CN117946128A - Method for removing cumene hydroperoxide byproduct and application thereof - Google Patents
Method for removing cumene hydroperoxide byproduct and application thereof Download PDFInfo
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- CN117946128A CN117946128A CN202211327671.XA CN202211327671A CN117946128A CN 117946128 A CN117946128 A CN 117946128A CN 202211327671 A CN202211327671 A CN 202211327671A CN 117946128 A CN117946128 A CN 117946128A
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- rectifying tower
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- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000006227 byproduct Substances 0.000 title claims abstract description 29
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000000463 material Substances 0.000 claims abstract description 131
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000010992 reflux Methods 0.000 claims abstract description 46
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000004821 distillation Methods 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 30
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 238000009776 industrial production Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012047 saturated solution Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 26
- 238000000066 reactive distillation Methods 0.000 description 19
- 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 description 9
- 239000000047 product Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 5
- 150000005673 monoalkenes Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical group CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for removing cumene hydroperoxide byproduct, which comprises the following steps: 1) Delivering dicyclopentadiene dioxide material into a rectifying tower with side discharge for rectification, wherein the temperature of the rectifying tower kettle is 160-200 ℃, and fully refluxing until cumene hydroperoxide is not detected in the material; 2) The dicyclopentadiene dioxide material is continuously fed, the temperature of distillation overhead is 26.3-43.2 ℃, the temperature of side stream discharge is 130.3-161.4 ℃, and the temperature of tower bottom material is 161.4-200.3 ℃; 3) Collecting distillation column top distillate, side stream discharge distillate of a distillation column, and material liquid in a distillation column kettle; the cumene hydroperoxide is decomposed into acetophenone and methanol in a tower kettle reboiler, the methanol is collected at the top of the tower through rectification separation, the acetophenone and the 2-phenyl-2-propanol are collected at a side discharge port, and the dicyclopentadiene dioxide with the mass fraction of more than 87% is obtained at the tower kettle.
Description
Technical Field
The invention belongs to the technical field of catalytic oxidation synthesis of organic epoxy compounds, and particularly relates to a method for removing cumene hydroperoxide in dicyclopentadiene dioxide by reaction rectification and separating acetophenone and methanol generated by thermal decomposition of hydrogen peroxide in dicyclopentadiene dioxide by rectification to improve the purity of dicyclopentadiene dioxide.
Background
Dicyclopentadiene Dioxide (DCPDDO) is a cycloaliphatic epoxy resin with excellent properties. Compared with common epoxy resin, dicyclopentadiene dioxide has better performances in the aspects of high temperature resistance, heat resistance, weather resistance, ultraviolet resistance, electric insulation and the like. Based on the properties, the dicyclopentadiene dioxide can be widely used in the aspects of high-temperature-resistant electrical casting materials, multifunctional electronic laminated composite materials, electronic component packaging materials, high-temperature-resistant carbon fiber composite materials and the like.
In the prior art, the industrial production of dicyclopentadiene dioxide is generally carried out by a peroxyacetic acid method. At present, the catalytic oxidation method which takes hydrogen peroxide as an oxidant and heteropolyacid as a catalyst for synthesizing dicyclopentadiene dioxide is a research hotspot in the field or is in a laboratory research stage. Chinese petrochemical technology is disclosed in which titanium-silicon molecular sieve is used as catalyst, cumene Hydroperoxide (CHP) is used as oxidant, and in the presence of inert solvent, a fixed bed continuous reaction process is adopted to oxidize dicyclopentadiene (DCPD) into dicyclopentadiene dioxide. Since the DCPD molecule has two double bonds, an excess of organic peroxide is necessary to completely convert the DCPD to dicyclopentadiene dioxide. And excessive organic peroxide causes a plurality of problems for product separation and purification. In order to remove peroxide in DCPDDO products which is not completely reacted, sodium sulfite or sodium sulfide aqueous solution is added into the reaction products to remove organic peroxide usually after the reaction is finished, so that a large amount of wastewater can be formed by the treatment method, and inorganic salt is introduced into dicyclopentadiene dioxide products to influence the application of DCPDDO in high-end electronic products.
In order to remove cumene hydroperoxide which is not completely reacted in DCPDDO products, CN114426546A discloses a method for removing cumene hydroperoxide, which comprises the steps of separating a solvent and most of 2-phenyl-2-propanol in DCPDDO reaction materials by rectification, mixing DCPDO and CHP mixed materials with excessive mono-olefin, feeding the mixed materials into another reactor filled with titanium silicalite molecular sieve catalyst for secondary epoxidation reaction, continuously reacting mono-olefin with CHP in dicyclopentadiene dioxide materials to generate alkylene oxide, and separating and recovering excessive mono-olefin by rectification. The method effectively removes CHP in DCPDDO products, but a plurality of rectification operation units are needed to be added in the subsequent product separation process, and alkylene oxide and mono-olefin are separated and recovered.
According to the invention, experiments show that DCPDDO materials are synthesized according to the method disclosed by the prior art CN114426546A, the solvent and most of materials obtained in a tower kettle after 2-phenyl-2-isopropanol are separated by rectification, and a thermal stability experiment is carried out for 30 hours at 160-200 ℃, and the experimental results show that DCPDDO materials are stable and do not undergo polymerization reaction or decomposition reaction, but CHP in the materials is decomposed to generate acetophenone and methanol.
The dicyclopentadiene dioxide material containing CHP and 2-phenyl-2-propanol is subjected to reduced pressure separation, and the fact that the temperature of the tower bottom material of the rectifying tower exceeds 160 ℃ is also found, the CHP in the tower bottom material is also decomposed, and the DCPDDO structure is kept unchanged.
The inventors have therefore proposed a process for efficiently removing CHP from DCPDDO materials by thermal decomposition, especially in the DCPD epoxidation stage, where the molar ratio of DCPD to CHP is controlled from 1:2 to 1:2.1, which is of great practical significance.
The inventor uses the characteristic of CHP and DCPD O materials to directly change the process of removing the CHP by catalytic epoxidation of two-stage monoolefin in the prior art into a thermal decomposition reaction process, adopts the method that the dicyclopentadiene material containing the CHP is conveyed into a rectifying tower for purification DCPDDO, the rectifying tower adopts a side discharge mode, the temperature of kettle materials is controlled between 160 ℃ and 200 ℃, on one hand, the CHP is decomposed in a rectifying tower reboiler by reactive rectification, on the other hand, the CHP is decomposed and generated by rectifying separation, the side discharge port of the rectifying tower collects acetophenone and 2-phenyl-2-propanol, the dicyclopentadiene dioxide with the mass fraction more than 87% is obtained at the kettle, and the CHP removal and the purification DCPDDO are completed in one rectifying tower. The method disclosed by the invention simplifies the technical flow of dicyclopentadiene dioxide synthesis and byproducts of acetophenone and methanol.
Disclosure of Invention
The technical scheme of the invention is specifically introduced as follows.
The invention provides a method for removing cumene hydroperoxide byproduct, which comprises the following steps:
1) Conveying dicyclopentadiene dioxide materials to a rectifying tower for rectification, wherein the temperature of the rectifying tower kettle is 160-200 ℃, and fully refluxing until cumene hydroperoxide cannot be detected in the materials;
2) The dicyclopentadiene dioxide material is continuously fed, the temperature of distillation overhead is 26.3-43.2 ℃, the temperature of side stream discharge is 130.3-161.4 ℃, and the temperature of tower bottom material is 161.4-200.3 ℃;
3) Collecting distillation column top distillate, side stream discharge distillate of a distillation column, and material liquid in a distillation column kettle;
Wherein,
The dicyclopentadiene dioxide material composition is 65.1 to 97.5 weight percent of dicyclopentadiene dioxide, 1.2 to 14.1 weight percent of 2-phenyl-2-propanol and 0.8 to 24.1 weight percent of cumene hydroperoxide.
The invention provides a method for removing cumene hydroperoxide byproduct, wherein the pressure at the top of a rectifying tower in the step 1) and the step 2) is 13-41 KPa.
The invention provides a method for removing cumene hydroperoxide byproduct, wherein the pressure at the top of a rectifying tower is 13-24 KPa.
The invention provides a method for removing cumene hydroperoxide byproduct, wherein the theoretical plate number of a rectifying tower is 15-30.
The invention provides a method for removing cumene hydroperoxide byproduct, wherein the reflux ratio of a rectifying tower in the step 2) is 3:1-6:1.
The invention provides a method for removing cumene hydroperoxide byproduct, wherein a lateral line discharge hole in the step 2) is arranged at the 4 th to 8 th tower plates.
The invention provides a method for removing cumene hydroperoxide byproduct, wherein the temperature of the tower kettle material in the step 2) is 161.4-181.2 ℃.
The invention provides a method for removing cumene hydroperoxide byproduct, wherein the rectifying tower top distillate in the step 3) is formed into 95.8-100 wt% methanol, 0.1-2.9 wt% acetophenone and 0.0-1.3 wt% 2-phenyl-2-propanol.
The invention provides a method for removing cumene hydroperoxide byproduct, wherein the composition of a side discharge fraction of a rectifying tower in the step 3) is 48.6wt% -97.8wt% acetophenone, 2.1wt% -51.3wt% 2-phenyl-2-propanol and 0.1wt% -0.2wt% methanol.
The invention provides a method for removing cumene hydroperoxide byproduct, wherein the composition of the rectifying tower kettle feed liquid in the step 3) is 87.2-93.6 wt% of dicyclopentadiene dioxide, 4-11.4 wt% of acetophenone and 1.0-6.1 wt% of 2-phenyl-2-propanol.
Preferably, the present invention also provides a method for removing cumene hydroperoxide byproduct according to the above, wherein the dicyclopentadiene dioxide feed composition is 74.0wt% to 78.9wt% dicyclopentadiene dioxide, 1.2wt% to 12.3wt% 2-phenyl-2-propanol, and 13.7wt% to 20.2wt% cumene hydroperoxide.
Preferably, the invention also provides a method for removing the cumene hydroperoxide byproduct, wherein the feed inlet in the step 2) is positioned at 15 th to 30 th tower plates of the rectifying tower.
Preferably, the invention also provides the method for removing the cumene hydroperoxide byproduct, and the application of the method in industrial production of dicyclopentadiene dioxide.
More preferably, the present invention also provides the above method for removing cumene hydroperoxide byproduct, wherein the cumene hydroperoxide removal rate is 100%.
More preferably, the invention also provides a method for removing the cumene hydroperoxide byproduct, and the method further comprises the step of crystallizing and separating the rectifying tower kettle feed liquid.
Wherein, the crystallization separation is to prepare a saturated solution of the material liquid in the rectifying tower kettle by cyclohexane under normal pressure and at 70-80 ℃, cool, separate out dicyclopentadiene dioxide, filter, separate and dry.
The drying is vacuum drying at 70-80 ℃.
Preferably, the invention also provides a method for removing cumene hydroperoxide byproduct, and the purity of the obtained dicyclopentadiene dioxide is more than or equal to 95 percent.
According to the method provided by the invention, the dicyclopentadiene dioxide material is conveyed into a rectifying tower with a lateral line discharge hole, the theoretical plate number of the rectifying tower is 15-30, the tower top pressure is controlled at 13-41 KPa, the tower top fraction temperature is controlled at 26.3-43.2 ℃, the lateral line discharge temperature is 130.3-161.4 ℃, the tower bottom material temperature is controlled at 161.4-200.3 ℃, the reflux ratio is 3:1-6:1, and the lateral discharge hole is arranged at the 4 th-8 th pedal. The CHP in dicyclopentadiene dioxide is subjected to thermal decomposition reaction in a reboiler of a tower kettle to generate acetophenone and methanol, the methanol is collected at the top of the tower through side stream discharge, acetophenone and 2-phenyl-2-propanol are collected at a side stream discharge port, and the dicyclopentadiene dioxide with improved purity is obtained at the tower kettle.
Compared with the prior art, the invention has the following advantages:
According to the preparation method provided by the invention, CHP in DCPDDO materials is removed by adopting a simple thermal decomposition reaction, so that the process flow of synthesizing DCPDDO is simplified, acetophenone and methanol are byproducts, equipment and energy consumption are reduced, and the process is easier to realize industrialization.
And the side discharge is skillfully added on the rectifying tower, so that the cumene hydroperoxide byproduct is not only completely thermally decomposed into methanol and acetophenone, but also the main component of the cumene hydroperoxide byproduct in the side discharge is acetophenone, and the overhead fraction of the rectifying tower is mainly methanol, so that the purity of the byproduct methanol and acetophenone and the value of subsequent utilization are increased.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein. For the purposes of the present invention, the following terms are defined below.
Dicyclopentadiene dioxide
The dicyclopentadiene dioxide has a chemical formula of C 10H12O2, and the English name is Dicyclopentadiene diepoxide and DCPDDO for short.
2-Phenyl-2-propanol
The invention relates to 2-Phenyl-2-propanol, which has the chemical formula: c 9H12 O.
Cumene hydroperoxide
The chemical formula of the cumene hydroperoxide is C 9H12O2, and the English name is Cumene hydroperoxide, CHP is short for CHP.
Dicyclopentadiene dioxide material
The dicyclopentadiene dioxide material of the present invention may also be referred to as a mixture comprising dicyclopentadiene dioxide or a material comprising dicyclopentadiene dioxide. The dicyclopentadiene dioxide material comprises 65.1 to 97.5 weight percent of dicyclopentadiene dioxide, 1.2 to 14.1 weight percent of 2-phenyl-2-propanol and 0.8 to 24.1 weight percent of cumene hydroperoxide. In addition, the dicyclopentadiene dioxide material can also be obtained by industrial production of dicyclopentadiene, and can also be prepared into dicyclopentadiene dioxide mixed material containing hydrogen peroxide isopropylbenzene according to the technology disclosed by CN114426546A in the prior art.
The dicyclopentadiene dioxide feed used in examples 1 to 16 consists of: 74.0 to 78.9 weight percent of dicyclopentadiene dioxide, 1.2 to 12.3 weight percent of 2-phenyl-2-propanol and 13.7 to 20.2 weight percent of cumene hydroperoxide.
Wherein the bisdicyclopentane dioxide used in examples 1 to 15 consists of: dicyclopentadiene dioxide 78.6wt%, 2-phenyl-2-propanol 1.2wt% and cumene hydroperoxide 20.2wt%. The bisglutaryl dioxide used in example 16 had a composition of: 74.0wt% of dicyclopentadiene dioxide, 12.3wt% of 2-phenyl-2-propanol and 13.7wt% of cumene hydroperoxide. The bisglutaryl dioxide used in example 17 had a composition of: dicyclopentadiene dioxide 78.9wt%, 2-phenyl-2-propanol 6.5wt% and cumene hydroperoxide 14.6wt%.
Rectifying tower
The rectifying tower is a stainless steel rectifying tower with a lateral line discharge hole, the height of the rectifying tower is 1200mm, the inner diameter of the rectifying tower is 50mm, the volume of a tower kettle is 10L, the packing filled in the rectifying tower is stainless steel theta ring packing, the packing specification phi 3mm is 3mm, the theoretical plate number of the rectifying tower is regulated by regulating the height of the packing, and the feed inlet and the lateral line discharge hole can be regulated. The feeding and discharging of the rectifying tower and the tower bottom adopt metering pumps, the distillate at the top of the tower is discharged from a lateral line, and the distillate overflows into a storage tank from a liquid receiving disc by utilizing the liquid level difference. The reflux condenser at the top of the tower adopts low-temperature water at the temperature of minus 5 ℃ to condense and cool materials, the evaporation of materials at the bottom of the tower adopts an intelligent control electric heating mode, the reflux ratio controller controls the reflux quantity at the top of the tower, and the vacuum system is provided by a 2XZ-4 rotary vane vacuum oil pump.
Removal of cumene hydroperoxide byproduct
The method for removing the cumene hydroperoxide by-product refers to removing or removing cumene hydroperoxide and acetophenone and methanol formed by thermal decomposition of the cumene hydroperoxide in dicyclopentadiene dioxide materials, and the method for removing the cumene hydroperoxide by-product refers to removing cumene hydroperoxide by a thermal decomposition method and rectifying and separating acetophenone and methanol formed by thermal decomposition of the cumene hydroperoxide.
Cumene hydroperoxide removal rate
The cumene hydroperoxide removal rate is calculated and obtained according to the following formula:
Cumene hydroperoxide removal = (CHP mass in 1-thermal isomerization reaction product/CHP mass in thermal isomerization reaction feed) 100%
In addition, technical features described below in the various embodiments of the present invention may be combined with each other as long as they do not collide with each other. The test methods in the following examples, in which specific conditions are not specified, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated.
Experimental materials used in the following examples include:
| Name of the name | Specification of specification | Source(s) |
| Dicyclopentadiene dioxide material | 65.1 To 97.5 weight percent of dicyclopentadiene dioxide | Shanghai petrochemical industry |
| Rectifying tower kettle | 10L | Tianjin North ocean |
| Cyclohexane | The mass fraction is 99% | Group of Chinese medicine |
The present invention is further illustrated by the following examples, but the present invention is not limited to the examples.
Reactive distillation was carried out under the process conditions shown in the following table, and experimental studies on the process conditions of the column bottom except CHP were specifically shown in examples 1 to 17.
TABLE 1 rectification process parameters for examples 1-17
Example 1: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 2 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 500g/h, the pressure of the rectifying tower top is 41KP, the temperature of a rectifying tower top fraction is 43.2 ℃, a lateral line discharge port is positioned at a 5 th tray, the lateral line discharge temperature is 161.4 ℃, the temperature of the rectifying tower kettle material is 200.3 ℃, and the reflux ratio is 6:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 2: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after 3 hours of total reflux operation, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 300g/h, the pressure of the rectifying tower top is 32KP, the temperature of a rectifying tower top fraction is 37.9 ℃, a lateral line discharge port is positioned at a 5 th tray, the lateral line discharge temperature is 153.3 ℃, the temperature of the rectifying tower kettle material is 191.3 ℃, and the reflux ratio is 6:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 3: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after 3 hours of total reflux operation, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 250g/h, the pressure of the rectifying tower top is 24KP, the temperature of a rectifying tower top fraction is 32 ℃, a lateral line discharge port is positioned on a 5 th tray, the lateral line discharge temperature is 143.8 ℃, the temperature of the rectifying tower kettle material is 181.2 ℃, the reflux ratio is 6:1, and rectifying tower top fractions, rectifying tower kettle feed liquid and standby are respectively collected.
Example 4: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 200g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at a 5 th tray, the lateral line discharge temperature is 134 ℃, the temperature of the rectifying tower kettle material is 171.7 ℃, the reflux ratio is 6:1, and rectifying tower top fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 5: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 8 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 50g/h, the pressure of the rectifying tower top is 13KP, the temperature of a rectifying tower top fraction is 20.2 ℃, a lateral line discharge port is positioned at a 5 th tray, the lateral line discharge temperature is 123.6 ℃, the temperature of the rectifying tower kettle material is 161.4 ℃, and the reflux ratio is 6:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 6: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 15 th tower plate arranged near the rectifying tower kettle, the number of the tower plates of the rectifying tower is 15, the feeding speed of the rectifying tower is 100g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at a 4 th tower plate, the lateral line discharge temperature is 131.5 ℃, the temperature of the tower kettle material is 171.7 ℃, and the reflux ratio is 6:1, and rectifying tower top fractions, rectifying tower kettle feed liquid and standby are respectively collected.
Example 7: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 15 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 15, the feeding speed of the rectifying tower is 50g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at a 4 th tray, the lateral line discharge temperature is 131.2 ℃, the temperature of the rectifying tower kettle material is 171.5 ℃, and the reflux ratio is 5:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 8: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 15 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 15, the feeding speed of the rectifying tower is 150g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at a 4 th tray, the lateral line discharge temperature is 130.3 ℃, the temperature of the rectifying tower kettle material is 171.4 ℃, and the reflux ratio is 4:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 9: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 15 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 15, the feeding speed of the rectifying tower is 50g/h, the pressure of the rectifying tower top is 18KPa, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at a 4 th tray, the lateral line discharge temperature is 128.7 ℃, the temperature of the rectifying tower kettle material is 171.0 ℃, and the reflux ratio is 3:1, and rectifying tower top fractions, rectifying tower kettle feed liquid and standby are respectively collected.
Example 10: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 30 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 30, the feeding speed of the rectifying tower is 200g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at an 8 th tray, the lateral line discharge temperature is 131.5 ℃, the temperature of the rectifying tower kettle material is 171.0 ℃, and the reflux ratio is 3:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 11: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 30 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 30, the feeding speed of the rectifying tower is 200g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at an 8 th tray, the lateral line discharge temperature is 134.8 ℃, the temperature of the rectifying tower kettle material is 171.5 ℃, and the reflux ratio is 5:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 12: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 50g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at a 5 th tray, the lateral line discharge temperature is 133.6 ℃, the temperature of the rectifying tower kettle material is 171.4 ℃, and the reflux ratio is 4:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 13: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 50g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at a 5 th tray, the lateral line discharge temperature is 131.3 ℃, the temperature of the rectifying tower kettle material is 171.0 ℃, the reflux ratio is 3:1, and rectifying tower top fractions, rectifying tower side line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 14: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 50g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at a4 th tray, the lateral line discharge temperature is 130.3 ℃, the temperature of the rectifying tower kettle material is 171.4 ℃, and the reflux ratio is 4:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 15: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 100g/h, the pressure of the rectifying tower top is 18KP, the temperature of a rectifying tower top fraction is 26.3 ℃, a lateral line discharge port is positioned at a 6 th tray, the lateral line discharge temperature is 133.8 ℃, the temperature of the rectifying tower kettle material is 171.4 ℃, and the reflux ratio is 4:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 16: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 6 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 250g/h, the pressure of the rectifying tower top is 21KP, the temperature of a rectifying tower top fraction is 29.5 ℃, a lateral line discharge port is positioned at a 5 th tray, the lateral line discharge temperature is 144.1 ℃, the temperature of the rectifying tower kettle material is 178.9 ℃, and the reflux ratio is 4:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Example 17: reactive distillation, thermal decomposition of distillation tower kettle to remove CHP in DCPDDO
5000 G of dicyclopentadiene dioxide material is put into a rectifying tower kettle, under the conditions that the temperature of the rectifying tower kettle is 160-200 ℃ and the pressure of the rectifying tower top is 13-41 KPa, after total reflux operation is carried out for 5 hours, namely after cumene hydroperoxide is not detected in the material, the dicyclopentadiene dioxide material is continuously fed from a feed inlet of a 20 th tray arranged near the rectifying tower kettle, the number of the rectifying tower trays is 20, the feeding speed of the rectifying tower is 300g/h, the pressure of the rectifying tower top is 21KP, the temperature of a rectifying tower top fraction is 29.3 ℃, a lateral line discharge port is positioned at a 5 th tray, the lateral line discharge temperature is 143.3 ℃, the temperature of the rectifying tower kettle material is 182.1 ℃, and the reflux ratio is 8:1, and rectifying tower top fractions, rectifying tower lateral line discharge fractions and rectifying tower kettle feed liquid are respectively collected for standby.
Test example 1: analysis of product composition after reactive distillation
Test sample: examples 1-17 rectifying column overhead, rectifying column sidedraw effluent, rectifying column bottoms feed.
The content of cumene hydroperoxide is determined by an iodometric method, and the determination method is shown in GB/T32102-2015.
DCPDDO, 2-phenyl-2-propanol, acetophenone, methanol were determined by gas chromatography, gas chromatography analysis method: analytical instrument Agilent 6890, detector FID, column HP-1, 50mm 0.2mm 0.5um. Carrier gas: nitrogen, temperature of the sample injector 260 ℃, temperature of the detector 260 ℃, split ratio 100:1 and sample injection amount 0.4ul. Programming temperature: the temperature is kept for 5min at 80 ℃, the temperature is increased to 260 ℃ at 10 ℃/min, the temperature is kept for 4min, and the external standard method is used for quantification.
And (3) examining the influence of different pressures, tower kettle temperatures and reflux ratios on the CHP removal effect in tower kettle materials, rectifying tower top fractions, rectifying tower side stream discharge fractions, and the mass percentage compositions of the material liquid in the rectifying tower kettle are shown in tables 2 and 3.
TABLE 2 composition of the distillation overhead fraction (unit: wt%)
TABLE 3 composition of the side offtake of the rectifying column (unit: wt%)
Table 4 the mass composition (unit:%)
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As can be seen from tables 2 to 4, the methanol enrichment tower top with the mass fraction of more than 95.8 to 100 percent is separated by reduced pressure rectification, the content of 2-phenyl-2-propanol in dicyclopentadiene dioxide materials in examples 1 to 15 is 1.2 weight percent, the mass fraction of acetophenone collected by side discharge is more than 94 percent, and the mass fraction of DCPDDO in tower bottom feed liquid reaches more than 87 percent after the separation by rectification. The mass fraction of CHP in the tower top fraction, the side-draw fraction and the tower kettle material is zero, and the CHP removal rate is 100%.
As shown in Table 4, the composition of the rectifying column bottoms liquid in example 15 was DCPDDO to 87.4wt%, acetophenone to 11.3wt% and 2-phenyl-2-propanol to 1.2wt%.
Example 18: crystallization separation and purification of dioxydicyclopentadiene
Weighing the material liquid and cyclohexane in the rectifying tower kettle of the example 15, wherein the mass ratio of the material liquid to the cyclohexane is 1:4, putting the materials liquid and the cyclohexane into 500 milliliters of round bottom glass with a reflux condenser tube to prepare DCPDDO saturated solution under the conditions of normal pressure and 70-80 ℃, then cooling the solution at 10-15 ℃, separating out DCPDDO from the cyclohexane in a solid form, filtering and separating out DCPDDO, carrying out vacuum drying at 2-3 KPa and 70-80 ℃ for 3-6 hours, and obtaining DCPDDO with the mass fraction of more than 95%.
Example 19: experiments on the thermal stability of mixtures of dicyclopentadiene dioxide and 2-phenyl-2-propanol
200 G of a mixture of 87% by mass of dicyclopentadiene dioxide and 12% by mass of 2-phenyl-2-propanol are put into a 500 ml autoclave, stirred, the temperature of the mixture is raised to 200 ℃, and the mixture is kept for 30 hours, and samples are taken every 10 hours for later use.
Test example 2: thermal stability test sample analysis
Test sample: example 19 thermal stability test 10 hours samples, example 19 thermal stability test 20 hours samples, example 19 thermal stability test 30 hours samples.
The composition of DCPDDO, 2-phenyl-2-propanol and the mixture with 87% dicyclopentadiene dioxide mass fraction and 12% 2-phenyl-2-propanol mass fraction were determined by gas chromatography and compared. The experimental results are shown in table 5.
TABLE 5 experiments on the thermal stability of mixtures of dicyclopentadiene dioxide and 2-phenyl-2-propanol
As is clear from Table 5, the mixture of dicyclopentadiene dioxide and 2-phenyl-2-propanol has a thermal stability as shown in the experiment, and the mixture of dicyclopentadiene dioxide and 2-phenyl-2-propanol has a thermal stability at 200℃for 10 hours, 20 hours and 30 hours, and the composition of the mixture is substantially the same as that of the raw materials, i.e., the mixture has a good stability at 200℃and does not undergo thermal decomposition or polymerization.
The invention is found and utilized to improve the temperature of the material at the bottom of the rectifying tower by utilizing the characteristic of the mixture of dicyclopentadiene dioxide and 2-phenyl-2-propanol, and CHP in the dicyclopentadiene dioxide material is effectively removed by a reactive rectifying process to obtain DCPDDO with mass fraction more than 87%, and acetophenone and methanol are byproducts.
While the preferred embodiments of the present application have been described in detail, the present application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present application, and these equivalent modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (19)
1. A method for removing cumene hydroperoxide byproduct comprising the steps of:
1) Delivering dicyclopentadiene dioxide material into a rectifying tower with side discharge for rectification, wherein the temperature of the rectifying tower kettle is 160-200 ℃, and fully refluxing until cumene hydroperoxide is not detected in the material;
2) The dicyclopentadiene dioxide material is continuously fed, the temperature of distillation overhead is 26.3-43.2 ℃, the temperature of side stream discharge is 130.3-161.4 ℃, and the temperature of tower bottom material is 161.4-200.3 ℃;
3) Collecting distillation column top distillate, side stream discharge distillate of a distillation column, and material liquid in a distillation column kettle;
wherein the dicyclopentadiene dioxide material composition is 65.1 to 97.5 weight percent of dicyclopentadiene dioxide, 1.2 to 14.1 weight percent of 2-phenyl-2-propanol and 0.8 to 24.1 weight percent of cumene hydroperoxide.
2. The method according to claim 1, wherein the pressure at the top of the rectifying column in the step 1) and the step 2) is 13 to 41KPa.
3. The method of claim 2, wherein the pressure at the top of the rectifying column is between 13 and 24KPa.
4. The method of claim 1, wherein the total reflux to the material at atmospheric pressure is for 2 to 8 hours without detecting cumene hydroperoxide.
5. The method of claim 1, wherein the theoretical plates of the rectifying column are 15 to 30.
6. The method according to claim 1, wherein the reflux ratio of the rectifying tower in the step 2) is 3:1 to 6:1.
7. The method according to claim 1, wherein the side offtake in step 2) is at trays 4 to 8.
8. The method of claim 1, wherein the temperature of the bottoms material in step 2) is 161.4 to 181.2 ℃.
9. The process according to claim 1, wherein the rectifying column overhead fraction in step 3) is formed into 95.8wt% to 100wt% methanol, 0.1wt% to 2.9wt% acetophenone and 0 to 1.3wt% 2-phenyl-2-propanol.
10. The process according to claim 1, wherein the composition of the rectifying column side offtake in step 3) is 48.6 to 97.8 wt.% acetophenone, 2.1 to 51.3 wt.% 2-phenyl-2-propanol and 0.1 to 0.2 wt.% methanol.
11. The process according to claim 1, wherein the composition of the rectifying still bottoms in step 3) is 87.2wt% to 93.6wt% dicyclopentadiene dioxide, 4wt% to 11.4wt% acetophenone and 1wt% to 6.1wt% 2-phenyl-2-propanol.
12. The method according to any one of claims 1 to 11, wherein the feed inlet in step 2) is located at the 15 th to 30 th tray of the rectifying column.
13. The process of any one of claims 1-11, wherein the dicyclopentadiene dioxide feed composition is 74.0wt% to 78.9wt% dicyclopentadiene dioxide, 1.2wt% to 12.3wt% 2-phenyl-2-propanol, and 13.7wt% to 20.2wt% cumene hydroperoxide.
14. Use of the method according to claim 13 for the industrial production of dicyclopentadiene dioxide.
15. The process of any one of claims 1-11, wherein the process has a cumene hydroperoxide removal rate of 100%.
16. The method of any one of claims 1-11, further comprising crystallizing the rectifying column bottoms feed.
17. The method of claim 16, wherein the crystallization separation is carried out by preparing saturated solution of material liquid in a rectifying tower kettle by cyclohexane under normal pressure at 70-80 ℃, cooling, separating out dicyclopentadiene dioxide, filtering, separating, and drying.
18. The method of claim 17, wherein the drying is vacuum drying at 70-80 ℃.
19. The dicyclopentadiene dioxide obtained by the method according to claim 18 has a purity of 95% or more.
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