CN115160334A - Method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds - Google Patents
Method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds Download PDFInfo
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- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 239000004593 Epoxy Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 109
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 150000001555 benzenes Chemical class 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 21
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 20
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 18
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- -1 benzene compound Chemical class 0.000 claims description 8
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 15
- 238000005516 engineering process Methods 0.000 abstract description 7
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 abstract 2
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000004064 recycling Methods 0.000 description 13
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 6
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011964 heteropoly acid Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229960001922 sodium perborate Drugs 0.000 description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
-
- 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
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds, which comprises two reaction processes; in the first-stage reaction, dicyclopentadiene and cumene hydroperoxide are used as raw materials, benzene compounds inert to a reaction system are used as solvents, the reaction raw materials are in contact with a titanium silicalite molecular sieve catalyst with an HMS structure in a first-stage reactor to react, DCPD is oxidized to generate DCPD DO, and the first-stage oxidation reaction is completed; the first stage reaction product is mixed with one other olefin and fed into the second stage reactor, and the excess CHP reacts with the added olefin to produce another epoxy compound. Mainly solves the problem of excessive CHP in the prior technology for preparing DCPDO by the hydrogen peroxide cumene method; by introducing another specific olefin in the second stage reaction process, excessive CHP in the first stage reaction product is completely converted, and simultaneously, another epoxy compound is co-produced, so that the process is safer, and a set of process is realized to produce two high-end epoxy compounds.
Description
Technical Field
The invention relates to a method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds.
Background
Dicyclopentadiene Dioxide (DCPDDO) is a special alicyclic epoxy resin monomer, the consumption of alicyclic epoxy resin accounts for about 5% of the consumption of the total epoxy resin, and among various alicyclic epoxy resin products, dicyclopentadiene dioxide epoxy resin products attract more attention. Because the DCPDDO and the cured substance of the anhydride have high crosslinking density and high rigidity, the cured substance still has higher strength at the thermal deformation temperature of more than 300 ℃, and the electrical property at high temperature is particularly excellent. Therefore, the dicyclopentadiene dioxide epoxy resin is suitable for being used as pouring insulation of outdoor mutual inductors, pouring materials of micro motor rotors, high-humidity resistant epoxy resin plastic packaging materials, carbon fiber (or glass fiber) winding high-pressure containers, high-elasticity modulus composite materials, resin alloy molds, high-temperature resistant laminated materials, high-strength weather-resistant glass fiber reinforced plastics, anti-irradiation coatings, aviation, aerospace and defense apparatus manufacturing and the like, and the DCPDDO can effectively replace bisphenol A resin in the application of high-end electronic and electrical fields by virtue of excellent electrical insulating property, so that the DCPDO has a good market prospect.
At present, the DCPDO is produced industrially mainly by peroxyacetic acid method, which comprises mixing glacial acetic acid with H 2 O 2 The peroxyacetic acid is produced by reaction, then the peroxyacetic acid is used as an oxidant, 98% concentrated sulfuric acid is used as a catalyst to catalyze and oxidize DCPD to produce DCPDDO, and the yield of the DCPDDO product is only about 80%. The process has low safety, serious equipment corrosion, large quantity of three wastes, small production scale and low yield, and limits the application range of the process. The only domestic dicyclopentadiene dioxide production enterprises are Jiangsu Taite Er, tianjin Jingdong and Yue Yangchang De, the technology is adopted, and the capacity and the yield are low.
The methods currently under investigation for the synthesis of dicyclopentadiene dioxide include the alkyl hydroperoxide method, the sodium perborate method and the sodium percarbonate method, H 2 O 2 Heteropoly acid compoundMethods, and the like. The alkyl hydroperoxide method can obtain more ideal yield, but has high reaction temperature, larger danger coefficient, strict requirements on water content and content of carbonyl byproducts, expensive price of oxidant and catalyst and difficult recycling. The sodium perborate method adopts sodium perborate with better safety as an oxidant, carries out epoxidation reaction at room temperature, has safe process and simple operation condition, but has longer reaction time, more side reactions and low yield of only 50 percent. The sodium percarbonate method carries out epoxidation reaction under the condition of ultrasonic radiation, shortens the reaction time, improves the yield of a target product, but the process has low economy and low yield and has a considerable distance from industrial production. H 2 O 2 The heteropoly acid compound method is characterized in that heteropoly acid and hydrogen peroxide in a water phase form peroxide, then the peroxide enters an oil phase under the action of a phase transfer catalyst and reacts with olefin in the oil phase to form an epoxy compound, the heteropoly acid and the phase transfer catalyst enter the water phase again and are combined with the hydrogen peroxide, and the process is repeatedly circulated until the reaction is finished. The method is environment-friendly, high in economy, high in yield, simple in process and free of equipment corrosion, but when the method is used for synthesizing the DCPDO, the catalyst and the water are mixed together, cannot be separated, cannot be recycled, and is difficult to industrially amplify. The titanium silicalite molecular sieve catalytic oxidation method adopts a titanium silicalite molecular sieve catalyst, takes organic peroxide as an oxidant, avoids using organic peroxy acid, does not need to form a large amount of organic acid salt through alkali neutralization, has the advantages of environmental protection and the like, and becomes a research and development hotspot recently. Patent CN201911336052.5 discloses a preparation method of a Ti-HMS catalyst using carbon nanofibers as a carrier, and the Ti-HMS catalyst is applied to a DCPDO synthesis process to obtain higher product yield. However, in order to obtain high DCPD conversion rate and high DCPDDO yield, CHP is required to be excessive, and CHP as an organic peroxide is easily decomposed at high temperature and releases heat, so that potential safety hazards are brought to the subsequent product refining and separating process, and the industrial application and conversion are limited.
Disclosure of Invention
The invention aims to solve the problem that in the existing technology for preparing DCPDDO by Cumene Hydroperoxide (CHP), CHP must be excessive in order to obtain high DCPD conversion rate and high DCPDDO yield, and CHP as an organic peroxide is easy to rapidly decompose and release heat at high temperature, thereby bringing potential safety hazard to the subsequent product refining and separating process and being incapable of industrialization. The invention aims to provide a method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds, which adopts two-stage reaction, completely converts excessive CHP in the first-stage reaction through the second-stage reaction to prepare DCPDO products and co-produce other epoxy compounds at the same time, and realizes that one set of device produces various high value-added epoxy compound products.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds comprises two reaction processes; in the first-stage reaction, dicyclopentadiene (DCPD) and Cumene Hydroperoxide (CHP) are used as raw materials, benzene compounds inert to a reaction system are used as solvents, the reaction raw materials are contacted with a titanium silicalite molecular sieve catalyst with an HMS structure in a first-stage reactor to react, the DCPD is oxidized to generate DCPD DO, and the first-stage oxidation reaction is completed; the first stage reaction product is mixed with one other olefin and fed into the second stage reactor, and the excess CHP reacts with the added olefin to produce another epoxy compound.
The reaction equations are respectively as follows:
DCPD, CHP and other olefin are taken as raw materials, benzene compounds inert to a reaction system are taken as a solvent, a Ti-HMS molecular sieve is taken as a catalyst, and the reaction conditions are kept as follows: CHP (CHP): inert solvent: the specific olefin molar ratio is 1: (2.1-4): (8-15): (0.4-8), carrying out two-stage reaction in two reactors.
In the first stage of reaction, the oxidation reaction temperature is 60-120 ℃, the reaction pressure is 0.5-1.5 MPagg, and the mass space velocity of the fed reaction material is 1-4 h -1 Under the condition, DCPD is oxidized by CHP to generate DCPDDO; the two-stage reaction process is carried out at the reaction temperature of 70-130 DEG CThe pressure is 0.8-6 MPagg, the mass airspeed of the fed reaction material is 1-4 h -1 Under the condition, the residual CHP in the first-stage reaction product reacts with other newly added olefin to generate other high-added-value epoxy compounds, and the CHP is completely converted.
In the invention, the specific olefin is one of propylene, butylene, cyclohexene and cyclopentene, the inert solvent is one of cumene or ethylbenzene, and the weight ratio of dicyclopentadiene by mole: CHP (CHP): inert solvent: other olefins =1: (2.1-4): (8-15): (0.4-8).
In the invention, the first-stage reactor and the second-stage reactor are both tubular fixed bed reactors.
In the invention, the preferable range of the first-stage reaction temperature is 0.8-1.2 MPag; the preferred range of the mass space velocity of the fed reaction material in the first step is 1 to 3 hours -1 。
In the invention, the preferable range of the second-stage reaction temperature is 1-5.5 MPag, and the preferable range of the mass space velocity of the reaction material feeding in the second step is 1-3 h -1 。
In the invention, the adopted catalyst is the Ti-HMS molecular sieve catalyst prepared by the method in patent CN 201110192680.8.
The invention has the following advantages:
compared with the existing peroxyacetic acid method, the method disclosed by the invention has the advantages that strong corrosive substances such as acid and alkali are not required, the requirement on equipment materials is low, continuous production can be realized, products and catalysts are naturally separated, three wastes are not generated theoretically, the process is simpler and more environment-friendly, and the production scale can be flexibly adjusted;
compared with the prior technology for preparing DCPDO by the CHP method, the CHP completely reacts, so that potential safety hazards caused by residual CHP in reaction products are avoided, and the subsequent purification is safer and more reliable;
the DCPD conversion rate is high and is more than 99%, and the DCPDDO selectivity is high and is more than 99%.
And the CHP conversion rate is high, the conversion is basically complete, and the selectivity of the epoxy compound by-product is high and is more than 99.9%.
The method mainly solves the problem of excessive CHP in the prior technology for preparing DCPDO by cumene hydroperoxide and method; by introducing another specific olefin in the second stage reaction process, excessive CHP in the first stage reaction product is completely converted, and simultaneously, another epoxy compound is co-produced, so that the process is safer, and a set of process is realized to produce two high-end epoxy compounds. On the premise of keeping high DCPD conversion rate and high DCPD DO selectivity, the excessive CHP in the first-stage reaction process is completely reacted through the second-stage reaction to generate a second high-end epoxy compound product, so that the potential safety hazard of residual CHP to a subsequent purification system in the existing technology of preparing DCPD DO by a CHP method is avoided, the industrial conversion is facilitated, two high-end epoxy compounds can be produced in a single-package mode, the productivity of the two products can be flexibly adjusted according to market demands, the benefit maximization is realized, and the method has a good industrial application prospect.
Drawings
FIG. 1: the invention is a schematic flow chart.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings, in which reference is made to the figures for the flow of examples as follows.
Example 1
Raw materials DCPD, CHP and solvent cumene according to the mol ratio of 1:2.1:8, mixing, feeding into a first-stage tubular fixed bed reactor, and feeding the total reaction materials at a mass airspeed of 1h -1 Under the reaction conditions that the oxidation reaction temperature is 60 ℃ and the reaction pressure is 0.5MPag, the DCPD is contacted with a Ti-HMS molecular sieve catalyst to react, and the DCPD is oxidized by CHP to generate DCPD O; the reaction product leaves the first-stage tubular fixed bed reactor, the first-stage reaction product is mixed with the added propylene and then enters the second-stage tubular fixed bed reactor to contact with a Ti-HMS molecular sieve catalyst, and the reaction product is reacted in a DCPD (propylene diene monomer) reactor: the propylene molar ratio is 1:0.4, the total reaction material feeding mass airspeed is 4h -1 And under the reaction conditions of the oxidation reaction temperature of 130 ℃ and the reaction pressure of 6MPag, propylene is oxidized by residual CHP in the first-stage reaction product to generate propylene oxide. Separating and purifying the second-stage reaction product, returning the separated isopropyl benzene to the inlet of the first-stage reactor for recycling, separating excessive propylene and returning the propylene to the inlet of the second-stage reactor for recycling, and obtaining DCPDDO and propylene oxide products. In this example, the DCPD conversion rate is 99.08%, the CHP conversion rate is 99.93%, the dcpdo selectivity is 99.86%, and the propylene oxide selectivity is 99.90%.
Example 2
The raw materials DCPD, CHP and solvent ethylbenzene are mixed according to the molar ratio of 1:2.3:10 are mixed and then enter a first-stage tubular fixed bed reactor, and the mass airspeed of the total reaction material feeding is 2h -1 Under the reaction conditions that the oxidation reaction temperature is 70 ℃ and the reaction pressure is 0.8MPag, the DCPD is in contact with a Ti-HMS molecular sieve catalyst to react, and the DCPD is oxidized by CHP to generate DCPDDO; the reaction product leaves a first-stage tubular fixed bed reactor, the first-stage reaction product is mixed with the added butylene and then enters a second-stage tubular fixed bed reactor to contact with a Ti-HMS molecular sieve catalyst, and the reaction product is subjected to reaction in a DCPD: the butene molar ratio is 1:1.2, the total reaction material feeding mass airspeed is 3h -1 Under the reaction conditions of the oxidation reaction temperature of 110 ℃ and the reaction pressure of 5.5MPag, butylene is oxidized by residual CHP in the first-stage reaction product to generate butylene oxide. And separating and purifying the second-stage reaction product, returning ethylbenzene separated out from the second-stage reaction product to the inlet of the first-stage reactor for recycling, returning excessive butene separated out from the second-stage reaction product to the inlet of the second-stage reactor for recycling, and obtaining DCPDO and butylene oxide products. In this example, the DCPD conversion rate was 99.61%, the CHP conversion rate was 99.97%, the DCPDDO selectivity was 99.93%, and the butylene oxide selectivity was 99.93%.
Example 3
Raw materials DCPD, CHP and solvent cumene according to the mol ratio of 1:2.5:11 are mixed and then enter a first-section tubular fixed bed reactor, and the space velocity of the total reaction material feeding mass is 3h -1 Under the reaction conditions that the oxidation reaction temperature is 90 ℃ and the reaction pressure is 1.0MPag, the DCPD is contacted with a Ti-HMS molecular sieve catalyst to react, and the DCPD is oxidized by CHP to generate DCPD O; the reaction product leaves the first-stage tubular fixed bed reactor, the first-stage reaction product is mixed with the added cyclohexene and then enters the second-stage tubular fixed bed reactor to contact with a Ti-HMS molecular sieve catalyst, and the reaction product is subjected to reaction in a DCPD (diethylene glycol dimethyl ether) mode: the cyclohexene molar ratio is 1:2, the total reaction material feeding mass airspeed is 2h -1 Under the reaction conditions of oxidation reaction temperature of 100 ℃ and reaction pressure of 2MPag, cyclohexene is coatedThe residual CHP in the first-stage reaction product is oxidized to generate cyclohexene oxide. And separating and purifying the second-stage reaction product, returning the separated cumene to the inlet of the first-stage reactor for recycling, and returning the separated excessive cyclohexene to the inlet of the second-stage reactor for recycling to obtain DCPDDO and cyclohexene oxide products. In this example, the DCPD conversion rate was 99.97%, the CHP conversion rate was 99.98%, the DCPDDO selectivity was 99.97%, and the cyclohexene oxide selectivity was 99.98%.
Example 4
Raw materials DCPD, CHP and solvent cumene according to the mol ratio of 1:3:13 are mixed and then enter a first-section tubular fixed bed reactor, and the space velocity of the total reaction material feeding mass is 4h -1 Under the reaction conditions that the oxidation reaction temperature is 100 ℃ and the reaction pressure is 1.2MPag, the DCPD is contacted with a Ti-HMS molecular sieve catalyst to react, and the DCPD is oxidized by CHP to generate DCPD O; the reaction product leaves the first-stage tubular fixed bed reactor, the first-stage reaction product is mixed with the added cyclohexene and then enters the second-stage tubular fixed bed reactor to contact with a Ti-HMS molecular sieve catalyst, and the reaction product is subjected to reaction in a DCPD (diethylene glycol dimethyl ether) mode: the cyclohexene molar ratio is 1:4, the total reaction material feeding mass space velocity is 1h -1 Under the reaction conditions of the oxidation reaction temperature of 90 ℃ and the reaction pressure of 1MPag, cyclohexene is oxidized by residual CHP in a first-stage reaction product to generate cyclohexene oxide. And separating and purifying the second-stage reaction product, returning the separated cumene to the inlet of the first-stage reactor for recycling, and returning the separated excessive cyclohexene to the inlet of the second-stage reactor for recycling to obtain DCPDDO and cyclohexene oxide products. In this example, the DCPD conversion rate was 99.91%, the CHP conversion rate was 99.98%, the dcpdo selectivity was 99.95%, and the cyclohexene oxide selectivity was 99.97%.
Example 5
Raw materials DCPD, CHP and a solvent ethylbenzene are mixed according to a molar ratio of 1:4:15 are mixed and then enter a first-section tubular fixed bed reactor, and the space velocity of the total reaction material feeding mass is 3h -1 Under the reaction conditions that the oxidation reaction temperature is 120 ℃ and the reaction pressure is 1.5MPag, the DCPD is contacted with a Ti-HMS molecular sieve catalyst to react, and the DCPD is oxidized by CHP to generate DCPD O; the reaction product leaves the first tubular fixed bed reactor, the first reaction product and the added ringMixing amylene, then feeding the mixture into a two-stage tubular fixed bed reactor, contacting with a Ti-HMS molecular sieve catalyst, and reacting in a DCPD: the cyclopentene molar ratio is 1:8, the total reaction material feeding mass airspeed is 2h -1 Under the conditions of the oxidation reaction temperature of 80 ℃ and the reaction pressure of 0.8MPag, cyclopentene is oxidized by residual CHP in a first-stage reaction product to generate cyclopentane epoxide. And separating and purifying the second-stage reaction product, returning the ethylbenzene separated out from the second-stage reaction product to the inlet of the first-stage reactor for recycling, returning the separated excessive cyclopentene to the inlet of the second-stage reactor for recycling, and obtaining DCPDO and cyclopentane epoxide products. In this example, the DCPD conversion rate was 99.94%, the CHP conversion rate was 99.93%, the DCPDDO selectivity was 99.88%, and the butylene oxide selectivity was 99.94%.
Example 6
The raw materials DCPD, CHP and solvent cumene are mixed according to the molar ratio of 1:2.2:9, mixing, feeding into a first-stage tubular fixed bed reactor, and feeding the total reaction materials at a mass airspeed of 2h -1 Under the reaction conditions that the oxidation reaction temperature is 100 ℃ and the reaction pressure is 1.1MPag, the DCPD is contacted with a Ti-HMS molecular sieve catalyst to react, and the DCPD is oxidized by CHP to generate DCPD O; the reaction product leaves a first-stage tubular fixed bed reactor, the first-stage reaction product is mixed with the added propylene and then enters a second-stage tubular fixed bed reactor to contact with a Ti-HMS molecular sieve catalyst, and the reaction product is subjected to reaction in a DCPD: the propylene molar ratio is 1:2.5, the total reaction material feeding mass airspeed is 2.5h -1 Under the reaction conditions of the oxidation reaction temperature of 120 ℃ and the reaction pressure of 3.5MPag, propylene is oxidized by residual CHP in the first-stage reaction product to generate propylene oxide. And separating and purifying the second-stage reaction product, returning the separated cumene to the inlet of the first-stage reactor for recycling, and returning the separated excessive propylene to the inlet of the second-stage reactor for recycling to obtain DCPDDO and propylene oxide products. In this example, the DCPD conversion rate is 99.99%, the CHP conversion rate is 100%, the dcpdo selectivity is 99.98%, and the propylene oxide selectivity is 99.96%.
The embodiment shows that the method can obtain extremely high raw material conversion rate and product yield which are both more than 99 percent and are far higher than the traditional peroxyacetic acid oxidation process, and simultaneously can avoid the potential safety hazard caused by excessive CHP in the technology of DCPDDO prepared by CHP method disclosed in the patent CN201911336052.5 to the subsequent separation and purification process, thereby having great industrial application prospect.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. A method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds is characterized by comprising two reaction processes; in the first-stage reaction, dicyclopentadiene (DCPD) and Cumene Hydroperoxide (CHP) are used as raw materials, benzene compounds inert to a reaction system are used as solvents, the reaction raw materials are in contact with a titanium silicalite molecular sieve catalyst with an HMS structure in a first-stage reactor to react, the DCPD is oxidized to generate dicyclopentadiene dioxide (DCPD DO), and the first-stage oxidation reaction is completed; the first stage reaction product is mixed with another olefin and fed into a second stage reactor, and the excess CHP reacts with the added olefin to form another epoxy compound.
2. The method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds as claimed in claim 1, wherein the molar ratio of DCPD to CHP in the first reaction is 1,
3. the method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds as claimed in claim 1, wherein the oxidation reaction temperature in the first stage is 60-120 ℃, the reaction pressure is 0.5-1.5 MPag, and the mass space velocity of the reaction material is 1-4 h-.
4. The method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds as claimed in claim 1, wherein the molar ratio of DCPD to other olefins in the two-stage reactor is 1.4-1:8.
5. The method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds as claimed in claim 1, wherein the reaction temperature in the second-stage reaction is 70-130 ℃, the reaction pressure is 0.8-6 MPag, and the mass space velocity of the reaction material is 1-4 h -1 。
6. The method of claim 1, wherein the other olefin is one of propylene, butene, cyclohexene and cyclopentene, and the benzene compound is one of cumene or ethylbenzene.
7. The method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds as claimed in claim 1, wherein the first-stage reactor and the second-stage reactor are tubular fixed bed reactors.
8. The method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds according to claim 1, characterized in that the reaction temperature of the first stage is 70-100 ℃; the reaction pressure is 0.8-1.2 MPag.
9. The method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds according to claim 1, characterized in that the reaction temperature of the second stage is 90-120 ℃; the reaction pressure is 1-5.5 MPag.
10. The method for producing dicyclopentadiene dioxide and co-producing other epoxy compounds as claimed in claim 1, wherein the mass space velocity of the fed reaction materials in the first-stage reactor and the second-stage reaction process is 1-3 h -1。 。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102874835A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Preparation method of HMS structured titanium silicalite molecular sieve |
| CN113087717A (en) * | 2019-12-23 | 2021-07-09 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene dioxide and olefin oxide by combining titanium silicalite molecular sieve catalyst |
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| CN102874835A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Preparation method of HMS structured titanium silicalite molecular sieve |
| CN113087717A (en) * | 2019-12-23 | 2021-07-09 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene dioxide and olefin oxide by combining titanium silicalite molecular sieve catalyst |
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