CN104650006B - A kind of olefin epoxidation method - Google Patents
A kind of olefin epoxidation method Download PDFInfo
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- CN104650006B CN104650006B CN201310578336.1A CN201310578336A CN104650006B CN 104650006 B CN104650006 B CN 104650006B CN 201310578336 A CN201310578336 A CN 201310578336A CN 104650006 B CN104650006 B CN 104650006B
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- alkene
- nitrous oxide
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- 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
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- 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
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Abstract
The invention provides a kind of olefin epoxidation method, this method includes：Nitrous oxide and alkene are contacted with catalyst.According to method of the present invention, nitrous oxide has higher conversion ratio, and in the method for the invention provided, leftover materials containing carrier gas and unreacted nitrous oxide after contact can be passed through in reactor again after simple process to react, therefore, the method according to the invention can dispose the nitrous oxide industrially produced, while can be with epoxidation of olefins, the use of hydrogen peroxide is avoided, and the higher epoxides of selectivity can be generated.
Description
Technical field
The present invention relates to a kind of olefin epoxidation method.
Background technology
Nitrous oxide（Nitrous Oxide）, also known as laughing gas is a kind of gas with greenhouse effects, is《Discuss in capital of a country
Agreement》One of defined 6 kinds of greenhouse gases.Compared with carbon dioxide, although the content of nitrous oxide in an atmosphere is very low, but
Its unimolecule heats 310 times that potentiality is carbon dioxide.Therefore the effect to Global Greenhouse Effect is more and more obvious, with big
The increase of nitrous oxide concentration in gas, has caused each area of the whole world and the very big concern of country.But industrial adipic acid
Can the substantial amounts of N of by-product in production process2O, directly discharge can cause the heavy damage of environment.
Nitrous oxide is a kind of colourless pleasantly sweet gas, harmless, and is acted on light anaesthesia, mainly as
Medical anesthetic agent, while the accelerator of engine and the oxidant of rocket are can be used for, but the nitrous oxide of these application consumption
Amount is smaller, it is impossible to the nitrous oxide produced by disposing completely in adipic acid production process.To avoid environmental pollution, currently
The industrialized treatment method of most common nitrous oxide is that heating is directly decomposed under catalysts conditions, produces nitrogen and oxygen.
But the method reaction effect is not obvious, high energy consumption during substantial amounts of nitrous oxide, simultaneous reactions, cost are still suffered from after processing
It is high.
Epoxide is a class purposes extremely wide Organic Chemicals and intermediate.The epoxides of light alkene, such as
1,2- epoxypentane is the intermediate of 1,2- pentanediols, and 1,2- pentanediol is a kind of important fine chemical material, is not only
The intermediate of a variety of chemical products is produced, is also the critical materials of synthesizing fungicide propiconazole, the annual whole world of 1,2- pentanediol
Consumption is more than 2000 tons；HEO is also a kind of important fine chemical material and intermediate, is such as used to close
Into novel agrochemical propargite, with high rigidity, high temperature resistant, acid and alkali-resistance unsaturated-resin, light-sensitive material, makrolon and oneself two
Aldehyde etc., it is also growing day by day to it demand with continually developing for 7-oxa-bicyclo[4.1.0 purposes.
The epoxidation reaction of alkene is the important channel of synthesizing epoxy compound.At present, it is industrial often using hydrogen peroxide as oxygen
Source oxyalkylene prepares epoxides, and the reaction is typically that wolframic acid or molybdic acid are loaded into the contracting of DMF dibutyl
It is in the presence of tributyltin chloride that C5-C6 alkene and 2- octenes etc. is anti-with hydrogen peroxide on activated carbon after aldehyde modification
Should.But hydrogen peroxide is low using profit in the course of reaction, while causing corrosion to reactor wall, the cost of catalyst is too high,
And the course of reaction complex process.
CN102442975A discloses a kind of olefin epoxidation method, and this method is in titanium silicon by alkene and hydrogen peroxide
Carry out epoxidation reaction in the presence of molecular sieve catalyst and macroporous strong basic anion exchange resin, the time required to the reaction compared with
It is short, and the conversion ratio of hydrogen peroxide can be up to more than 90%, but the process needs to use substantial amounts of solvent to make hydrogen peroxide and alkene
Molten is a phase, while production can also produce substantial amounts of waste water, waste residue, greatly pollution is caused to environment.
In order to solve the above problems, a kind of new olefin epoxidation method of exploitation is needed badly.
The content of the invention
It is an object of the invention to overcome the epoxidation technique of nitrous oxide poor processing effect in the prior art, alkene to answer
There is provided a kind of new olefin epoxidation method for the defect that miscellaneous and cost is high, environmental pollution is serious.
The invention provides a kind of olefin epoxidation method, this method includes：By nitrous oxide and alkene and catalysis
Agent is contacted.
In method of the present invention, the conversion ratio of nitrous oxide is higher, and excessive nitrous oxide is through letter after reaction
It can reenter in reactor after single processing, it is to avoid the secondary emission of nitrous oxide.Moreover, epoxidation of olefins of the present invention
Method is without using hydrogen peroxide, so as to avoid the corrosion to reactor wall, also prevent the use of a large amount of solvents to environment
The pollution caused, therefore, method of the present invention have the characteristics of simple to operate, cost is relatively low and environmentally friendly.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of olefin epoxidation method, this method includes：By nitrous oxide and alkene and catalysis
Agent is contacted.
In the present invention, the reactor of the alkene epoxidation can be various conventional reactors, for example, can be kettle
Formula reactor and fixed fluidized-bed reactor.
Method according to the present invention, the mol ratio of the alkene and nitrous oxide can be 1-6：1, preferably 2-
4：1, more preferably 2-3：1.
Method according to the present invention, the contact of the nitrous oxide and alkene with catalyst is preferably deposited in carrier gas
In lower progress.The carrier gas can be any gas not reacted in olefin epoxidation process with raw material and product,
For example, the one or more in nitrogen, helium, neon and argon gas.The mol ratio of the carrier gas, nitrous oxide and alkene can be with
For 1-10：1：1-6, preferably 3-6：1：2-4, more preferably 3-5：1：2-3.
In the present invention, the nitrous oxide can be the nitrous oxide in various sources, for example, can be industrial system
Primary product when accessory substance and ammonium nilrite when standby adipic acid, ketoxime, polyamide etc. are thermally decomposed, may originate from automobile
The tail gas discharged.The nitrous oxide in above-mentioned source can be by purifying or without after purification for the present invention, preferable case
Under, above-mentioned nitrous oxide is purified to nitrous oxide content to be used for the present invention after 98.5-99.999 volumes %.
Method according to the present invention, the condition of the contact can include：Temperature is 250-380 DEG C, is preferably
270-360 DEG C, more preferably 320-350 DEG C；Contact is 0.001-0.2MPa, preferably 0.001-0.1MPa.
In the present invention, the pressure refers to meter pressure.
Method according to the present invention, when the epoxidation reaction of olefines is carried out in fixed fluidized-bed reactor,
The condition of the contact also total air speed of charging including carrier gas, nitrous oxide and alkene is 1000-6000h-1, preferably air speed is
2000-3000h-1.In the present invention, the air speed is volume space velocity.
Under method according to the present invention, preferable case, the alkene is C3-C6 chain olefin or C5-C6 ring-types
Alkene, it is further preferred that the alkene be butylene, amylene, hexene and cyclohexene in one kind.
Method according to the present invention, the catalyst can be the molecular sieve of various load irons.
Method according to the present invention, on the basis of the molecular sieve gross weight of the load iron, the load capacity of iron can be with
For 0.1-3 weight %, preferably 0.5-1 weight %, SiO in the molecular sieve2/Al2O3Mol ratio can be 1：1-100.The present invention
There is no special limitation to the size of the molecular sieve of load iron, but be easily isolated from catalyst and ensure that obtaining higher catalysis lives
From the aspect of property, the particle diameter of the molecular sieve catalyst of the load iron of the shaping is preferably 5-30 mesh.
In the present invention, the molecular sieve of the load iron can be the molecular sieve of various conventional structures, for example, can be
One or more in Fe-ZSM-5, Fe-TS-1, Fe-MCM-22, Fe-Beta and Fe-SBA-15.
According to the embodiment of the present invention, Fe-SBA-15 catalytic effect is substantially better than point of the load iron of other structures
Son sieve, it is therefore preferred that the catalyst is Fe-SBA-15.
According to method of the present invention, in order to eliminate the acidity of the catalyst surface, make the iron thing of catalyst surface
Plant and further disperseed, so that the catalyst has under more preferable absorption property and catalytic performance, preferable case, institute
Stating the molecular sieve surface of load iron need to be modified through alkali metal salt, so that the catalyst, i.e. the molecular sieve of load iron
Contain alkali metal ion in surface.
In the present invention, the alkali metal salt can be at least one of sodium salt, sylvite and lithium salts.Under preferable case,
The alkali metal salt be sylvite, the sylvite can be potassium chloride, potassium fluoride, KBr, KI and potassium acetate at least
One kind, preferably potassium chloride and/or KBr.
According to method of the present invention, in the catalyst, alkali metal ion and ferro element in alkali metal salt rub
Your ratio can be 3-6, preferably 4-5.
In the present invention, described to be prepared through alkali metal modified catalyst, preparation method may be referred to《Fe adulterates
SBA-15 synthesis, the research for characterizing and being catalyzed Benzene to phenol》（Pei Jinfeng, Wang Yong.Science and technology and engineering, 2012,12（9）：
2082-2085）Described in method be proportionally added into after alkali metal salt be made.
In the present invention, this method also includes isolating epoxides from products therefrom after contact, and leftover materials are passed through
Base extraction is simultaneously passed through in reactor after drying again, and reaction is participated in again.According to the present invention, containing for the leftover materials be not anti-
The nitrous oxide answered and carrier gas, can use the sour gas contained in alkali liquor absorption leftover materials, and leftover materials are dried
It is passed through again in reactor afterwards.
In following examples, using the analysis respectively constituted in gas-chromatography carry out system, determined by correcting normalization method
Amount, can refer to prior art progress, the evaluation indexes such as conversion ratio, the selectivity of product of reactant is calculated on this basis.
In the present invention, the conversion ratio calculation formula of nitrous oxide is as follows：
In the present invention, the conversion ratio calculation formula of alkene is as follows：
In the present invention, the selective calculation formula of epoxides is as follows：
Wherein, X is conversion ratio；S is selectivity；M is the quality of component；N is the amount of the material of component；Wherein m0And n0Point
Quality and mole before Biao Shi not reacting.
The present invention will be described in detail by way of examples below.
In following examples, potassium chloride modification after Fe-SBA-15 prepare it is as follows：《Fe doping SBA-15 synthesis,
Characterize and be catalyzed the research of Benzene to phenol》（Pei Jinfeng, Wang Yong.Science and technology and engineering, 2012,12（9）：2082-2085）Institute
Potassium chloride is proportionally added into the method stated.
The preparation method of Fe-ZSM-5 after potassium chloride modification is as follows：According to " high-temperature roasting is handled to Fe-ZSM-5 molecules
Sieve the influence of performance "（Zhang Xianguo, Guo Quanhui, Li Jianwei, Li Yingxia, that heroic bearing, Journal of Henan University（Natural science edition）,
2007,37（4）：366-370）Described method is proportionally added into after potassium chloride and is made.
Nitrous oxide is purchased from Hunan Province Central China special gas Co., Ltd, and purity is 99.995 volume %.
Embodiment 1
By helium, 1- amylenes and nitrous oxide using mol ratio as 3：2：1 is added to the Fe- after being modified equipped with potassium chloride
SBA-15（K and Fe mol ratio is 5.0, and the load capacity of iron is Fe-SBA-15 1.0 weight %, SiO2/Al2O3Mol ratio be
10）Fixed fluidized-bed reactor in, reaction temperature control be 350 DEG C, Stress control is normal pressure, charging cumulative volume air speed be
3000h-1, so that 1,2- epoxypentanes are made.
Embodiment 2
By helium, cyclohexene and nitrous oxide using mol ratio as 6：4：1 is added to the Fe- after being modified equipped with potassium chloride
SBA-15（K and Fe mol ratio is 5.0, and the load capacity of iron is Fe-SBA-15 1.0 weight %, SiO2/Al2O3Mol ratio be
10）Fixed fluidized-bed reactor in, reaction temperature control be 350 DEG C, Stress control is normal pressure, charging cumulative volume air speed be
3000h-1, so that HEO is made.
Embodiment 3
By helium, 1- amylenes and nitrous oxide using mol ratio as 6：4：1 is added to the Fe- after being modified equipped with potassium chloride
SBA-15（K and Fe mol ratio is 5.0, and the load capacity of iron is Fe-SBA-15 1.0 weight %, SiO2/Al2O3Mol ratio be
10）Fixed fluidized-bed reactor in, reaction temperature control be 300 DEG C, Stress control is normal pressure, charging cumulative volume air speed be
3000h-1, so that 1,2- epoxypentanes are made.
Embodiment 4
Method according to embodiment 3 carries out epoxidation to alkene, except that, charging cumulative volume air speed is
6000h-1, so that 1,2- epoxypentanes are made.
Embodiment 5
Method according to embodiment 3 carries out epoxidation to alkene, except that, 1- amylenes are changed into equimolar
Propylene, so that expoxy propane is made.
Embodiment 6
Method according to embodiment 3 carries out epoxidation to alkene, except that, with the potassium chloride of same molar
Fe-ZSM-5 after modification（K and Fe mol ratio is 5.0, and the load capacity of iron is Fe-ZSM-5 1.0 weight %, SiO2/Al2O3
Mol ratio be 25）Fe-SBA-15 after being modified instead of potassium chloride, so that 1,2- epoxypentanes are made.
Embodiment 7
Method according to embodiment 3 carries out epoxidation to alkene, except that, Fe-SBA-15 is without potassium chloride
Modification, so that 1,2- epoxypentanes are made.
After continuous feed 2 hours, the selectivity of the conversion ratio of nitrous oxide and alkene, epoxides in embodiment 1-7
It is shown in Table 1.
Table 1
| Embodiment is numbered | Conversion ratio/% of nitrous oxide | Conversion ratio/% of alkene | Selectivity/% of epoxides |
| Embodiment 1 | 85 | 55 | 72 |
| Embodiment 2 | 92 | 24 | 85 |
| Embodiment 3 | 70 | 15 | 88 |
| Embodiment 4 | 65 | 14 | 84 |
| Embodiment 5 | 83 | 18 | 76 |
| Embodiment 6 | 60 | 11 | 71 |
| Embodiment 7 | 58 | 23 | 35 |
As it can be seen from table 1 according to method oxyalkylene of the present invention, nitrous oxide has higher conversion
In rate, and the present invention, the leftover materials containing carrier gas and unreacted nitrous oxide after contact can be again after simple process
It is passed through in reactor and reacts, therefore, the method according to the invention can dispose the nitrous oxide industrially produced, also simultaneously
Can be with epoxidation of olefins, it is to avoid the use of hydrogen peroxide, and selectivity can be generated according to the preferred embodiment of the present invention
Higher epoxides.
Claims (19)
1. a kind of olefin epoxidation method, it is characterised in that this method includes：Nitrous oxide and alkene are connect with catalyst
Touch, wherein, the catalyst is the molecular sieve of load iron；The molecular sieve surface of the load iron is modified with alkali metal salt,
The alkali metal salt is sylvite；The mol ratio of alkali metal ion and ferro element in the alkali metal salt is 3-6；The alkene with
The mol ratio of nitrous oxide is 1-6：1；The sylvite be potassium chloride, potassium fluoride, KBr, KI and potassium acetate in extremely
Few one kind；The temperature of the contact is 250-380 DEG C.
2. according to the method described in claim 1, wherein, the mol ratio of the alkene and nitrous oxide is 2-4：1.
3. according to the method described in claim 1, wherein, the mol ratio of the alkene and nitrous oxide is 2-3：1.
4. according to the method described in claim 1, wherein, the contact of the nitrous oxide and alkene with catalyst is deposited in carrier gas
Carried out lower, the mol ratio of the carrier gas, nitrous oxide and alkene is 1-10：1：1-6.
5. according to the method described in claim 1, wherein, the contact of the nitrous oxide and alkene with catalyst is deposited in carrier gas
Carried out lower, the mol ratio of the carrier gas, nitrous oxide and alkene is 3-6：1：2-4.
6. according to the method described in claim 1, wherein, the contact of the nitrous oxide and alkene with catalyst is deposited in carrier gas
Carried out lower, the mol ratio of the carrier gas, nitrous oxide and alkene is 3-5：1：2-3.
7. according to the method described in claim 1, wherein, the condition of the contact includes：Pressure is 0.001-0.2MPa.
8. according to the method described in claim 1, wherein, the condition of the contact includes：Temperature is 270-360 DEG C.
9. according to the method described in claim 1, wherein, the condition of the contact includes：Temperature is 320-350 DEG C.
10. according to the method described in claim 1, wherein, the condition of the contact includes：Pressure is 0.001-0.1MPa.
11. the method according to any one in claim 4-10, wherein, the contact is in fixed fluidized-bed reactor
Carry out, the condition also charging cumulative volume air speed including carrier gas, nitrous oxide and alkene of the contact is 1000-6000h-1。
12. the method according to any one in claim 4-10, wherein, the contact is in fixed fluidized-bed reactor
Carry out, the condition also charging cumulative volume air speed including carrier gas, nitrous oxide and alkene of the contact is 2000-3000h-1。
13. the method according to any one in claim 1-10, wherein, the alkene for C3-C6 chain olefin or
C5-C6 cyclic olefin.
14. the method according to any one in claim 1-10, wherein, the alkene is butylene, amylene, hexene and ring
One kind in hexene.
15. the method according to any one in claim 1-10, wherein, with the gross weight of the molecular sieve of the load iron
On the basis of, the load capacity of iron is 0.1-3 weight %.
16. the method according to any one in claim 1-10, wherein, with the gross weight of the molecular sieve of the load iron
On the basis of, the load capacity of iron is 0.5-1 weight %.
17. the method according to any one in claim 1-10, wherein, the sylvite is potassium chloride and/or KBr.
18. the method according to any one in claim 1-10, wherein, alkali metal ion in the alkali metal salt with
The mol ratio of ferro element is 4-5.
19. according to the method described in claim 1, wherein, this method also include epoxy is isolated from products therefrom after contact
Compound, leftover materials are passed through in reactor again after base extraction and drying, and reaction is participated in again.
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| CN110252272B (en) * | 2019-06-17 | 2022-04-22 | 万华化学集团股份有限公司 | Method and device for continuously preparing olefin epoxidation catalyst on large scale |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296479A (en) * | 1998-11-26 | 2001-05-23 | 克雷维斯技术及创新股份有限公司 | Method for producing epoxy resins gas phase epoxidation |
| CN102905782A (en) * | 2010-03-17 | 2013-01-30 | 陶氏技术投资有限责任公司 | Catalytic fixed bed reactor for producing ethylene oxide by partial oxidation of ethylene |
-
2013
- 2013-11-18 CN CN201310578336.1A patent/CN104650006B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296479A (en) * | 1998-11-26 | 2001-05-23 | 克雷维斯技术及创新股份有限公司 | Method for producing epoxy resins gas phase epoxidation |
| CN102905782A (en) * | 2010-03-17 | 2013-01-30 | 陶氏技术投资有限责任公司 | Catalytic fixed bed reactor for producing ethylene oxide by partial oxidation of ethylene |
Non-Patent Citations (1)
| Title |
|---|
| Fe掺杂SBA—15的合成、表征及催化苯制苯酚的研究;裴金凤等;《科学技术与工程》;20120331;第12卷(第9期);2082-2085 * |
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