CN110437178A - A kind of method of green high-efficient synthesizing epoxypropane - Google Patents
A kind of method of green high-efficient synthesizing epoxypropane Download PDFInfo
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- CN110437178A CN110437178A CN201910835117.4A CN201910835117A CN110437178A CN 110437178 A CN110437178 A CN 110437178A CN 201910835117 A CN201910835117 A CN 201910835117A CN 110437178 A CN110437178 A CN 110437178A
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- hydrogen peroxide
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 230000003197 catalytic effect Effects 0.000 claims abstract description 44
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 239000000470 constituent Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 230000003647 oxidation Effects 0.000 abstract description 14
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000002356 single layer Substances 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 description 18
- 230000009466 transformation Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- JHZRQBKLEHQTKF-UHFFFAOYSA-N 2-methyloxirane;prop-1-ene Chemical compound CC=C.CC1CO1 JHZRQBKLEHQTKF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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
- Y02P20/10—Process efficiency
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The present invention provides a kind of methods of green high-efficient synthesizing epoxypropane.The technical solution is based on propylene ring oxidation reaction and prepares propylene oxide, using hydrogen peroxide direct oxidation method, using propylene as raw material, epoxidation reaction occurs in catalytic rectifying tower under the action of TS-1 microspherical catalyst, reactant obtains the propylene oxide of high concentration after separating-purifying.The present invention reacts no coupling product and generates, and single layer conversion ratio >=97%, selectivity >=99%, is a kind of method of green syt propylene oxide, is suitble to large-scale industrial production.This method atom utilization is high, selectivity is high, product yield is high and reaction no coupling product, environmentally friendly.
Description
Technical field
The present invention relates to field of chemical technology, and in particular to a kind of method of green high-efficient synthesizing epoxypropane.
Background technique
Propylene oxide is one of important derivatives of propylene, is a kind of important Organic Chemicals, in the derivative of propylene
It is only second to polypropylene and acrylonitrile in object, occupies third position.Due to containing-C-O-C- ternary ether structure in epoxide, have
Biggish surface tension, thus have very high reactivity, to acid and nucleopilic reagent it is very sensitive, can with hydrogen halides, water, alcohol,
The plurality of reagents such as amine are reacted and open loop, and a variety of halohydrins, propylene glycol, ether alcohol, secondary amine alcohol or quaternary amine alcohol etc. are produced.Propylene oxide is most
Big purposes is as main material production polyether polyol, reproduction polyurethane；Next can be used for producing widely used third
Glycol, propylene glycol etc.；Can also be used in other field include production nonionic surface active agent, oil field demulsifier, fire retardant,
Syntholube, farm chemical emulgent, unsaturated acid ester, adhesive etc..
Currently, preparing there are mainly three types of the methods of propylene oxide: chlorohydrination, conjugated oxidation and direct oxidation method.
Chlorohydrination is with propylene, chlorine, quick lime and water.Chlorohydrin action is occurred by chlorine gas and water and propylene first, it is raw
Produce intermediate chloropropyl alcohol, then with limewash and its occur saponification be made propylene oxide, by reaction product be sent into primary distillation tower with
Rectifying column carries out product separation, obtains product.Chlorohydrination industrialization is more than 80 years existing, and technique is more mature, and advantage is technique stream
Journey is short, small investment, operating flexibility is big, selectivity is good, production is safer.But there is also more disadvantages: the process requirement is a large amount of
Chlorine, severe corrosion to equipment；The waste water, waste residue and exhaust emission environment of a large amount of chloride containing calcium is discharged.
Conjugated oxidation is to react synthesizing epoxypropane by organic peroxide and propylene.Not according to raw material and joint product
Together, the conjugated oxidation of use mainly includes iso-butane cooxidation technique, ethylbenzene cooxidation technique, cumyl hydroperoxide method.Altogether
Oxidizing process overcomes the disadvantages of chlorohydrination corrosion is big, sewage is more, and product cost is low, and environmental pollution is also relatively small.But it should
Process flow is long, raw material variety is more, requires purified propylene high；Technological operation need to carry out at a higher pressure, want to equipment
Ask high, construction investment is also corresponding higher.
Direct oxidation method technique uses oxidant direct oxidation propylene synthesizing epoxypropane, is divided into according to the difference of oxidant
Hydrogen peroxide direct oxidation method and oxygen direct oxidation method.For chlorohydrination and conjugated oxidation, direct oxidation method process
It is relatively easy, by-product is less and pollution-free.Although having above-mentioned advantage on technology path, popular response mode can be generated
Certain by-product, and there is selectivity it is lower, product yield is not high the defects of.In this case, how based on direct
The technical issues of technology path of oxidizing process develops a kind of new propylene oxide synthesis technology, becomes urgently and solves.
Summary of the invention
The present invention is directed to be directed to the technological deficiency of the prior art, a kind of method of green high-efficient synthesizing epoxypropane is provided,
To solve in the prior art, the propylene oxide based on direct oxidation method is conventionally synthesized technique, and selective lower, product yield is not
High technical problem.
Another technical problem to be solved by the present invention is that the propylene oxide based on direct oxidation method is conventionally synthesized technique, can give birth to
At certain by-product.
The invention solves another technical problem be how to fully ensure that propylene oxide synthesis technology to environment green, nothing
Pollution.
To realize the above technical purpose, the invention adopts the following technical scheme:
A kind of method of green high-efficient synthesizing epoxypropane, this method are in the catalytic distillation that TS-1 microspherical catalyst is housed
In tower, with 100~160 DEG C of temperature, the pressure of 0.3~0.6MPa, propylene, solvent, hydrogen peroxide are subjected to hybrid reaction.
Preferably, the above method is the following steps are included: the rectifying section of catalytic rectifying tower is paved with the TS-1 microballoon catalysis
Agent, propylene, hydrogen peroxide, solvent become mixing gas phase after feed system pretreatment and enter catalytic rectifying tower；The gaseous mixture
Mutually enter rectifying section and carry out epoxidation reaction, obtains heavy constituent reaction solution；The heavy constituent reaction solution enters stripping section, separates
To propylene oxide.
Preferably, the TS-1 microspherical catalyst is using butyl titanate as titanium source, tetraethyl orthosilicate is silicon source, 4 third
Base ammonium hydroxide is what template was prepared.
Preferably, the TS-1 microspherical catalyst is prepared by the following method:
1) with SiO in tetraethyl orthosilicate2Molal quantity: the molal quantity of tetrapropylammonium hydroxide: TiO in butyl titanate2's
Molal quantity: the molal quantity of water is 1:0.3~1:0.02~0.05:30~50 ratio, by the aqueous solution of tetrapropylammonium hydroxide
It is uniformly mixed with the aqueous solution of tetraethyl orthosilicate, is then under agitation added thereto butyl titanate, mix, it is quiet
Set 8~12h；
2) by step 1) products therefrom with 80~90 DEG C of crystallization for 24 hours, then with 110~130 DEG C of 2~10h of crystallization, then with
160~180 DEG C of crystallization for 24 hours, product are filtered, washed, is dried, is roasted to get TS-1 fine catalyst is arrived；
3) step 2) products therefrom is uniformly mixed with the silicon dioxde solution that mass fraction is 30%, is sprayed onto high speed rotation
On turntable, it is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres, collects the dry matter fallen to get micro- to the TS-1
Sphere catalyst.
Preferably, the dosage of the TS-1 microspherical catalyst is the 0.1~15% of material gross mass.
Preferably, the molal quantity of propylene: the molal quantity of hydrogen peroxide: the molal quantity of solvent is 1:2~3:5~7.5.
Preferably, reaction velocity is 1500-4000h-1。
Preferably, isobutylene feed speed is 0.01~30mL/min, acetic acid charging rate is 0.01~6mL/min,
Oxygen feeding speed is 10~1000mL/min, and nitrogen feed speed is 20~8000mL/min.
Preferably, the solvent be methanol, ethyl alcohol, propyl alcohol, isopropanol, the tert-butyl alcohol, acetonitrile, acetone, butanone wherein
A kind of or in which any two kinds of mixture.
The present invention provides a kind of methods of green high-efficient synthesizing epoxypropane.It is anti-that the technical solution is based on epoxidation of propylene
Propylene oxide should be prepared, using hydrogen peroxide direct oxidation method, using propylene as raw material, under the action of TS-1 microspherical catalyst in
Epoxidation reaction occurs in catalytic rectifying tower, reactant obtains the propylene oxide of high concentration after separating-purifying.Present invention reaction
No coupling product generates, single layer conversion ratio >=97%, and selectivity >=99%, is a kind of method of green syt propylene oxide, is suitble to
Large-scale industrial production.This method atom utilization is high, selectivity is high, product yield is high and reaction no coupling product, to environment
It is friendly.
Specific embodiment
Below by specific embodiments of the present invention will be described in detail.In order to avoid excessive unnecessary details, In
It will not be described in detail in following embodiment to belonging to well known structure or function.Approximation used in following embodiment
Language can be used for quantitative expression, show to allow quantity to have certain variation in the case where not changing basic function.It is fixed except having
Adopted outer, technical and scientific term used in following embodiment has the phase being commonly understood by with those skilled in the art of the invention
Same meaning.
Embodiment 1
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, reaction
Device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, weight after reaction
Component enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 2
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2:6.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, reaction
Device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, weight after reaction
Component enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 3
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2:5.5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, instead
Answer device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, after reaction
Heavy constituent enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 4
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2:7.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, reaction
Device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, weight after reaction
Component enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 5
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2:6.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, reaction
Device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, weight after reaction
Component enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 6
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2.4:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, instead
Answer device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, after reaction
Heavy constituent enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 7
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2.1:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, instead
Answer device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, after reaction
Heavy constituent enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 8
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, reaction
Device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, weight after reaction
Component enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 9
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2.7:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, instead
Answer device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, after reaction
Heavy constituent enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 10
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2.6:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, instead
Answer device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, after reaction
Heavy constituent enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 11
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2.5:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, instead
Answer device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, after reaction
Heavy constituent enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 12
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2.4:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, instead
Answer device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, after reaction
Heavy constituent enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 13
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2.3:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, instead
Answer device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, after reaction
Heavy constituent enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 14
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:3:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, reaction
Device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, weight after reaction
Component enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 15
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2:7.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, reaction
Device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, weight after reaction
Component enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=97.2%, selectivity >=99%.
Embodiment 16
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:3:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, reaction
Device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, weight after reaction
Component enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=97.8%, selectivity >=99%.
Embodiment 17
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2.2:5.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, instead
Answer device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, after reaction
Heavy constituent enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=98%, selectivity >=99%.
Embodiment 18
TS-1 microspherical catalyst 300ml, feedstock ratio are as follows: material proportion (molar ratio) third are loaded in catalytic rectifying tower
Alkene: hydrogen peroxide: solvent=1:2:7.Air speed is 1500h-1.It is 150 DEG C that reaction bed temperature is controlled in reaction process, reaction
Device inlet pressure 0.6MPa.Propylene, hydrogen peroxide, solvent are to enter catalytic rectifying tower after mixing in preheated device, weight after reaction
Component enters stripping section, and propylene oxide is obtained after separating-purifying.Single transformation rate >=97%, selectivity >=99%.
The embodiments of the present invention have been described in detail above, but content is only the preferred embodiment of the present invention,
It is not intended to limit the invention.All any modifications, equivalent replacements, and improvements etc. done in application range of the invention, should all
It is included within protection scope of the present invention.
Claims (9)
1. a kind of method of green high-efficient synthesizing epoxypropane, it is characterised in that: this method is equipped with TS-1 microspherical catalyst
Catalytic distillation tower in, with 100~160 DEG C of temperature, the pressure of 0.3~0.6MPa, propylene, solvent, hydrogen peroxide are carried out
Hybrid reaction.
2. a kind of method of green high-efficient synthesizing epoxypropane according to claim 1, which is characterized in that including following step
Rapid: the rectifying section of catalytic rectifying tower is paved with the TS-1 microspherical catalyst, and propylene, hydrogen peroxide, solvent are located in advance in feed system
Become mixing gas phase after reason and enters catalytic rectifying tower；The mixing gas phase enters rectifying section and carries out epoxidation reaction, is recombinated
Divide reaction solution；The heavy constituent reaction solution enters stripping section, isolated propylene oxide.
3. a kind of method of green high-efficient synthesizing epoxypropane according to claim 1, it is characterised in that the TS-1 is micro-
Sphere catalyst is using butyl titanate as titanium source, and tetraethyl orthosilicate is silicon source, and tetrapropylammonium hydroxide is prepared for template
's.
4. a kind of method of green high-efficient synthesizing epoxypropane according to claim 1, it is characterised in that the TS-1 is micro-
Sphere catalyst is prepared by the following method:
1) with SiO in tetraethyl orthosilicate2Molal quantity: the molal quantity of tetrapropylammonium hydroxide: TiO in butyl titanate2Mole
Number: the molal quantity of water is 1:0.3~1:0.02~0.05:30~50 ratio, by the aqueous solution and silicon of tetrapropylammonium hydroxide
The aqueous solution of sour tetra-ethyl ester is uniformly mixed, and is then under agitation added thereto butyl titanate, is mixed, and stands 8
~12h；
2) by step 1) products therefrom with 80~90 DEG C of crystallization for 24 hours, then with 110~130 DEG C of 2~10h of crystallization, then with 160
~180 DEG C of crystallization for 24 hours, product are filtered, washed, is dried, is roasted to get TS-1 fine catalyst is arrived；
3) step 2) products therefrom is uniformly mixed with the silicon dioxde solution that mass fraction is 30%, is sprayed onto high speed rotation turntable
On, it is centrifuged material of dishing out, is fallen in 400 DEG C of nitrogen atmospheres, is collected the dry matter fallen and urged to get to the TS-1 microballoon
Agent.
5. a kind of method of green high-efficient synthesizing epoxypropane according to claim 1, it is characterised in that the TS-1 is micro-
The dosage of sphere catalyst is the 0.1~15% of material gross mass.
6. a kind of method of green high-efficient synthesizing epoxypropane according to claim 1, it is characterised in that mole of propylene
Number: the molal quantity of hydrogen peroxide: the molal quantity of solvent is 1:2~3:5~7.5.
7. a kind of method of green high-efficient synthesizing epoxypropane according to claim 1, it is characterised in that reaction velocity is
1500-4000h-1。
8. a kind of method of green high-efficient synthesizing epoxypropane according to claim 7, it is characterised in that isobutylene feed
Speed is 0.01~30mL/min, and acetic acid charging rate is 0.01~6mL/min, and oxygen feeding speed is 10~1000mL/min,
Nitrogen feed speed is 20~8000mL/min.
9. a kind of method of green high-efficient synthesizing epoxypropane according to claim 1, it is characterised in that the solvent is
Methanol, ethyl alcohol, propyl alcohol, isopropanol, the tert-butyl alcohol, acetonitrile, acetone, the one of which of butanone or in which any two kinds of mixture.
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Cited By (1)
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|---|---|---|---|---|
| CN116199647A (en) * | 2021-12-01 | 2023-06-02 | 中国石油化工股份有限公司 | Method for producing epoxypropane |
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2019
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116199647A (en) * | 2021-12-01 | 2023-06-02 | 中国石油化工股份有限公司 | Method for producing epoxypropane |
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