperature with mol ratio be 2：1 NaOH and Na2CO3Alkali lye carries out catalyst preparation using coprecipitation.
Precipitation process is sufficiently stirred for, and it is 12 to be adjusted to pH value, keeps aged at room temperature 6h, filtering, washing, 120 DEG C of dry 10h, 700 DEG C
It is calcined 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：6, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 8wt.% of ethylene carbonate, and reaction temperature is 30 DEG C, and reaction pressure is normal pressure, and the reaction time is
4h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
50.9, dimethyl carbonate yield is 47.1%, and ethylene glycol yield is 45.1%.
Embodiment 5
Catalyst mole composition is Ni60Al30La10, and corresponding nitrate is dissolved into deionized water, is configured as
1.5mol/L mixed solution, is at room temperature 2 with mol ratio：1 NaOH and Na2CO3Alkali lye is catalyzed using coprecipitation
It is prepared by agent.Precipitation process is sufficiently stirred for, and it is 12 to be adjusted to pH value, keeps aged at room temperature 10h, filtering, washing, 110 DEG C of dryings
10h, 500 DEG C of roasting 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：4, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 2wt.% of ethylene carbonate, and reaction temperature is 40 DEG C, and reaction pressure is normal pressure, and the reaction time is
2h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
75.4%, dimethyl carbonate yield is 73.8%, and ethylene glycol yield is 70.4%.
Embodiment 6
Catalyst mole composition is Zn60Al20Ce20, and corresponding nitrate is dissolved into deionized water, is configured as
1mol/L mixed solution, is at room temperature 2 with mol ratio：1 NaOH and Na2CO3Alkali lye carries out catalyst using coprecipitation
Prepare.Precipitation process is sufficiently stirred for, and it is 11 to be adjusted to pH value, keeps aged at room temperature 12h, filtering, washing, 110 DEG C of dryings
10h, 600 DEG C of roasting 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：5, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 3wt.% of ethylene carbonate, and reaction temperature is 50 DEG C, and reaction pressure is normal pressure, and the reaction time is
3h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
68.7%, dimethyl carbonate yield is 66.5%, and ethylene glycol yield is 65.1%.
Embodiment 7
Catalyst mole composition is Co50Mg30Al20, and corresponding nitrate is dissolved into deionized water, is configured as
1mol/L mixed solution, is at room temperature 2 with mol ratio：1 NaOH and Na2CO3Alkali lye carries out catalyst using coprecipitation
Prepare.Precipitation process is sufficiently stirred for, and it is 11 to be adjusted to pH value, keeps aged at room temperature 10h, filtering, washing, 110 DEG C of dryings
10h, 600 DEG C of roasting 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：4, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 2wt.% of ethylene carbonate, and reaction temperature is 45 DEG C, and reaction pressure is normal pressure, and the reaction time is
0.5h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
70.7%, dimethyl carbonate yield is 70.5%, and ethylene glycol yield is 69.7%.
Embodiment 8
Catalyst mole composition is Zn40Mg40Al20, and corresponding nitrate is dissolved into deionized water, is configured as
1mol/L mixed solution, is at room temperature 2 with mol ratio：1 NaOH and Na2CO3Alkali lye carries out catalyst using coprecipitation
Prepare.Precipitation process is sufficiently stirred for, and it is 10 to be adjusted to pH value, keeps aged at room temperature 8h, is filtered, is washed, 110 DEG C of dry 10h,
500 DEG C of roasting 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：6, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 3wt.% of ethylene carbonate, and reaction temperature is 50 DEG C, and reaction pressure is normal pressure, and the reaction time is
3h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
62.5%, dimethyl carbonate yield is 60.8%, and ethylene glycol yield is 58.6%.
Embodiment 9
Catalyst mole composition is Zn60Al20La20, and corresponding nitrate is dissolved into deionized water, is configured as
1.5mol/L mixed solution, is at room temperature 2 with mol ratio：1 NaOH and Na2CO3Alkali lye is catalyzed using coprecipitation
It is prepared by agent.Precipitation process is sufficiently stirred for, and it is 10 to be adjusted to pH value, keeps aged at room temperature 12h, filtering, washing, 110 DEG C of dryings
10h, 600 DEG C of roasting 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：5, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 1wt.% of ethylene carbonate, and reaction temperature is 55 DEG C, and reaction pressure is normal pressure, and the reaction time is
2h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
58.6%, dimethyl carbonate yield is 55.3%, and ethylene glycol yield is 51.7%.
Embodiment 10
Catalyst mole composition is Ni40Mg40Al20, and corresponding nitrate is dissolved into deionized water, is configured as
1mol/L mixed solution, is at room temperature 2 with mol ratio：1 NaOH and Na2CO3Alkali lye carries out catalyst using coprecipitation
Prepare.Precipitation process is sufficiently stirred for, and it is 10 to be adjusted to pH value, keeps aged at room temperature 12h, filtering, washing, 110 DEG C of dryings
10h, 900 DEG C of roasting 5h.
According to mol ratio it is 1 by ethylene carbonate and methanol：5, ester exchange is carried out on O composite metallic oxide catalyst
Reaction, catalyst amount is the 3wt.% of ethylene carbonate, and reaction temperature is 45 DEG C, and reaction pressure is normal pressure, and the reaction time is
6h.After reaction terminates, catalyst is separated, gas-chromatography carries out product composition analysis, ethylene carbonate ester conversion rate is
70.3%, dimethyl carbonate yield is 68.5%, and ethylene glycol yield is 67.4%.
The invention is not limited in above-described embodiment, on the basis of technical scheme disclosed by the invention, the skill of this area
Art personnel are according to disclosed technology contents, it is not necessary to which performing creative labour just can make one to some of which technical characteristic
A little to replace and deform, these are replaced and deformed within the scope of the present invention.
Claims (6)
1. a kind of O composite metallic oxide catalyst that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction, its feature
It is, the catalyst contains the component of following molar percentages：Active component 40-85%；Auxiliary agent 15-60%；
The active component is a kind of oxide in transition metal Mn, Fe, Co, Ni, Cu, Zn；
The auxiliary agent is MgO, Y2O3、ZrO2、La2O3、CeO2、Al2O3One or more in metal oxide.
2. a kind of composition metal that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction described in a kind of claim 1
The preparation method of oxide catalyst, it is characterised in that comprise the following steps：
1) according to catalyst metals proportion of composing, prepared and active component transition metal and auxiliary agent gold according to molar percentage
Belong to the corresponding nitrate solution of metallic element in oxide；
2) it is at ambient temperature, 2 by corresponding nitrate solution and mol ratio：1 NaOH and Na2CO3Alkali lye is using co-precipitation
Method prepares catalyst, and precipitation process is sufficiently stirred for, and is adjusted to pH value for 9-12, keeps aged at room temperature, and filtering, washing are dried,
Roasting, the amount that the consumption of each component makes final active component molar percentage account for catalyst is 40-85%, auxiliary agent Mole percent
Amount than accounting for catalyst is 15-60%.
3. a kind of composition metal that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction according to claim 2
The preparation method of oxide catalyst, it is characterised in that the step 1) in, corresponding nitrate is dissolved in deionized water
In, form the mixed solution that concentration is 0.5-2mol/L.
4. a kind of composition metal that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction according to claim 2
The preparation method of oxide catalyst, it is characterised in that the step 2) in, aged at room temperature 3-12h is kept, filters, wash,
110-120 DEG C of dry 10h, 300-900 DEG C of roasting 5h.
5. a kind of O composite metallic oxide catalyst answering in ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction
With, it is characterised in that by ethylene carbonate and methanol according to mol ratio it is 1：(2-10) ratio is mixed, by metal composite oxide
Catalyst adds the 1-8wt.% that molar percentage is ethylene carbonate amount when carrying out ester exchange reaction, and reaction temperature is 30-
70 DEG C, reaction pressure is normal pressure, and the reaction time is 0.5-6h.
6. O composite metallic oxide catalyst according to claim 5 is preparing ethylene glycol coproduction carbon for ester exchange reaction
Application in dimethyl phthalate, it is characterised in that use and cause ethylene glycol coproduction carbonic acid diformazan after O composite metallic oxide catalyst
Ethylene carbonate ester conversion rate in ester is not less than 60.2%, and dimethyl carbonate yield is not less than 47.1%, and ethylene glycol yield is not low
In 45.1%.
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| CN201710543610.XA CN107243345A (en) | 2017-07-05 | 2017-07-05 | A kind of O composite metallic oxide catalyst that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction |
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| CN109364959A (en) * | 2018-09-29 | 2019-02-22 | 中国科学院山西煤炭化学研究所 | The solid base catalyst and preparation method of a kind of ester-interchange method synthesis of dialkyl carbonates and application |
| CN110841663A (en) * | 2019-11-25 | 2020-02-28 | 陕西煤业化工技术研究院有限责任公司 | Catalyst for synthesizing anisole by taking phenol and dimethyl carbonate as raw materials, preparation method and application |
| CN113509947A (en) * | 2021-07-21 | 2021-10-19 | 陕西煤业化工技术研究院有限责任公司 | Catalyst for synthesizing p-methyl anisole and preparation method and application thereof |
| CN114749168A (en) * | 2022-04-06 | 2022-07-15 | 扬州大学 | High-activity zirconium dioxide/zinc oxide catalyst and preparation method and application thereof |
| CN114904542A (en) * | 2022-04-25 | 2022-08-16 | 中国科学院青岛生物能源与过程研究所 | Composite catalyst for catalyzing and degrading polyester/polycarbonate plastics and preparation method and application thereof |
| CN114989015A (en) * | 2022-06-30 | 2022-09-02 | 华东师范大学 | Method for preparing dimethyl carbonate by ester exchange reaction catalyzed by inorganic salt |
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| CN108101739A (en) * | 2017-12-19 | 2018-06-01 | 西安近代化学研究所 | The continuous method for preparing tri- fluoro- 1,2- propylene glycol of 3,3,3- |
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| CN109364959A (en) * | 2018-09-29 | 2019-02-22 | 中国科学院山西煤炭化学研究所 | The solid base catalyst and preparation method of a kind of ester-interchange method synthesis of dialkyl carbonates and application |
| CN110841663A (en) * | 2019-11-25 | 2020-02-28 | 陕西煤业化工技术研究院有限责任公司 | Catalyst for synthesizing anisole by taking phenol and dimethyl carbonate as raw materials, preparation method and application |
| CN110841663B (en) * | 2019-11-25 | 2022-06-28 | 陕西煤业化工技术研究院有限责任公司 | Catalyst for synthesizing anisole by taking phenol and dimethyl carbonate as raw materials, preparation method and application |
| CN113509947A (en) * | 2021-07-21 | 2021-10-19 | 陕西煤业化工技术研究院有限责任公司 | Catalyst for synthesizing p-methyl anisole and preparation method and application thereof |
| CN113509947B (en) * | 2021-07-21 | 2023-09-26 | 陕西煤业化工技术研究院有限责任公司 | Catalyst for synthesizing p-methylanisole as well as preparation method and application thereof |
| CN114749168A (en) * | 2022-04-06 | 2022-07-15 | 扬州大学 | High-activity zirconium dioxide/zinc oxide catalyst and preparation method and application thereof |
| CN114904542A (en) * | 2022-04-25 | 2022-08-16 | 中国科学院青岛生物能源与过程研究所 | Composite catalyst for catalyzing and degrading polyester/polycarbonate plastics and preparation method and application thereof |
| CN114989015A (en) * | 2022-06-30 | 2022-09-02 | 华东师范大学 | Method for preparing dimethyl carbonate by ester exchange reaction catalyzed by inorganic salt |
| CN114989015B (en) * | 2022-06-30 | 2023-09-26 | 华东师范大学 | Method for preparing dimethyl carbonate by catalyzing transesterification with inorganic salt |
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