CN103721697B - The catalyst of a kind of synthesizing acrylic ester and preparation method and application - Google Patents
The catalyst of a kind of synthesizing acrylic ester and preparation method and application Download PDFInfo
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- CN103721697B CN103721697B CN201410001620.7A CN201410001620A CN103721697B CN 103721697 B CN103721697 B CN 103721697B CN 201410001620 A CN201410001620 A CN 201410001620A CN 103721697 B CN103721697 B CN 103721697B
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Abstract
The composite oxide that the catalyst of a kind of synthesizing acrylic ester is made up of active component zinc oxide and auxiliary agent oxide, consisting of the mass content of Zn is 1 99%, the mass content of auxiliary element is 1 99%.The present invention has low cost, selectivity is high, conversion ratio is high, reaction condition is gentle, good stability, the advantage that reactant is easily isolated.
Description
Technical field
The invention belongs to catalyst and the preparation method and application of a kind of synthesizing acrylic ester.
Background technology
One of main uses of Allyl carbonate (PC) is as high-efficiency desulfurization decarburization (CO2) to be applied to natural gas clean for solvent
The industrial departments such as change and hydrogen manufacturing.Being also used as intensive polar solvent to be applied in petrochemical industry, fiber and printing and dyeing industry, it is to take out
Carry the good solvent of the indissoluble things such as petroleum distillate, Resina Toxicodendri verniciflui, plasticizer.Meanwhile, also it is the former of dimethyl carbonate production by transesterification
Material.It addition, use Allyl carbonate to make the electrolyte in battery can bear the light under relatively mal-condition, heat and chemical change,
Can substitute for phenolic resin and make wood adhesive.It mixes by a certain percentage with isocyanates, wood chip can be bonded into intensity very
High plank, is used as construction material.
The main route of propylene carbonate Lipase absobed has: phosgenation, halohydrin method, ester-interchange method, alkene and carbon dioxide
Direct oxidation method, CO2Cycloaddition method and urea method etc..In above-mentioned several method, phosgenation due to environmental conservation reason
Through being gradually eliminated.And in additive method, owing to employing traditional petroleum path just getable raw material, therefore its price is very
It is easily subject to the impact of oil price fluctuation, and reaction condition is harsher.At present industrialization generate PC mainly with expoxy propane with
CO2For raw material, pyridine is catalyst, and at 240 DEG C, 14 MPa have prepared PC, and reaction is carried out under conditions of High Temperature High Pressure, epoxy
Firing of propane is dangerous big, needs to add antidetonator.Reaction condition and catalyst are improved by Myrl et al. further,
Use ammonium halide to make catalyst, at 100-225 DEG C, under conditions of 2.17MPa, synthesize PC.This method simplifies technique, and catalyst can
Reusing, the yield of PC reaches as high as 89%.The researcher of various countries is anti-with the cycloaddition of carbon dioxide to epoxide subsequently
Answer catalyst system to carry out substantial amounts of research, but these catalyst exist low catalysis activity or selectivity, low stability
Or need the condition of cosolvent, high pressure or high temperature.Current industrialized production is based on homogeneous catalysis system, efficiently and environment friend
Good catalyst system and catalyzing, and carry out under mild conditions carbon dioxide fixing come synthesizing annular carbonate be still faced with the biggest
Challenge, separation and recycling to homogeneous catalysis system simultaneously is still that a subject matter.Twentieth century 90 years
Propose the process of carbamide and diol reaction synthesizing annular carbonate for Texaco company of the U.S., the dihydroxylic alcohols used is with fat
Fat race α-dihydroxylic alcohols is main.The major advantage of this route is: low in raw material price, is easy to get, and reaction condition is the gentleest, by-product
Ammonia can be recycled to the production unit of urea synthesis, and raw material can be easily separated with product；Whole process does not uses (or generation) to have
Poison, burn into are inflammable, explosive materials concealed, are the synthetic routes of real " green ".This synthetic method visible can realize " zero
Discharge ", meet the requirement of green chemical industry, have good development prospect.1993, MIT on the basis of Su et al.
Vicinal diamines reaction below Doya et al. proposition carbamide and 6 carbon generates alkylene carbonates, and the conjunction to carbonic acid alkene ester
Reaction is become to be improved, under reduced pressure, with zinc-magnesium lead calcium simple substance and compound thereof as catalyst, the yield of carbonic acid alkene ester
Had a significant raising, and the highest yield oneself reach 97.2%.Li Qi violent winds etc. use the oxide catalysts such as ZnO, catalyst amount
Being 2%, react 2h at 170 DEG C, result ZnO activity is the highest, and PC yield reaches 98.9%.Zhao Xin is strong etc. have studied zinc acetate catalysis
Carbamide and 1,2 propylene glycol are synthesized Allyl carbonate, and the highest yield is 93.7%.Zinc acetate is loaded on the activated carbon, most preferably
Load capacity is 15%, and the highest yield of propylene carbonate vinegar is 78%, when investigating repeatability, is found to have the loss of active component.
Summary of the invention
It is an object of the invention to provide a kind of low cost, selectivity is high, conversion ratio is high, reaction condition is gentle, good stability,
Carbamide that reactant is easily isolated and the catalyst of 1,2 propylene glycol synthesizing acrylic esters and preparation method and application.
The composite oxide that the catalyst of the present invention is made up of active component zinc oxide and auxiliary agent oxide, its composition
For, the mass content of Zn is 1-99%, and the mass content of auxiliary element is 1-99%.
Auxiliary element as above is one or more in alkaline-earth metal and transition metal.
Alkaline-earth metal as above is Mg, Ca, Ba etc., and transition metal is Pb, Al, Fe, Mn, Zr etc..
The catalyst preparation of the present invention is as follows:
1, coprecipitation: catalyst forms the soluble-salt of metal, according to catalyst composition mass ratio configuration 5-50
The precursor water solution of wt%, configures the precipitant aqueous solution of 5-50 wt% simultaneously, is slowly dropped to precipitant at 10-80 DEG C
In solution, the pH value controlling process is 6-13, the rear aging 0.5-24h of precipitation, is then washed with deionized to noresidue
K+Or Na+Till detection, the product obtained is after filtering at 60-150 DEG C of dry 1-24h, finally at a temperature of 300-900 DEG C
Calcining 0.5-12h, obtains catalyst.
The soluble-salt of metal is acetate, chloride or nitrate as mentioned above.
Precipitant as above is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate
Deng.
2, urea precipitation method: the aqueous solution of urea of configuration 1-60 wt%, forms the soluble-salt of metal by catalyst, according to
Catalyst constitutive molar ratio is configured to the solution of 1-60 wt%, and mixes with above-mentioned urea liquid, then by mixed solution liter
Temperature carries out homogeneous precipitation reaction to 30-150 DEG C, and the response time is 0.5-72h, carries out sucking filtration, so with the product obtained after reaction
After at 60-150 DEG C of dry 1-24h, finally at 300-900 DEG C of temperature lower calcination 0.5-12h, obtain catalyst.
The soluble-salt of metal is acetate, chloride or nitrate as mentioned above.
The application of the present invention is as follows:
Reaction condition is: propylene glycol is 1-10:1 with the mol ratio of carbamide, temperature 100-250 DEG C, vacuum 50mmHg-
650mmHg, catalyst is 0.001-0.1 with the mass ratio of carbamide, response time 0.5h-20h.
The present invention compared with prior art, has the advantage that
1) catalyst preparation process is simple, has good stability, and reusability is good；
2) catalyst performance is good, is also easy to separate with product, it is easy to accomplish industry is amplified；
3) reaction raw materials is cheap and easy to get, and product yield is high, and by-product is less, the economy highly significant of building-up process；
4) course of reaction is simple, it is easy to operation.
Detailed description of the invention
Embodiment 1:
99:1 in mass ratio configures the nitrate solution of zinc and calcium and is dissolved in distilled water the mixed solution forming 15 wt%.
At 80 DEG C, the sodium carbonate liquor with 30Wt% is co-precipitated, and precipitation process need to be sufficiently stirred for, and keeps pH=10, the most aging
0.5h, precipitates through distilled water wash to detecting without sodium ion, is dried 12h and through 300 DEG C of roasting 12h, obtains at 60 DEG C
The composite oxide that catalyst quality is formed than ZnO Yu CaO for 99:1.
Carbamide and 1,2 propylene glycol reactions are carried out in there-necked flask, and reaction condition is as follows: propylene glycol and the mol ratio of carbamide
10, vacuum: 300mmHg, T=170 DEG C, catalyst is 0.03 with the mass ratio of carbamide, response time 0.5h.After reaction through from
The heart separates, and then forms with gas chromatographic analysis product, and obtaining PC yield is 82%.
Example 2.
1:1 in mass ratio configures the acetate solution of zinc and magnesium and is dissolved in distilled water the mixed solution forming 5wt%.?
At 60 DEG C, the sodium carbonate liquor with 50wt% is co-precipitated, and precipitation process need to be sufficiently stirred for, and keeps pH=7, the most aging 12h,
Precipitate through distilled water wash to detecting without sodium ion, at 150 DEG C, be dried 1h, and prepare through 900 DEG C of roasting 0.5h, obtain
The composite oxide that catalyst quality is formed than ZnO Yu MgO for 1:1.
Carbamide and 1, the reaction condition of 2 propylene glycol is as follows: propylene glycol and the mol ratio 1 of carbamide, vacuum: 500mmHg, T=
140 DEG C, catalyst is 0.01 with the mass ratio of carbamide, through centrifugation after response time 2h. reaction, then divides by gas chromatogram
Division thing forms, and obtaining PC yield is 90%.
Example 3.
The mixing that the nitrate solution being dissolved in distilled water of the configuration zinc-magnesium ferrum of 1:98:1 in mass ratio forms 50wt% is molten
Liquid.At 10 DEG C, the sodium carbonate liquor with 45wt% is co-precipitated, and precipitation process need to be sufficiently stirred for, and keeps pH=13, the most always
Change 8h, precipitate through distilled water wash to detecting without sodium ion, at 100 DEG C, be dried 10h and prepare through 450 DEG C of roasting 6h,
Catalyst quality is than ZnO, MgO and the Fe for 1:98:12O3The composite oxide formed.
Carbamide and 1, the reaction condition of 2 propylene glycol is as follows: propylene glycol and the mol ratio 3 of carbamide, vacuum: 650mmHg, T=
100 DEG C, catalyst is 0.04 with the mass ratio of carbamide, through centrifugation after response time 12h. reaction, then uses gas chromatogram
Assay products forms, and obtaining PC yield is 84%.
Example 4.
4:2:1 in mass ratio configures the nitrate solution of zinc-aluminium ferrum and is dissolved in distilled water the mixed solution forming 40wt%.
At 60 DEG C, the sodium carbonate liquor with 5wt% is co-precipitated, and precipitation process need to be sufficiently stirred for, and keeps pH=6, the most aging 24h,
Precipitate through distilled water wash to detecting without sodium ion, at 150 DEG C, be dried 14h and prepare catalysis through 650 DEG C of roasting 0.5h
Agent.Catalyst quality is than ZnO, the Al for 4:2:12O3With Fe2O3The composite oxide formed.
Carbamide and 1, the reaction condition of 2 propylene glycol is as follows: propylene glycol and the mol ratio 5 of carbamide, vacuum: 200mmHg, T=
170 DEG C, catalyst is 0.02 with the mass ratio of carbamide, response time 2h.Through centrifugation after reaction, then divide by gas chromatogram
Division thing forms, and obtaining PC yield is 98%.
Example 5.
1:99 in mass ratio configures the acetate solution of zinc calcium and is dissolved in distilled water the mixed solution forming 30wt%, so
Mix with the aqueous solution of urea of 60wt% afterwards.Mixed solution being warming up to 150 DEG C and carries out homogeneous precipitation reaction, the response time is
12h.Carry out sucking filtration with the product obtained after reaction, in 60 DEG C of baking ovens, be then dried 24h, finally at 900 DEG C of temperature lower calcinations
12h prepares, the composite oxide that catalyst quality is formed than ZnO Yu CaO for 2:1.
Carbamide and 1, the reaction condition of 2 propylene glycol is as follows: propylene glycol and the mol ratio 4 of carbamide, vacuum: 50mmHg, T=
200 DEG C, catalyst is 0.001 with the mass ratio of carbamide, response time 6h.Through centrifugation after reaction, then use gas chromatogram
Assay products forms, and obtaining PC yield is 85%.
Example 6.
The configuration nitrate solution of zinc-aluminium of 1:1 in mass ratio is also dissolved in distilled water the mixed solution forming 1%, then with
Precipitant is the aqueous solution of urea mixing of 1%.Mixed solution being warming up to 120 DEG C and carries out homogeneous precipitation reaction, the response time is
24h.Carry out sucking filtration with the product obtained after reaction, in 150 DEG C of baking ovens, be then dried 12h, finally at 350 DEG C of temperature lower calcinations
12h prepares, and catalyst quality is than ZnO and Al for 1:12O3The composite oxide formed。
Carbamide and 1, the reaction condition of 2 propylene glycol is as follows: propylene glycol and the mol ratio 3 of carbamide, vacuum: 600mmHg, T=
250 DEG C, catalyst is 0.1 with the mass ratio of carbamide, through centrifugation after response time 20h. reaction, then divides by gas chromatogram
Division thing forms, and obtaining PC yield is 86%.
Example 7.
1:1:1 in mass ratio configures the chloride solution of zinc-magnesium ferrum and is dissolved in distilled water the mixed solution forming 60%, so
Mix with the aqueous solution of urea that precipitant is 50% afterwards.Mixed solution is warming up to 30 DEG C and carries out homogeneous precipitation reaction, response time
For 0.5h.Carry out sucking filtration with the product obtained after reaction, in 60 DEG C of baking ovens, be then dried 12h, finally forge at a temperature of 550 DEG C
Burning 4h to prepare, catalyst quality is than ZnO, MgO and the Fe for 1:1:12O3The composite oxide formed.
Carbamide and 1, the reaction condition of 2 propylene glycol is as follows: propylene glycol and the mol ratio 2 of carbamide, vacuum: 600mmHg, T=
180 DEG C, catalyst is 0.001 with the mass ratio of carbamide, through centrifugation after response time 6h. reaction, then uses gas chromatogram
Assay products forms, and obtaining PC yield is 87%.
Example 8.
1:98:1 in mass ratio configures the chloride solution of zinc ferrozirconium and is dissolved in distilled water the mixed solution forming 40%,
Then mix with the aqueous solution of urea that precipitant is 60%.Mixed solution is warming up to 120 DEG C and carries out homogeneous precipitation reaction, reaction
Time is 72h.Carry out sucking filtration with the product obtained after reaction, in 150 DEG C of baking ovens, be then dried 12h, finally 300 DEG C of temperature
Lower calcining 4h prepares, and catalyst quality is than ZnO, the ZrO for 2:1:22With Fe2O3The composite oxide formed.
Carbamide and 1, the reaction condition of 2 propylene glycol is as follows: propylene glycol and the mol ratio 2 of carbamide, vacuum: 500mmHg, T=
250 DEG C, catalyst is 0.1 with the mass ratio of carbamide, through centrifugation after response time 0.5h. reaction, then uses gas chromatogram
Assay products forms, and obtaining PC yield is 83%.
Claims (3)
1. the catalyst of a synthesizing acrylic ester, it is characterised in that catalyst is to be aoxidized by active component zinc oxide and auxiliary agent
The composite oxide of thing composition, consisting of the mass content of Zn is 1-99%, the mass content of auxiliary element is 1-99%, its
Middle auxiliary element is the complex of Fe and Zr；
And preparation by the following method:
Method one: catalyst forms the soluble-salt of metal, according to the forerunner of catalyst composition mass ratio configuration 5-50 wt%
Body aqueous solution, configures the precipitant aqueous solution of 5-50 wt% simultaneously, is slowly dropped in precipitant solution at 10-80 DEG C, control
The pH value of process processed is 6-13, the rear aging 0.5-24h of precipitation, is then washed with deionized the K to noresidue+Or Na+Inspection
Till going out, the product obtained is after filtering at 60-150 DEG C of dry 1-24h, finally at 300-900 DEG C of temperature lower calcination 0.5-
12h, obtains catalyst；
Or method two: the aqueous solution of urea of configuration 1-60 wt%, catalyst is formed the soluble-salt of metal, according to catalyst group
Become mol ratio to be configured to the solution of 1-60 wt%, and mix with above-mentioned urea liquid, then mixed solution is warming up to 30-
150 DEG C carry out homogeneous precipitation reaction, and the response time is 0.5-72h, carry out sucking filtration, then at 60-with the product obtained after reaction
150 DEG C of dry 1-24h, finally at 300-900 DEG C of temperature lower calcination 0.5-12h, obtain catalyst；
Described precipitant is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate.
The catalyst of a kind of synthesizing acrylic ester the most as claimed in claim 1, it is characterised in that the solubility of described metal
Salt is acetate, chloride or nitrate.
The application of the catalyst of a kind of synthesizing acrylic ester the most as claimed in claim 1 or 2, it is characterised in that include as follows
Step:
The mol ratio of propylene glycol and carbamide is 1-10:1, temperature 100-250 DEG C, vacuum 50mmHg-650mmHg, catalyst with
The mass ratio of carbamide is 0.001-0.1, response time 0.5h-20h.
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| CN103933961A (en) * | 2014-04-17 | 2014-07-23 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing propylene carbonate as well as preparation method and application of catalyst |
| CN104961720A (en) * | 2015-08-02 | 2015-10-07 | 何肖凤 | Preparation method of propylene carbonate |
| CN105435768B (en) * | 2015-11-10 | 2017-10-31 | 北京石油化工学院 | The process of alcoholysis of urea for synthesizing propylene carbonate and the preparation method of catalyst |
| CN107243345A (en) * | 2017-07-05 | 2017-10-13 | 陕西煤业化工技术研究院有限责任公司 | A kind of O composite metallic oxide catalyst that ethylene glycol co-producing dimethyl carbonate is prepared for ester exchange reaction |
| CN114917891A (en) * | 2022-05-26 | 2022-08-19 | 山东海科新源材料科技股份有限公司 | Synthetic method and application of non-noble metal supported catalyst |
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| CN1416949A (en) * | 2002-12-18 | 2003-05-14 | 河北工业大学 | Metal oxide catalyst for synthesizing methyl carbonate by urea process and its prepn |
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| 尿素与1，2-丙二醇催化合成碳酸丙烯酯反应研究;张艳;《中国优秀博硕士学位论文全文库数据库（硕士）工程科技I辑》;20040915(第03期);第13页最后1段，第14页第1段，第48页第1段，第49页表6.1，第50页第3段 * |
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