CN1415608A - Cleanly method for producing propylene oxide from propylene with low-pressure and low concentration - Google Patents
Cleanly method for producing propylene oxide from propylene with low-pressure and low concentration Download PDFInfo
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- CN1415608A CN1415608A CN02145329A CN02145329A CN1415608A CN 1415608 A CN1415608 A CN 1415608A CN 02145329 A CN02145329 A CN 02145329A CN 02145329 A CN02145329 A CN 02145329A CN 1415608 A CN1415608 A CN 1415608A
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- propylene
- reaction
- hydrogen phosphide
- propylene oxide
- phosphide cumene
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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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- 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
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Abstract
A process for preparing epoxy propane from low-pressure low-concentration propane without generation of alkaline sewage features that the propene gas and the solution of hydrogen peroxide in isophenylbenzene take part in reaction under existance of multi-phase Mo-series catalyst. Its advantages are high selectivity and clean process.
Description
Technical field
The present invention relates to the production method of propylene oxide, particularly be raw material, be the production method of oxygenant, more relate to the catalyzer that uses in this production process with hydrogen phosphide cumene (CHP) with the lower concentration propylene.
Background technology
Propylene oxide (PO) is important basic Organic Chemicals, and in acryloyl derivative, output is only second to polypropylene, vinyl cyanide.Because propylene oxide has the very big oxygen ring of tension force, chemical property is active, not only can produce polyether glycol (producing the raw material of urethane), propylene glycol, also be the important source material of producing number of chemical product such as nonionogenic tenside, oil field emulsion splitter, farm chemical emulgent.Present industrial production propylene oxide mainly adopts chlorohydrination and Halcon method (indirect oxidation method).On the basis of the original production technique of technological transformation, to having the catalytic H of eco-friendly Ti-Si zeolite
2O
2Direct oxidation method, oxygen gas phase direct oxidation method, the synthetic H of original position
2O
2Novel process and methods such as oxidation style, photochemical catalysis are synthetic are the problems that domestic and international investigator paid close attention to always, and the indirect oxidation method adopts the organo-peroxide propylene oxide to get propylene oxide.Organo-peroxide can be an organic hydroperoxide, also can be the percarboxylic acids thing.These superoxide can selectively be transferred to the oxygen of their peroxides part on the alkene, generate epoxide, self are converted into alcohol or ketone, and percarboxylic acids is converted into organic acid.At present, the indirect oxidation method is in industrial extensive use, and commonly used is Trimethylmethane method and ethylbenzene method.Hydrogen phosphide cumene is a raw material of producing phenol and acetone.It is generated as the oxygenant oxidation with air by isopropyl benzene.If can utilize conventional device and raw material in the petrochemical plant, the comprehensive utilization energy under the situation of not appending more investments, is produced propylene oxide, is more satisfactory technology at present.For this reason, the patent of sumitomo chemical company provides and adopted hydrogen phosphide cumene is the technological process of oxidant production propylene oxide, the technology of reporting as following document and patent:
(1)AUTHOR(S)Oku，Noriaki；Seo，Tateo(CORPORATE?SOURCESumitomo?Chemical?Company，Limited，Japan).SOURCE?PCT?Int.Appl.WO?2001005778?A1?25?Jan?2001；
(2)AUTHOR(S)?Tsuji，Junpei；Yamamoto，Jun；Ishino，Masaru(CORPORATE?SOURCE?Sumitomo?Chemical?Co.，Ltd.，Japan).SOURCEJpn.Kokai?Tokkyo?Koho?JP?2001270875?A2?2?Oct?2001；
(3)AUTHOR(S)Ito，Sadaaki；Seo，Takeo(CORPORATE?SOURCESumitomo?Chemical?Co.，Ltd.，Japan).SOURCE?Jpn.Kokai?Tokkyo?KohoJP?2001270880?A2?2?Oct?2001；
(4)AUTHOR(S)Oku，Noriaki；Omae，Toshikazu(CORPORATESOURCE?Sumitomo?Chemical?Company，Limited，Japan).SOURCE?PCTInt.APPl.WO?2001070715?A1?27?Sep?2001；
(5)AUTHOR(S)Seo，Takeo；Tsuji，Junpei(CORPORATE?SOURCESumitomo?Chemical?Company，Limited，Japan).SOURCE?PCT?Int.Appl.WO?2001070714?A1?27?Sep?2001；
(6)AUTHOR(S)Tsuji，Junpei；Yamamoto，Jun(CORPORATESOURCE?Sumitomo?Chemical?Company，Limited，Japan).SOURCE?PCTInt.Appl.WO?2001070710?A1?27?Sep?2001；
The disclosed technology of above-mentioned patent all adopts titaniferous silicon oxide catalyst.At first, isopropyl benzene is oxidized to hydrogen phosphide cumene; Secondly, hydrogen phosphide cumene and propylene reaction generate propylene oxide and α, alpha-alpha-dimethyl benzylalcohol, and temperature of reaction 25-200, reaction pressure should make reaction mixture keep liquid; At last, joint product α, alpha-alpha-dimethyl benzylalcohol is converted into isopropyl benzene by catalytic hydrogenolytic cleavage, uses as raw material again.
AUTHOR(S)Yamamoto，Jun；Tsuji，Junpei(CORPORATE?SOURCESumitomo?Chemical?Company，Ltd.，Japan).SOURCE?PCT?Int.Appl.WO2001056693?A1?9?Aug?2001；
AUTHOR(S)Yamamoto，Jun；Tsuji，Junpei(CORPORATE?SOURCESumitomo?Chemical?Co.，Ltd.，Japan).SOURCE?Jpn.Kokai?Tokkyo?KohoJP?2000117101?A2?25?Apr?2000；
It is raw material that the disclosed technology of above-mentioned patent all needs to adopt the propylene of high density, in order to improve the selectivity of reaction process propylene oxide, need in reaction process, add alkaline matter, thereby have alkaline waste liquor to produce in process of production, will produce pollution environment.
Summary of the invention
The technical issues that need to address of the present invention are the clean preparation methods that disclose a kind of low pressure lower concentration propylene production propylene oxide, to adopt the propylene of high density be the generation that alkaline waste liquor is arranged in raw material and the production process to overcome needs that prior art exists, causes the defective of environmental pollution.
Method of the present invention comprises the steps:
With propylene in the presence of heterogeneous molybdenum series catalyst with solvent in hydrogen phosphide cumene solution react, reaction pressure is 0.1-1MPa, temperature of reaction is 90-120 ℃, the reaction times is 1-4h, can obtain propylene oxide.
Wherein: can adopt propylene gas, concentration is 2～98%wt, also can adopt liquid third rare, and hydrogen phosphide cumene solution is the cumene solution that contains the 20-30%wt hydrogen phosphide cumene, and the solvent of being addressed is C
2-C
6Unit alcohol or polyvalent alcohol, preferred tertiary butanols, its consumption be the hydrogen phosphide cumene liquor capacity 0.5-2.0 doubly.
The result shows that at 110 ℃ of reaction 2h, the transformation efficiency of hydrogen phosphide cumene is 84%, and propylene oxide is 89% to the selectivity of CHP.
The major ingredient of said heterogeneous molybdenum series catalyst comprises MoO
3And SiO
2(contain Ti, K, Na, Mg, Ca, Cr, one or both among the W or do not contain wherein any), specifically consist of:
MoO
3 5-25％wt
TiO
2 0-10％wt
SiO
2 60-95％wt
Other 0-5%wt
Catalyst consumption is counted 0.5-5wt% with hydrogen phosphide cumene solution.
Above-mentioned catalyzer is preparation like this: get 40mL tetraethoxy (TEOS) and 40mL dehydrated alcohol in there-necked flask, the HCl solution adjusting pH value that adds 0.0001-0.1N is 2-5, behind stirring reaction 1h under 80 ℃ of constant temperature, cool to room temperature under agitation, be added dropwise to the organism (as 1,2-propylene glycol, glycerol, polyoxyethylene glycol, ethanamide, methane amide and N, one or more in the dinethylformamide) of 1-10%wt then, continue to stir after 2 minutes, be added dropwise to (the NH of 80mL
4)
6Mo
7O
244H
2O (contain Ti, K, Na, Mg, Ca, Cr, one or both among the W or do not contain wherein any), stop after dropwising stirring, 3h, aged at room temperature 48h ℃ are left standstill in temperature rise to 80 again.The gained gel is through 110 ℃ of dryings with after grinding, and roasting 5h in 550 ℃ of air of retort furnace makes light yellow mixed oxide catalyst.
Method of the present invention has very significant advantage:
(1) need not to add the selectivity that any alkaline matter improves propylene oxide in the reaction system, can eliminate the generation of existing technology neutral and alkali waste liquid, realize cleaner production.
(2) can be applicable to the recycling of propylene gas on a small quantity in the tail gas of chemical plant, the propylene oxide of production high added value.
(3) can be applicable to pure third rare gas (or liquid third is rare) oxidation step system propylene oxide.
Embodiment
Embodiment 1
Get 20mL hydrogen phosphide cumene (technical grade, content 30%), 0.2g catalyzer (15%wtMoO
3, 85%wt SiO
2) and the 20mL trimethyl carbinol, join in the 0.3L stainless steel cauldron, in still, feed propylene (98%) gas, treat that pressure reaches and reactor is put into oil bath behind the 0.6MPa and heat, behind 110 ℃ of reaction 2h, place ice-water bath to cool off reactor, reaction product is analyzed after centrifugation.The transformation efficiency of CHP is 89%, and PO is 80% to the selectivity of CHP.
Embodiment 2
Get 20mL hydrogen phosphide cumene (technical grade, content 20%), 0.2g catalyzer (15%wt MoO
3, 84.9%wt SiO
2, 0.1%wt K
2O) and the 20mL trimethyl carbinol, join in the 0.3L stainless steel cauldron, in still, feed propylene (50%) gas, treat that pressure reaches and reactor is put into oil bath behind the 0.6MPa and heat, behind 110 ℃ of reaction 2h, place ice-water bath to cool off reactor, reaction product is analyzed after centrifugation.The CHP transformation efficiency is 92.7%, and PO is 43.6% to the selectivity of CHP.
Embodiment 3
Get 20mL hydrogen phosphide cumene (technical grade, content 30%), 0.2g catalyzer (15%wt MoO
3, 84.9%wt SiO
20.1%wt MgO) and the 20mL trimethyl carbinol, join in the 0.3L stainless steel cauldron, in still, feed propylene (10%) gas, treat that pressure reaches and reactor is put into oil bath behind the 0.6MPa and heat, behind 110 ℃ of reaction 2h, place ice-water bath to cool off reactor, reaction product is analyzed after centrifugation.The CHP transformation efficiency is 88.9%, and PO is 47.2% to the selectivity of CHP.
Embodiment 4
Get 20mL hydrogen phosphide cumene (technical grade, content 30%), 0.2g catalyzer (15%wt MoO
3, 84.9%wt SiO
2, 0.1%wt Na
2O) and the 20mL trimethyl carbinol, join in the 0.3L stainless steel cauldron, in still, feed propylene (2%) gas, treat that pressure reaches and reactor is put into oil bath behind the 0.6MPa and heat, behind 90 ℃ of reaction 2h, place ice-water bath to cool off reactor, reaction product is analyzed after centrifugation.Through the catalyzer of modification of sodium carbonate preparation, the CHP transformation efficiency is 81.8%, and PO is 70.5% to the selectivity of CHP.
Embodiment 5
Get 20mL hydrogen phosphide cumene (technical grade, content 30%), 0.2g catalyzer (10%wt MoO
3, 90%wt SiO
2) and trimethyl carbinol 20mL, join in the 0.3L stainless steel cauldron, in still, feed propylene gas (98%), treat that pressure reaches and reactor is put into oil bath behind the 0.6MPa and heat, behind 110 ℃ of reaction 2h, place ice-water bath to cool off reactor, reaction product is analyzed after centrifugation.The CHP transformation efficiency is 84%, and PO is 89% to the selectivity of CHP.
Embodiment 6
Get 20mL hydrogen phosphide cumene (technical grade, content 30%), 0.2g catalyzer (10%wt MoO
3, 85%wt SiO
2, 5%wt TiO
2) and trimethyl carbinol 20mL, join in the 0.3L stainless steel cauldron, in still, feed propylene (98%), treat that pressure reaches and reactor is put into oil bath behind the 0.6MPa and heat, behind 105 ℃ of reaction 2h, place ice-water bath to cool off reactor, reaction product is analyzed after centrifugation.The CHP transformation efficiency is 95%, and PO is 78% to the selectivity of CHP.
Embodiment 7
Get 20mL hydrogen phosphide cumene (technical grade, content 30%), 0.2g catalyzer (20%wt MoO
3, 80%wt SiO
2) trimethyl carbinol 20mL, join in the 0.3L stainless steel cauldron, in still, feed propylene (98%) gas, treat that pressure reaches and reactor is put into oil bath behind the 0.6MPa and heat, behind 110 ℃ of reaction 1h, place ice-water bath to cool off reactor, reaction product is analyzed after centrifugation.MoO
3When charge capacity was 10%wt, the CHP transformation efficiency was 95%, and PO is 59% to the selectivity of CHP.
Embodiment 8
Get 20mL hydrogen phosphide cumene (technical grade, content 30%), 0.2g catalyzer (15%wt MoO
3, 85%wt SiO
2) and the 20mL trimethyl carbinol, join in the 0.3L stainless steel cauldron, in still, feed propylene (20%) gas, treat that pressure reaches and reactor is put into oil bath behind the 0.6MPa and heat, behind 120 ℃ of reaction 4h, place ice-water bath to cool off reactor, reaction product is analyzed after centrifugation.The CHP transformation efficiency is 98.5%, and PO is 43.9% to the selectivity of CHP.
Claims (9)
1. the production method of a propylene oxide is characterized in that comprising the steps:
With propylene in the presence of heterogeneous molybdenum series catalyst with solvent in hydrogen phosphide cumene solution react, the major ingredient of said heterogeneous molybdenum series catalyst comprises:
MoO
3 5-25％wt
TiO
2 0-10％wt
SiO
2 60-95％wt
Other 0-5%wt.
2. method according to claim 1 is characterized in that reaction pressure is 0.1-1MPa.
3. method according to claim 1 is characterized in that temperature of reaction is 90-120 ℃.
4. method according to claim 1 is characterized in that the reaction times is 1-4h.
5. method according to claim 1 is characterized in that the solvent of being addressed is C
2-C
6Unit alcohol or polyvalent alcohol.
6. method according to claim 5 is characterized in that the solvent of being addressed is the trimethyl carbinol.
7. method according to claim 1 is characterized in that propylene is a gas, and concentration is 2-98%wt, or liquid third is rare.
8. method according to claim 1 is characterized in that hydrogen phosphide cumene solution is the cumene solution that contains the 20-30%wt hydrogen phosphide cumene.
9. according to each described method of claim 1～8, it is characterized in that catalyst consumption counts 0.5-5wt% with hydrogen phosphide cumene solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021453292A CN1252059C (en) | 2002-11-21 | 2002-11-21 | Cleanly method for producing propylene oxide from propylene with low-pressure and low concentration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021453292A CN1252059C (en) | 2002-11-21 | 2002-11-21 | Cleanly method for producing propylene oxide from propylene with low-pressure and low concentration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1415608A true CN1415608A (en) | 2003-05-07 |
| CN1252059C CN1252059C (en) | 2006-04-19 |
Family
ID=4750855
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021453292A Expired - Fee Related CN1252059C (en) | 2002-11-21 | 2002-11-21 | Cleanly method for producing propylene oxide from propylene with low-pressure and low concentration |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497045B (en) * | 2009-03-11 | 2011-03-30 | 华东理工大学 | Catalyst for producing epoxypropane by liquid phase one-step oxidation of propylene and preparation method |
| CN103539762A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for producing epoxypropane by propylene epoxidation |
| CN104230854A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Cumyl hydroperoxide and propylene epoxidation method for preparing epoxypropane |
| CN104437450A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Titanium-containing silicon dioxide catalyst and preparation method and use thereof |
| CN104557781A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing propylene oxide |
| CN104557780A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of epoxypropane |
| CN104557779A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| CN105272813A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Propylene recovery method |
| CN105294379A (en) * | 2014-07-24 | 2016-02-03 | 中国石油化工股份有限公司 | Propylene recovery equipment |
| CN110947375A (en) * | 2019-11-26 | 2020-04-03 | 红宝丽集团股份有限公司 | Catalyst for preparing propylene oxide and preparation method thereof |
| CN114426547A (en) * | 2020-09-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for producing dicyclopentadiene dioxide by using molybdenum-based homogeneous catalyst and obtained dicyclopentadiene dioxide |
-
2002
- 2002-11-21 CN CNB021453292A patent/CN1252059C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497045B (en) * | 2009-03-11 | 2011-03-30 | 华东理工大学 | Catalyst for producing epoxypropane by liquid phase one-step oxidation of propylene and preparation method |
| CN103539762A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for producing epoxypropane by propylene epoxidation |
| CN103539762B (en) * | 2012-07-12 | 2016-01-13 | 中国石油化工股份有限公司 | Epoxidation of propylene produces the method for propylene oxide |
| CN104230854A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Cumyl hydroperoxide and propylene epoxidation method for preparing epoxypropane |
| CN104437450A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Titanium-containing silicon dioxide catalyst and preparation method and use thereof |
| CN104557779A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| CN104557780A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of epoxypropane |
| CN104557781A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing propylene oxide |
| CN105272813A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Propylene recovery method |
| CN105294379A (en) * | 2014-07-24 | 2016-02-03 | 中国石油化工股份有限公司 | Propylene recovery equipment |
| CN105294379B (en) * | 2014-07-24 | 2017-10-27 | 中国石油化工股份有限公司 | Propylene recovery equipment |
| CN110947375A (en) * | 2019-11-26 | 2020-04-03 | 红宝丽集团股份有限公司 | Catalyst for preparing propylene oxide and preparation method thereof |
| WO2021103437A1 (en) * | 2019-11-26 | 2021-06-03 | 红宝丽集团股份有限公司 | Catalyst for preparing propylene epoxide and a preparation method therefor |
| CN114426547A (en) * | 2020-09-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for producing dicyclopentadiene dioxide by using molybdenum-based homogeneous catalyst and obtained dicyclopentadiene dioxide |
| CN114426547B (en) * | 2020-09-29 | 2024-01-05 | 中国石油化工股份有限公司 | Method for producing dicyclopentadiene dioxide by molybdenum-based homogeneous catalyst and obtained dicyclopentadiene dioxide |
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| Publication number | Publication date |
|---|---|
| CN1252059C (en) | 2006-04-19 |
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