CN101279959A - Method for synthesizing epoxypropane - Google Patents
Method for synthesizing epoxypropane Download PDFInfo
- Publication number
- CN101279959A CN101279959A CNA2008100313937A CN200810031393A CN101279959A CN 101279959 A CN101279959 A CN 101279959A CN A2008100313937 A CNA2008100313937 A CN A2008100313937A CN 200810031393 A CN200810031393 A CN 200810031393A CN 101279959 A CN101279959 A CN 101279959A
- Authority
- CN
- China
- Prior art keywords
- reaction
- solution
- value
- hydrogen peroxide
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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
Landscapes
- Epoxy Compounds (AREA)
Abstract
The invention discloses a method to synthesize propylene oxide, which is characterized in that alcohol with low content of carbon, propylene and oxydol(mol ratio 1-15:0.5-5:1) are put into a reactor which is fed with catalyzer; the propylene and the oxydol react and produce propylene oxide, and the condition for the reaction includes: temperature 30-90 DEG C, pressure 0.5-4.5MPa, ph value of the solution 5,0-8.0, and airspeed of the solution 0.1-7h-1; wherein the temperature and ph value of the solution in the whole process are adjusted according to the conversion rate of the oxydol, and once the conversion rate of the oxydol drops to 88.5%, the ph value and the temperature of the solution are increased. The method is simple in process, mild in condition, the conversion rate of the oxydol is high and the propylene oxide is of selectivity; meanwhile, the life of the catalyzer is prolonged to over 1200h through the adjustment of the ph value and the temperature of the solution.
Description
One, technical field
The present invention relates to a kind of method of synthesizing epoxypropane, particularly relating to a kind of is oxygenant with the hydrogen peroxide, the method for titanium molecular sieve catalysis propylene ring oxidation reaction synthesizing epoxypropane.
Two, background technology
Propylene oxide is the third-largest organic chemical industry's product that output is only second to polypropylene and vinyl cyanide in the acryloyl derivative, be mainly used in and produce polyethers, propylene glycol, Yi Bingchunan, non-polyether glycol etc., and then produce important source material such as unsaturated polyester resin, urethane, tensio-active agent, fire retardant.
Propylene oxide adopts chlorohydrination and conjugated oxidation production in the world.During the chlorohydrination synthesizing epoxypropane, equipment corrosion is serious, consumes a large amount of Cl
2, produce a large amount of waste water, waste residue, environment has been caused very big pollution, along with the raising day by day of environmental protection requirement, this industry finally is eliminated; The conjugated oxidation long flow path, investment is big, produces to be subjected to the restriction that the by product outlet is used.Therefore, the production method of existing propylene oxide has restricted the production of propylene oxide.
With the hydrogen peroxide is oxygenant, titanium molecular sieve catalysis epoxidation of propylene synthesizing epoxypropane, this process has mild condition, the friendly advantage such as pollution-free of process environment, meeting the requirement of Green Chemistry and atom economy idea of development, is the novel environment-friendly process of producing propylene oxide.
US5675026 adopt in reaction system, add neutral or with the method for the salt of acid-respons, for example Na
2SO
4, NH
3, (NH
4)
2SO
4, Na
2HPO
4, NaH
2PO
4Deng, the productive rate and the selectivity of propylene oxide are higher, activity of such catalysts begins to descend when proceeding to 60h but react, and life of catalyst is short, needs frequent regeneration.
The US6300506B1 employing adds buffered soln and comes regulator solution pH to 5.5～8.0 in reaction system, the productive rate and the selectivity of propylene oxide are higher, yet catalyzer proceeds to 30 hours, H
2O
2Transformation efficiency quickly fall to 75% from 90%, life of catalyst is short.
Therefore be oxygenant with the hydrogen peroxide, the subject matter that titanium molecular sieve catalysis propylene ring oxidation reaction synthesizing epoxypropane technology exists is that the work-ing life of catalyzer is short.
Three, summary of the invention
The objective of the invention is to propose a kind of long service life of catalyzer, and can keep the high reaction activity and high and the method for synthesizing epoxypropane optionally.
The objective of the invention is to be achieved through the following technical solutions: a kind of method of synthesizing epoxypropane, it is characterized in that: mol ratio (1～15): (0.5～5): 1 low-carbon alcohol, propylene, hydrogen peroxide are in being equipped with the reactor of catalyzer, propylene and hydrogen peroxide initial ring oxidizing reaction obtain propylene oxide, described reaction conditions is 30 ℃～90 ℃ of temperature of reaction, reaction pressure 0.5～4.5Mpa, pH value of solution 5.0～8.0, liquid air speed 0.1～7h
-1, wherein pH value of solution and temperature of reaction are regulated according to the hydrogen peroxide transformation efficiency in entire reaction course at any time, and hydrogen peroxide transformation efficiency one is reduced to 88.5%, just improves pH value of solution and temperature of reaction.
Described low-carbon alcohol exists as reaction solvent, and molecular formula is C
nH
2n+1OH, n in the formula 〉=1, a kind of in particular methanol, ethanol, propyl alcohol, the butanols.
Add tensio-active agent in the described reaction, its addition is 0～1%.Epoxidation of propylene belongs to gas, solid, liquid phase reaction, because solubleness is less in the water of propylene in hydrogen peroxide, so it is relatively poor that propylene participates in response capacity, solubleness is less in the water of the propylene oxide of Sheng Chenging in hydrogen peroxide simultaneously, prolonged the residence time at catalyst surface, the carrying out of aggravation side reaction causes the reaction preference variation, and catalyst life is short.In reaction system, add tensio-active agent, water in propylene and the hydrogen peroxide has formed emulsion, and the solubleness of propylene in system increases, and the propylene effective rate of utilization increases, thereby speed of response is accelerated, simultaneously, the propylene oxide of generation and emulsion intermiscibility increase, and have accelerated the velocity of diffusion of propylene oxide at catalyst surface, shortened the residence time at catalyst surface, slowed down the carrying out of side reaction, reaction preference improves, and catalyst life is elongated.
The tensio-active agent that adopts among the present invention is the commercially available prod, can be water-soluble, and for example tween (Tween) series, Ni Nale (Ninol) also can be oil-soluble, for example sapn (Span) series, TX-10, OP-10, or both interworkings.
Described catalyzer is the HTS of HTS powder or moulding.Wherein HTS is modifying titanium-silicon molecular sieve or the HTS that does not have modification, or their mixture.
Described reactor is fixed-bed reactor or slurry bed reactor.
With the hydrogen peroxide is oxygenant, and during titanium molecular sieve catalysis propylene ring oxidation reaction synthesizing epoxypropane, main side reaction is: propylene oxide and alcohol compound generate propylene glycol; Propylene oxide and hydrate generate propylene glycol, and these two side reactions mainly are to carry out under strong acid or highly basic catalysis.Since raw material hydrogen peroxide cause reaction soln to be strongly-acid than strongly-acid, pH is 3.0～4.0.In such strong acid environment, side reaction is certain to take place, thereby has reduced the selectivity of propylene oxide.For avoiding the generation of side reaction, can in reaction soln, add alkaline matter, improve the pH of solution.But pH value of solution is too high, and solution is strong basicity, not only can cause the generation of side reaction, and can cause the inactivation of catalyzer.Therefore, the present invention is controlled at pH value of solution between 5.0～8.0.
The adjusting of pH value of solution can change by the amount of neutral salt, basic salt or alkali in the control adding reaction system, for example adds Na
2SO
4, KOH, NH
3, NaOH, K
2CO
3, Na
2CO
3, KHCO
3, Li
2CO
3, LiHCO
3, Na
2HPO
4, NH
4OAc, ammoniacal liquor, triethylamine, pyridine etc.; The adjusting of pH value of solution can also change the pH value of solution value by the air speed of control solution by resin bed, reduces air speed, and the pH value of solution value improves.
With the hydrogen peroxide is oxygenant, and during titanium molecular sieve catalysis propylene ring oxidation reaction synthesizing epoxypropane, temperature is very big to the reaction influence.Reduce temperature, the hydrogen peroxide transformation efficiency reduces, and side reaction reduces, and the selectivity of propylene oxide improves; Elevated temperature, the hydrogen peroxide transformation efficiency increases, and accelerates the carrying out of side reaction, though reduced the selectivity of propylene oxide, also can accelerate the desorption of propylene oxide and by product simultaneously, helps prolonging life of catalyst.
The present invention prolongs the catalyst life of synthesizing epoxypropane by regulator solution pH and temperature of reaction, need change reaction parameter according to practical situation, is a dynamic process.When just beginning to react, the pH value of solution value is lower, and the hydrogen peroxide transformation efficiency is higher, and side reaction is accelerated, and the selectivity of propylene oxide is lower, at this moment should adopt than low reaction temperatures and higher pH value of solution value, with transformation efficiency that reduces hydrogen peroxide and the selectivity that increases propylene oxide.Along with the carrying out of reaction, the hydrogen peroxide transformation efficiency can reduce gradually, and the selectivity of propylene oxide reduces, and should progressively improve the pH value of temperature and solution this moment, with the transformation efficiency of maintenance hydrogen peroxide and the selectivity of propylene oxide.
The whole process of the present invention is simple, pollution-free, propylene oxide selectivity height, prolongs life of catalyst by adding tensio-active agent, regulator solution pH and temperature of reaction simultaneously, and catalyst life can reach more than 1200 hours.
Four, embodiment:
Following embodiment will the present invention is further illustrated:
Embodiment 1:
60gHTS mixes with 20g kaolin, 66g silicon sol, 5g methylcellulose gum, 2ml concentrated nitric acid and suitable quantity of water, extruded moulding then, and catalyst size is 2 * 2 millimeters.
Embodiment 2:
Embodiment 1 catalyzer is loaded in the fixed-bed reactor, and loaded catalyst is 15ml, and catalyzer is adorned the porcelain ring filler up and down.Reaction raw materials is earlier by being equipped with the bed of resin, enter fixed-bed reactor then, every 4 hours sampling analysis hydrogen peroxide transformation efficiencys, when the hydrogen peroxide transformation efficiency is reduced to 88.5% when following, reduce reaction raw materials by the bed air speed of resin is housed, then pH improves, and improves temperature of reaction simultaneously, do not add tensio-active agent in the reaction raw materials, experimental result is as shown in table 1.Table 1 shows that this catalyst life is long, reaches 1218 hours.
Table 1 optimization of process conditions is to the influence of catalyzer
| Reaction times/h | Methyl alcohol/hydrogen peroxide (mol) | Propylene/hydrogen peroxide (mol) | Pressure (MPa) | pH | Temperature (℃) | Air speed (h -1) | Hydrogen peroxide transformation efficiency (%) | Propylene oxide selectivity (%) |
| 17.00 | 15 | 0.5 | 0.5 | 5.00 | 40.00 | 7.00 | 88.85 | 99.45 |
| 200.00 | 7 | 2.0 | 2.0 | 5.00 | 40.00 | 2.00 | 96.25 | 94.28 |
| 608.00 | 7 | 2.0 | 2.8 | 5.50 | 55.00 | 1.30 | 92.63 | 92.04 |
| 700.00 | 7 | 2.0 | 3.0 | 6.10 | 60.00 | 1.30 | 92.06 | 92.52 |
| 966.00 | 7 | 2.0 | 3.8 | 6.80 | 66.00 | 1.30 | 90.07 | 92.60 |
| 1206.00 | 4 | 4.0 | 4.5 | 7.50 | 75.00 | 0.50 | 89.40 | 88.52 |
| 1218.00 | 1 | 5.0 | 4.5 | 8.00 | 90.00 | 0.10 | 88.75 | 80.32 |
Embodiment 3:
Embodiment 1 catalyzer is loaded in the fixed-bed reactor, and loaded catalyst is 15ml, and catalyzer is adorned the porcelain ring filler up and down.The sorbester p17 (Span) of adding 0.90% and 0.05% tween 80 (Tween) in the reaction raw materials, every 4 hours sampling analysis hydrogen peroxide transformation efficiencys, when the hydrogen peroxide transformation efficiency is reduced to 88.5% when following, add ammoniacal liquor and improve pH value of solution, improve temperature of reaction simultaneously.Experimental result is as shown in table 3, and as can be seen from Table 3, by regulator solution pH, conditioned reaction temperature and adding tensio-active agent, catalyst life further prolongs.
Table 2 optimization of process conditions is to the influence of catalyzer
| Reaction times/h | Methyl alcohol/hydrogen peroxide (mol) | Propylene/hydrogen peroxide (mol) | Pressure (MPa) | pH | Temperature (℃) | Air speed (h -1) | Hydrogen peroxide transformation efficiency (%) | Propylene oxide selectivity (%) |
| 50.00 | 7 | 1.5 | 2.5 | 5.10 | 30.00 | 1.30 | 98.26 | 98.25 |
| 350.00 | 7 | 1.5 | 2.5 | 5.10 | 45.00 | 1.30 | 95.45 | 94.27 |
| 950.00 | 7 | 1.5 | 2.5 | 6.00 | 66.00 | 1.30 | 96.05 | 96.10 |
| 1000.00 | 7 | 1.5 | 2.5 | 6.00 | 66.00 | 1.30 | 95.70 | 95.98 |
| 1200.00 | 7 | 1.5 | 2.5 | 7.50 | 70.00 | 1.30 | 95.65 | 95.08 |
| 1450.00 | 7 | 1.5 | 2.5 | 8.00 | 80.00 | 1.30 | 95.01 | 95.01 |
Embodiment 4
Embodiment 1 catalyzer is loaded in the fixed-bed reactor, and loaded catalyst is 15ml, and catalyzer is adorned the porcelain ring filler up and down.Reaction raw materials adds 0.1% sorbester p17 (Span), every 4 hours sampling analysis hydrogen peroxide transformation efficiencys, when the hydrogen peroxide transformation efficiency is reduced to 88.5% when following, adding Na
2CO
3Improve pH value of solution, improve temperature of reaction simultaneously.The result is as shown in table 3.
Table 3 optimization of process conditions is to the influence of catalyzer
| Reaction times/h | Methyl alcohol/hydrogen peroxide (mol) | Propylene/hydrogen peroxide (mol) | Pressure (MPa) | pH | Temperature (℃) | Air speed (h -1) | Hydrogen peroxide transformation efficiency (%) | Propylene oxide selectivity (%) |
| 40.00 | 6 | 2 | 2.5 | 5.10 | 40.00 | 1.30 | 98.12 | 97.28 |
| 400.00 | 6 | 2 | 2.5 | 5.10 | 45.00 | 1.30 | 95.40 | 93.10 |
| 530.00 | 6 | 2 | 2.5 | 5.7 | 50.00 | 1.30 | 97.01 | 96.07 |
| 750.00 | 6 | 2 | 2.5 | 5.7 | 60.00 | 1.30 | 96.42 | 95.67 |
| 960.00 | 6 | 2 | 2.5 | 6.10 | 66.00 | 1.30 | 96.00 | 95.19 |
| 1180.00 | 6 | 2 | 2.5 | 7.60 | 70.00 | 1.30 | 95.37 | 94.32 |
| 1420.00 | 6 | 2 | 2.5 | 8.00 | 80.00 | 1.30 | 94.58 | 93.25 |
Embodiment 5
HTS is loaded in the slurry bed reactor, and total liquid volume is 3 liters, and loaded catalyst accounts for 5% of total amount of liquid.Reaction raw materials adds 0.5% sorbester p17 (Span), every 4 hours sampling analysis hydrogen peroxide transformation efficiencys, when the hydrogen peroxide transformation efficiency is reduced to 88.5% when following, adds triethylamine raising pH value of solution, improves temperature of reaction simultaneously.The result is as shown in table 4.
Table 4 optimization of process conditions is to the influence of catalyzer
| Reaction times/h | Methyl alcohol/hydrogen peroxide (mol) | Propylene/hydrogen peroxide (mol) | Pressure (MPa) | pH | Temperature (℃) | Air speed (h -1) | Hydrogen peroxide transformation efficiency (%) | Propylene oxide selectivity (%) |
| 80.00 | 7 | 1.2 | 2.5 | 5.00 | 40.00 | 1.80 | 98.36 | 96.32 |
| 350.00 | 7 | 1.2 | 2.5 | 5.00 | 45.00 | 1.80 | 96.20 | 95.21 |
| 600.00 | 7 | 1.2 | 2.5 | 5.8 | 55.00 | 1.80 | 96.42 | 94.32 |
| 893.00 | 7 | 1.2 | 2.5 | 6.50 | 66.00 | 1.80 | 96.12 | 93.98 |
| 1002.00 | 7 | 1.2 | 2.5 | 7.80 | 70.00 | 1.80 | 95.03 | 92.54 |
| 1250.00 | 7 | 1.2 | 2.5 | 7.80 | 75.00 | 1.80 | 95.21 | 90.86 |
| 1417.00 | 7 | 1.2 | 2.5 | 8.00 | 80.00 | 1.80 | 94.97 | 88.74 |
Claims (6)
1, a kind of method of synthesizing epoxypropane, it is characterized in that: mol ratio (1～15): (0.5～5): 1 low-carbon alcohol, propylene, hydrogen peroxide are in being equipped with the reactor of catalyzer, propylene and hydrogen peroxide initial ring oxidizing reaction obtain propylene oxide, described reaction conditions is 30 ℃～90 ℃ of temperature of reaction, reaction pressure 0.5～4.5Mpa, pH value of solution 5.0～8.0, liquid air speed 0.1～7h
-1, wherein pH value of solution and temperature of reaction are regulated according to the hydrogen peroxide transformation efficiency in entire reaction course at any time, and hydrogen peroxide transformation efficiency one is reduced to 88.5%, just improves pH value of solution and temperature of reaction.
2, method according to claim 1 is characterized in that: described low-carbon alcohol particular methanol, ethanol, butanols.
3, method according to claim 1 is characterized in that: add tensio-active agent in the described reaction, its addition is 0～1%.
4, method according to claim 3 is characterized in that: described tensio-active agent is a kind of in water soluble surfactant active, the oil soluble surfactant or their interworking.
5, method according to claim 1 is characterized in that: the adjusting of described pH value of solution changes by the amount that control adds neutral salt, basic salt or alkali in the reaction system.
6, method according to claim 1 is characterized in that: the adjusting of described pH value of solution is achieved by the air speed of control solution by resin bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100313937A CN101279959B (en) | 2008-05-21 | 2008-05-21 | Method for synthesizing epoxypropane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100313937A CN101279959B (en) | 2008-05-21 | 2008-05-21 | Method for synthesizing epoxypropane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101279959A true CN101279959A (en) | 2008-10-08 |
| CN101279959B CN101279959B (en) | 2010-12-01 |
Family
ID=40012651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100313937A Active CN101279959B (en) | 2008-05-21 | 2008-05-21 | Method for synthesizing epoxypropane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101279959B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012048530A1 (en) | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Refining method for crude propylene oxide product and preparation method for propylene oxide |
| WO2012048529A1 (en) * | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Method for producing oxidized olefin through olefin epoxidation |
| WO2012048528A1 (en) * | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Epoxidation method for olefin |
| CN102442976A (en) * | 2010-10-11 | 2012-05-09 | 中国石油化工股份有限公司 | Method for epoxidizing olefinic hydrocarbon |
| WO2012149827A1 (en) | 2011-05-05 | 2012-11-08 | 中国石油化工股份有限公司 | Method for oxidating cyclohexane |
| CN102952003A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method of preparing ethylene glycol monomethyl ether by using one-step ethylene method |
| CN102951998A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method of preparing glycol by using one-step ethylene method |
| CN104211665A (en) * | 2013-05-31 | 2014-12-17 | 中国石油化工股份有限公司 | Alkene oxidation method |
| CN104447628A (en) * | 2013-09-12 | 2015-03-25 | 中国石油化工股份有限公司 | Method for prolonging alkene epoxidation stable operation time |
| CN104447627A (en) * | 2013-09-12 | 2015-03-25 | 中国石油化工股份有限公司 | Alkene epoxidation method |
| CN104447626A (en) * | 2013-09-12 | 2015-03-25 | 中国石油化工股份有限公司 | Alkene oxidation method |
| CN104803953A (en) * | 2014-01-28 | 2015-07-29 | 中国石油化工股份有限公司 | Olefin epoxidation method |
| CN105439815A (en) * | 2014-08-21 | 2016-03-30 | 中国石油化工股份有限公司 | Method for preparing propylene glycol |
| CN105481798A (en) * | 2014-09-29 | 2016-04-13 | 中国石油化工股份有限公司 | Method for oxidating alkene |
| CN105524019A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Olefin oxide preparation method |
| CN105524018A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Olefin epoxidation method |
| CN105524026A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Method for oxidation of olefin |
| CN105524020A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Oxidation method for olefin |
| CN105524021A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Oxidation method for olefin |
| CN105524025A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Method for oxidizing olefin |
| CN105597631A (en) * | 2014-09-29 | 2016-05-25 | 中国石油化工股份有限公司 | Fixed bed reaction device and alkene oxidation reaction system |
| CN106243064A (en) * | 2016-08-01 | 2016-12-21 | 中触媒新材料股份有限公司 | The application of auxiliary agent in a kind of propylene ring oxidation reaction |
-
2008
- 2008-05-21 CN CN2008100313937A patent/CN101279959B/en active Active
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8859791B2 (en) | 2010-10-11 | 2014-10-14 | China Petroleum & Chemical Corporation | Process for producing an alkylene oxide by olefin epoxidation |
| WO2012048529A1 (en) * | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Method for producing oxidized olefin through olefin epoxidation |
| WO2012048528A1 (en) * | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Epoxidation method for olefin |
| CN102442976A (en) * | 2010-10-11 | 2012-05-09 | 中国石油化工股份有限公司 | Method for epoxidizing olefinic hydrocarbon |
| RU2576620C2 (en) * | 2010-10-11 | 2016-03-10 | Чайна Петролеум Энд Кемикал Корпорейшн | Olefin epoxidation method |
| RU2567749C2 (en) * | 2010-10-11 | 2015-11-10 | Чайна Петролеум Энд Кемикал Корпорейшн | Method of producing alkylene oxide by olefin epoxidation |
| WO2012048530A1 (en) | 2010-10-11 | 2012-04-19 | 中国石油化工股份有限公司 | Refining method for crude propylene oxide product and preparation method for propylene oxide |
| CN102442976B (en) * | 2010-10-11 | 2014-01-15 | 中国石油化工股份有限公司 | Method for epoxidizing olefinic hydrocarbon |
| WO2012149827A1 (en) | 2011-05-05 | 2012-11-08 | 中国石油化工股份有限公司 | Method for oxidating cyclohexane |
| US8940939B2 (en) | 2011-05-05 | 2015-01-27 | China Petroleum & Chemical Corporation | Process of oxidizing cyclohexane |
| CN102952003B (en) * | 2011-08-24 | 2015-04-01 | 岳阳蓬诚科技发展有限公司 | Method of preparing ethylene glycol monomethyl ether by using one-step ethylene method |
| CN102951998B (en) * | 2011-08-24 | 2015-07-01 | 岳阳蓬诚科技发展有限公司 | Method of preparing glycol by using one-step ethylene method |
| CN102951998A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method of preparing glycol by using one-step ethylene method |
| CN102952003A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method of preparing ethylene glycol monomethyl ether by using one-step ethylene method |
| CN104211665A (en) * | 2013-05-31 | 2014-12-17 | 中国石油化工股份有限公司 | Alkene oxidation method |
| CN104211665B (en) * | 2013-05-31 | 2016-10-05 | 中国石油化工股份有限公司 | A kind of method of olefin oxidation |
| CN104447628A (en) * | 2013-09-12 | 2015-03-25 | 中国石油化工股份有限公司 | Method for prolonging alkene epoxidation stable operation time |
| CN104447627A (en) * | 2013-09-12 | 2015-03-25 | 中国石油化工股份有限公司 | Alkene epoxidation method |
| CN104447626A (en) * | 2013-09-12 | 2015-03-25 | 中国石油化工股份有限公司 | Alkene oxidation method |
| CN104803953B (en) * | 2014-01-28 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of olefin epoxidation method |
| CN104803953A (en) * | 2014-01-28 | 2015-07-29 | 中国石油化工股份有限公司 | Olefin epoxidation method |
| CN105439815A (en) * | 2014-08-21 | 2016-03-30 | 中国石油化工股份有限公司 | Method for preparing propylene glycol |
| CN105439815B (en) * | 2014-08-21 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of method for preparing propane diols |
| CN105524021A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Oxidation method for olefin |
| CN105524020B (en) * | 2014-09-29 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of olefin oxidation method |
| CN105481798A (en) * | 2014-09-29 | 2016-04-13 | 中国石油化工股份有限公司 | Method for oxidating alkene |
| CN105524025A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Method for oxidizing olefin |
| CN105597631A (en) * | 2014-09-29 | 2016-05-25 | 中国石油化工股份有限公司 | Fixed bed reaction device and alkene oxidation reaction system |
| CN105524026A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Method for oxidation of olefin |
| US10400179B2 (en) | 2014-09-29 | 2019-09-03 | China Petroleum & Chemical Corporation | Olefin oxidation process, reaction apparatus and system |
| CN105524018A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Olefin epoxidation method |
| CN105524019A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Olefin oxide preparation method |
| CN105524020A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Oxidation method for olefin |
| CN105524019B (en) * | 2014-09-29 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of preparation method of oxyalkylene |
| CN105524018B (en) * | 2014-09-29 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of olefin epoxidation method |
| CN105524021B (en) * | 2014-09-29 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of olefin oxidation method |
| CN105524025B (en) * | 2014-09-29 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method of oxyalkylene |
| CN105481798B (en) * | 2014-09-29 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of olefin oxidation method |
| CN105524026B (en) * | 2014-09-29 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of method of oxyalkylene |
| CN105597631B (en) * | 2014-09-29 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of fixed-bed reactor and olefin hydrocarbon oxidation reaction system |
| CN106243064A (en) * | 2016-08-01 | 2016-12-21 | 中触媒新材料股份有限公司 | The application of auxiliary agent in a kind of propylene ring oxidation reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101279959B (en) | 2010-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101279959B (en) | Method for synthesizing epoxypropane | |
| CN100556880C (en) | A kind of method of synthesis of propylene glycol | |
| CN112537998B (en) | Process for producing neopentyl glycol by continuous catalytic hydrogenation | |
| CN111389401B (en) | For the efficient catalytic conversion of CO2Preparation method of microorganism coupling catalytic system | |
| CN112876395B (en) | Preparation method of vitamin A acetate | |
| CN103785414A (en) | Carboxylic acid hydrogenation catalyst, preparation method and application thereof | |
| CN103787829B (en) | A kind of cobalt silver catalyst hydrogenation of carboxylic acids prepares the method for alcohol | |
| CN106478586B (en) | Synthesis process of ethylene carbonate | |
| CN105032420A (en) | Cu/SiO2 catalyst and method therefor for synthesizing tetrahydrofuran | |
| CN102211978A (en) | Method for synthesizing glycol by hydrogenation of dimethyl oxalate | |
| CN106478583A (en) | The synthetic method of ethylene carbonate | |
| CN102516029A (en) | Method for synthesising methanol by complete cycle of carbon monoxide, carbon dioxide and hydrogen | |
| CN114085136A (en) | Method for preparing cyclopentanone by catalyzing furfural | |
| CN101328158B (en) | Method for synthesizing butyl oxide linkage | |
| CN111905830A (en) | Catalyst for selective hydrogenation of furfural | |
| CN106699507A (en) | Preparation method for alpha-phenethanol | |
| CN102974342A (en) | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof | |
| CN114950505B (en) | Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide, and preparation method and application thereof | |
| CN114436773B (en) | Method for improving hydrogenation conversion rate of carbon dioxide through coupling dehydration | |
| CN102755910A (en) | Titanium silicon molecular sieve and resin composite modified catalyst and preparation method thereof | |
| CN105771998A (en) | Catalyst for preparing hydroxypivalaldehyde and method for applying catalyst | |
| CN113134362B (en) | Heterogeneous catalyst for preparing lactaldehyde by non-ligand hydroformylation of acetaldehyde and synthesis gas and preparation method and application thereof | |
| CN1337386A (en) | Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn | |
| CN110862302A (en) | Method for preparing 1, 4-butanediol by combining slurry bed hydrogenation and fixed bed hydrogenation | |
| CN114409520A (en) | Method for preparing trimethylolpropane by hydrogenation with high condensation yield |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 414012 Lu Kou Zhen Chang Lian Long Kou, Yunxi District, Yueyang City, Hunan Province (opposite to Chang Lian hospital) Patentee after: Hunan Changlian New Material Technology Co.,Ltd. Patentee after: Lin Rongwei Address before: 414012 Yunxi District, Hunan City, Yueyang Province, Changling Patentee before: HUNAN CHANGLING PETROCHEMICAL TECHNOLOGY DEVELOPMENT Co.,Ltd. Patentee before: Lin Rongwei |
|
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Hua Inventor after: Wang Wei Inventor after: He Chijian Inventor after: Wu Xiaoju Inventor after: Gao Jizao Inventor before: Li Hua Inventor before: Wang Wei Inventor before: Lin Rongwei Inventor before: He Chijian Inventor before: Wu Xiaoju Inventor before: Gao Jizao |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230601 Address after: 414012 Lu Kou Zhen Chang Lian Long Kou, Yunxi District, Yueyang City, Hunan Province (opposite to Chang Lian hospital) Patentee after: Hunan Changlian New Material Technology Co.,Ltd. Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: CHANGLING BRANCH, CHINA PETROLEUM CHEMICAL Corp. Address before: 414012 Lu Kou Zhen Chang Lian Long Kou, Yunxi District, Yueyang City, Hunan Province (opposite to Chang Lian hospital) Patentee before: Hunan Changlian New Material Technology Co.,Ltd. Patentee before: Lin Rongwei |