CN1781887A - Process for producing high purity dicyclo pentylene - Google Patents
Process for producing high purity dicyclo pentylene Download PDFInfo
- Publication number
- CN1781887A CN1781887A CN 200510060841 CN200510060841A CN1781887A CN 1781887 A CN1781887 A CN 1781887A CN 200510060841 CN200510060841 CN 200510060841 CN 200510060841 A CN200510060841 A CN 200510060841A CN 1781887 A CN1781887 A CN 1781887A
- Authority
- CN
- China
- Prior art keywords
- dcpd
- high purity
- depolymerization
- production technique
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 title claims description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000005120 petroleum cracking Methods 0.000 claims abstract description 5
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 71
- 238000006471 dimerization reaction Methods 0.000 claims description 37
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 230000015556 catabolic process Effects 0.000 claims description 15
- 238000006731 degradation reaction Methods 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000012691 depolymerization reaction Methods 0.000 claims description 5
- -1 magnesium aluminate Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000010458 rotten stone Substances 0.000 claims 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 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 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 abstract description 8
- 230000000447 dimerizing effect Effects 0.000 abstract 2
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 44
- 239000000047 product Substances 0.000 description 14
- 238000004821 distillation Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- 238000004939 coking Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a technological process of producing high purity dicyclopentadiene (DCPD) with petroleum cracking C5 fraction as main material. The process includes the following steps: 1. dimerizing C5 fraction and eliminating light components to obtain coarse DCPD; 2. catalytically depolymerizing the coarse DCPD at 100-200 deg.c in the presence of inorganic carrier supported acid catalyst to obtain high purity CPD; and 3. dimerizing CPD and eliminating light components to obtain high purity DCPD. The present invention is a low temperature catalytic depolymerizing process with low scaling, and effectively raised depolymerizing reaction rate and depolymerizing reaction selectivity.
Description
(1) technical field
The present invention relates to a kind of production technique of dicyclopentadiene.
(2) background technology
Dicyclopentadiene (being called for short DCPD) is the by product of petroleum cracking system ethene and coal coking.Because DCPD contains active methylene radical and two conjugated double bonds, reactive behavior is very high, and with multiple olefin-copolymerization or participate in multiple organic chemical reactions, make it have purposes widely at aspects such as synthetic rubber, resin, medicine, coating, fuel, softening agent, organic syntheses.
The special purpose of DCPD is in thermoset polymeric material, and the purity of the performance of thermoset polymeric material and used DCPD is closely related.The purity of DCPD is not only relevant with purposes, but also influences the performance of final polymeric material, also may influence the time of polyreaction.The DCPD that is used for thermoset polymeric material then needs 99% purity at least.
The main raw material that DCPD produces is the C 5 fraction of petroleum cracking, and general elder generation becomes DCPD with CPD dimerization wherein, then separation and purification DCPD.Because C 5 fraction composition complexity, the diolefin and the alkene that wherein contain a large amount of C4-C6, character is very unstable, in the process of CPD dimerization and separation and purification, can be because variation generation dimerization, codimerization, poly, decomposition and other chemical reaction of conditions such as temperature, pressure, particularly the unstable of product D CPD causes the production of high purity DCPD very difficult.
Main impurity has two classes among the technical grade DCPD, and a class is lower-boiling impurity (unsaturated hydrocarbons that comprises the C4-C6 of CPD), and the polymeric type reaction takes place in technological process for they, except that the CPD dimerization, can produce high boiling impurity.Another kind of is high-boiling-point impurity, and codimerization product (as: the codimers PNB of CPD and m-pentadiene), trimerization CPD etc. are wherein arranged, and they can resolve into lower boiling impurity in technological process.Technology by the DCPD of technical grade DCPD purifying high-purity can be divided into rectification method and depolymerization-dimerization-rectification method.
JP 174939 adopts the method for twice underpressure distillation, removes light constituents such as C4-C6 earlier, steams product then, but contains the propenyl norbornylene in the product, is difficult to remove, and needs to add oxidation inhibitor, influences the application of product in the RIM material.JP 193038 adopts the method for three rectifications under vacuum, removes light constituents such as C4-C6 earlier, removes the propenyl norbornylene then, steams product at last.But rectifying condition harshness, the oxidation inhibitor consumption is big, and working cost is very high.
The method technology of rectifying is comparatively simple, earlier removes lower-boiling impurity by the low tower that boils, and the low then tower still discharging of boiling is advanced the height tower that boils and removed high-boiling-point impurity.But for preventing DCPD high temperature depolymerization in the low tower still that boils, need to adopt decompression operation, thus the recovery difficulty of lower-boiling impurity, even can take away a large amount of products, cause the technology total recovery very low.And the boiling point of high boiling impurity and product is approaching, is difficult to remove fully in height boils tower, causes the purity of product to be difficult to reach requirement.
USP3719718 proposes the progressively quantitative method of depolymerization of dicyclopentadiene, is raw material with the C 5 fraction of pyrolysis gasoline.In stage number is in the reactive distillation reactor of 2-10 piece, at the bottom of the still temperature between 170-250 ℃, wherein the content of the codimerization thing of isoprene dipolymer and cyclopentadiene, isoprene and m-pentadiene between 10-70%, 50 ℃ of tower top temperatures.Cracking product yield 91%, wherein the content of cyclopentadiene about 92%.Discharge material at the bottom of the tower and enter a thin-film evaporator, under the condition of 225 ℃ of wall temperatures, steam undecomposed raw material, a small amount of jelly discharges from base of evaporator.After both combinations, continuous production 1500 hours, the total recovery of cyclopentadiene reaches 90-95%.
USP5321177 proposes the production process of a kind of high purity DCPD, and its production process is: the dimerization of C 5 fraction; Rectifying obtains the thick DCPD of content 70% (wt%); In tubular reactor, 250-450 ℃, mix or not under the condition of mixing water steam the complete cracking of DCPD; Progressively cooling obtains CPD; The CPD dimerization; Unreacted light constituent is removed in distillation; Rectifying obtains high purity DCPD, heavy constituent circulation depolymerization.The concentration of DCPD surpasses 97%.
USP5401891 proposes the technology that a kind of polymerization-grade DCPD produces, main step comprises: (a) thick DCPD is depolymerized to and contain multiple monomeric fluid (comprising the diolefine of C4 and C5, CPD and methyl cyclopentadiene etc.); (b) reclaim the also above-mentioned fluid of rectifying, obtain being rich in the fluid of CPD; (c) 60-85%CPD dimerization; (d) unconverted monomer obtains purity and surpasses 98% DCPD by membrane sepn.
In depolymerization-dimerization processes, depolymerization is one of critical step, because difficult decomposition such as propenyl norbornylene, low temperature depolymerization selectivity is higher, but depolymerization speed is slow, and the CPD in the codimerization thing such as propenyl norbornylene can't utilize.When the codimerization thing content among the thick DCPD was big, the total yield of DCPD was not high.It is heating agent that USP 2453044 adopts water vapour, carries out the gas phase depolymerization reaction in temperature of reaction is 350 ℃-450 ℃ tubular reactor, and the reaction times is about 1-3 second, and dimeric depolymerization rate is about 90%.USP2831954, JP50227537 and SU1328343 etc. adopt logistics of high temperature heat-carrying and thick DCPD to mix the method for carrying out gas phase or liquid phase depolymerization under normal pressure and hot conditions.Ger often 2425289 and Ger often 2425290 propositions as solvent, are reduced to 180 ℃ with the temperature of depolymerization with lower boiling organic compound such as pentamethylene.USP5877366 proposes to improve the depolymerization temperature with the inertia heat-transfer medium, promotes the method that CPD shifts, and improves transformation efficiency and the yield of DCPD, and the transformation efficiency of its DCPD reaches 98-100%, and monomer purity reaches 97-100%.EP0509445 feeds tube cracking furnace after with thick DCPD preheating, after 300-350 ℃ of following cracking, removes heavy constituent; Behind the dimerization reaction, twice underpressure distillation obtains high purity DCPD.The speed of response of high temperature gas phase depolymerization process is fast, depolymerization degree height, and codimers such as propenyl norbornylene also decompose, and make that the CPD in the codimers also can obtain utilizing.But high-temperature technology coking severity, the continuity that influence is produced and total yield.
CN1334262A proposes a kind of specific equipment of DCPD depolymerization, under the prerequisite of not using thermal barrier, by changing the layout of heat-transfer surface, strengthen the vaporization rate of DCPD, improve the depolymerization temperature and increase the residence time, thereby avoided the pollution and the loss of thermal barrier, also avoided loss of material.The pressure of depolymerization is normal pressure, and temperature is 240-260 ℃.
CN1292369A proposes the preparation method of a kind of high purity DCPD, thick DCPD is mixed into moment decomposition reaction in the gas phase cleavage column with batching gas, enter the separation column of a particular design then, carry out dimerization reaction and sepn process simultaneously, obtain DCPD purity greater than 98%.
CN10935280 proposes the preparation method of a kind of high purity endocyclic DCPD, adopt concentration expressed in percentage by weight greater than 30-60 ℃ of the liquid CPD process of 95% high purity, and the product after 70-90 ℃ of two sections dimerization through gas carry with rectification under vacuum after obtain purity and surpass 99.5% endocyclic DCPD, total recovery surpasses 80%.
In a word, depolymerization-dimerization processes utilizes CPD and DCPD to reach the purpose of purified product with respect to the mutual easily character that transforms of other copolymerization impurity under different temperature condition.But the temperature of depolymerization is too low, influences the speed of depolymerization; And the temperature height then can cause serious coking.
(3) summary of the invention
For overcoming slow, the coking important disadvantages of depolymerization reaction speed in the prior art, the invention provides a kind of technology of producing the high purity dicyclo cyclopentadiene.
The production technique of described high purity dicyclo pentylene is with the C of petroleum cracking
5Cut is a raw material, comprises following sequential steps:
(1) with C
5The cut dimerization removes light constituent and gets thick DCPD;
(2) acidic substance with the inorganic carrier load are catalyzer, and thick DCPD carries out catalytic degradation at 100～200 ℃ and gets high-purity C PD;
(3) remove light constituent after the CPD dimerization and get high purity DCPD.
Be applied in the step of the present invention (2) catalyzer in the cracking process comprise at least a inorganic carrier (preferably from salic, tripoli, aluminum oxide-silicon, aluminum phosphate, pottery, molecular sieve, titanium dioxide, zirconium dioxide, hafnium oxide, IIA family metal oxide (such as MgO, CaO, SrO, BaO), the IIIB family metal oxide is (such as Sc
2O
3, La
2O
3, CeO
2), magnesium aluminate, calcium aluminate, zinc oxide, Zinc aluminate, zinc titanate, ferric oxide, select in the gac, can also from these compounds, select in any mixture more than two kinds or two kinds) and one or more acidic substance (preferably from sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, oxalic acid heteropolyacid etc. select) of load.The technology of preparation catalyzer that the front is mentioned comprises corresponding natural or synthesizing inorganic solid support material is contacted with acidic substance, perhaps handles carrier with acidic solution.Described catalyzer is preferably SiO
2The sulfuric acid of load or hydrochloric acid or phosphoric acid are as being the SiO of 10% vitriolization
2, the SiO of 10% salt acid treatment
2, the SiO that 30% phosphoric acid is handled
2Deng.Catalyzer can be Powdered, but particulate state preferably.
The catalytic degradation temperature is preferably 140～170 ℃ in the described step (2).Catalytic degradation is recommended in the tank reactor of a band rectifying tower and carries out, and catalyzer places the bottom of still or tower, and rectifying tower can be board-like, also can be filler, theoretical plate number between the 3-10 piece, preferably 4～6.
The CPD dimerization is recommended in the autoclave and carries out in the described step (3), and temperature of reaction is 30～100 ℃, and pressure is the saturated vapor pressure of material.
CPD dimerization reaction temperature in above-mentioned steps (1), (3) is preferably 40～70 ℃.
Above-mentioned remove light constituent and can carry out in vacuum still, its pressure is 10～30mmHg, is preferably 15～20mmHg.
May also have a little not DCPD of depolymerization behind the catalytic degradation in the step of the present invention (2), in order further to improve utilization ratio of raw materials, depolymerization is not partly carried out the high temperature depolymerization reaction again, and the depolymerization product that obtains is used for the raw material of step (1).Described high temperature depolymerization can be carried out in tubular reactor, and the depolymerization temperature is 200～400 ℃, preferably 280～350 ℃.Inert media is water vapor preferably.
The present invention adopts the method for low-temperature catalyzed depolymerization, under the prerequisite that reduces coking, has effectively improved the selectivity of depolymerization speed of response and depolymerization reaction.
(4) description of drawings
Fig. 1 is the schematic flow sheet of production technique of the present invention.
(5) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
With reference to Fig. 1,1 is thick C
5Cut carries out entering 3 behind the dimerization reaction in 2; 3 is lightness-removing column, removes the C of unpolymerized 8,8 main right and wrong CPD
5Component; Product in 3 after the polymerization enters 4; 4 is the catalytic degradation rectifying tower, and high-purity C PD enters 5 from cat head; 5 is high pressure dimerization still, enters 6 behind the dimerization reaction and sloughs unpolymerized CPD to obtain 7,7 be high purity DCPD; In 4 not the depolymerization material to enter 9,9 be the high temperature depolymerizing reactor, depolymerization product is mixed with 1; 10 are inert media employing water vapor.
Embodiment 1
The thick C of 400g
5Cut obtains DCPD content through 40 ℃ of dimerization 1 hour (technology 2) with after taking off light component (technology 3) be 80.2% thick DCPD 323g; Enter intermittently catalytic degradation (technology 4), the stage number of the rectifying tower on the depolymerizing reactor is 10, and catalyzer is the SiO after 10% vitriolization
2, the depolymerization temperature is 150-160 ℃, obtains the DCPD+CPD total content and surpasses 99% cut 242g; Enter and obtain 240g purity after 100 ℃ of dimerization (technology 5) and the underpressure distillation (technology 6) and reach 99.5% DCPD.
Embodiment 2
The thick C of 400g
5Cut obtains DCPD content through 40 ℃ of dimerization 1 hour (technology 2) with after taking off light component (technology 3) be 80.8% thick DCPD 320g; Enter intermittently catalytic degradation (technology 4), the stage number of the rectifying tower on the depolymerizing reactor is 10, and catalyzer is the SiO after the 10% salt acid treatment
2, the depolymerization temperature is 150-160 ℃, obtains the DCPD+CPD total content and surpasses 99% cut 232g; Enter and obtain 229g purity after 100 ℃ of dimerization (technology 5) and the underpressure distillation (technology 6) and reach 99.5% DCPD.
The thick C of 400g
5Cut obtains DCPD content through 40 ℃ of dimerization 1 hour (technology 2) with after taking off light component (technology 3) be 81.3% thick DCPD334g; Enter intermittently catalytic degradation (technology 4), the stage number of the rectifying tower on the depolymerizing reactor is 10, and catalyzer is the Al after 10% vitriolization
2O
3, the depolymerization temperature is 150-160 ℃, obtains the DCPD+CPD total content and surpasses 99% cut 255g; Enter and obtain 251g purity after 100 ℃ of dimerization (technology 5) and the underpressure distillation (technology 6) and reach 99.5% DCPD.
Catalytic degradation is depolymerization still liquid 40g/hr and 40g/hr water not, gets 38.6g/hr C after 300 ℃ of depolymerization (technology 9) layering dehydration
5Cut; The above-mentioned C of 50g
5With the fresh thick C of 350g
5Mix after 40 ℃ of dimerization 1 hour (technology 2) and take off light component (technology 3) after to obtain DCPD content be 80.5% thick DCPD328g; Enter intermittently catalytic degradation (technology 4), the stage number of the rectifying tower on the depolymerizing reactor is 10, and catalyzer is the SiO after 10% vitriolization
2, the depolymerization temperature is 150-160 ℃, obtains the DCPD+CPD total content and surpasses 99% cut 244g; Enter and obtain 239g purity after 100 ℃ of dimerization (technology 5) and the underpressure distillation (technology 6) and reach DCPD more than 99%.
100g/hr C
5Cut is through 40 ℃ of continuous dimerization, 1 hour residence time (technology 2) and take off light component (technology 3) after to obtain DCPD content be 81.5% thick DCPD 83.2g/hr; Enter continuous catalysis depolymerization (technology 4), catalyzer is the SiO after 30% phosphoric acid is handled
2, the stage number of the rectifying tower on the depolymerizing reactor is 5, the depolymerization temperature is 150 ℃, obtains the DCPD+CPD total content and surpasses 99% cut 72.1g/hr; Enter and obtain purity after 90 ℃ of continuous dimerization (technology 5) and the underpressure distillation (technology 6) and reach DCPD 71.9g/hr more than 99%.
Embodiment 6
105g/hr C
5Cut is through 40 ℃ of continuous dimerization, 1 hour residence time (technology 2) and take off light component (technology 3) after to obtain DCPD content be 80.4% thick DCPD 85.2g/hr; Enter continuous catalysis depolymerization (technology 4), catalyzer is the activated carbon after 20% phosphoric acid is handled, and the stage number of the rectifying tower on the depolymerizing reactor is 5, and the depolymerization temperature is 155 ℃, obtains the DCPD+CPD total content and surpasses 99% cut 69.8g/hr; Enter and obtain purity after 90 ℃ of continuous dimerization (technology 5) and the underpressure distillation (technology 6) and reach DCPD 69.0g/hr more than 99%.
Embodiment 7
The thick C of 400g
5Cut obtains DCPD content through 60 ℃ of dimerization 1 hour (technology 2) with after taking off light component (technology 3) be 82.8% thick DCPD 320g; Enter intermittently catalytic degradation (technology 4), the stage number of the rectifying tower on the depolymerizing reactor is 10, and catalyzer is the SiO after the 10% salt acid treatment
2, the depolymerization temperature is 140-150 ℃, obtains the DCPD+CPD total content and surpasses 99% cut 232g; Enter and obtain 230g purity after 100 ℃ of dimerization (technology 5) and the underpressure distillation (technology 6) and reach 99.6% DCPD.
Claims (10)
1, a kind of production technique of high purity dicyclo pentylene is with the C of petroleum cracking
5Cut is a raw material, it is characterized in that comprising following sequential steps:
(1) with C
5The cut dimerization removes light constituent and gets thick DCPD;
(2) acidic substance with the inorganic carrier load are catalyzer, and thick DCPD carries out catalytic degradation at 100～200 ℃ and gets high-purity C PD;
(3) remove light constituent after the CPD dimerization and get high purity DCPD.
2, according to the production technique of the described high purity dicyclo pentylene of claim 1, it is characterized in that described inorganic carrier is one of following or the mixture more than two kinds: aluminum oxide, tripoli, molecular sieve, aluminum oxide-silicon, aluminum phosphate, pottery, metal oxide, magnesium aluminate, calcium aluminate, Zinc aluminate, zinc titanate, gac, described acidic substance are one of following or any mixture more than two kinds: sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, oxalic acid, heteropolyacid.
3,, it is characterized in that described catalyzer is SiO according to the production technique of the described high purity dicyclo pentylene of claim 2
2The sulfuric acid of load or hydrochloric acid or phosphoric acid.
4,, it is characterized in that described catalytic degradation temperature is 140～170 ℃ according to the production technique of the described high purity dicyclo pentylene of claim 1.
5,, it is characterized in that described catalytic degradation carries out in the tank reactor of a band rectifying tower according to the production technique of the described high purity dicyclo pentylene of one of claim 1～4.
6, according to the production technique of the described high purity dicyclo pentylene of one of claim 1～4, it is characterized in that the CPD dimerization is carried out in the described step (3) in autoclave, temperature of reaction is 30～100 ℃.
7,, it is characterized in that described CPD dimerization reaction temperature is 40～70 ℃ according to the production technique of the described high purity dicyclo pentylene of claim 6.
8, according to the production technique of the described high purity dicyclo pentylene of one of claim 1～4, it is characterized in that the described light constituent that removes carries out in vacuum still, its pressure is 10～30mmHg.
9, according to the production technique of the described high purity dicyclo pentylene of claim 1, it is characterized in that the part of the not depolymerization behind the catalytic degradation is carried out the high temperature depolymerization reaction again in the described step (2), the depolymerization product that obtains is used for the raw material of step (1).
10, according to the production technique of the described high purity dicyclo pentylene of claim 9, it is characterized in that described high temperature depolymerization carries out in tubular reactor, the depolymerization temperature is 280～350 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100608412A CN1304341C (en) | 2005-09-21 | 2005-09-21 | Process for producing high purity dicyclo pentylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100608412A CN1304341C (en) | 2005-09-21 | 2005-09-21 | Process for producing high purity dicyclo pentylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1781887A true CN1781887A (en) | 2006-06-07 |
| CN1304341C CN1304341C (en) | 2007-03-14 |
Family
ID=36772575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100608412A Expired - Fee Related CN1304341C (en) | 2005-09-21 | 2005-09-21 | Process for producing high purity dicyclo pentylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1304341C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399123A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene and dimethylcyclopentadiene |
| CN102442875A (en) * | 2010-10-25 | 2012-05-09 | 南通派斯第农药化工有限公司 | Preparation process for cyclopentadiene |
| CN102951985A (en) * | 2011-08-17 | 2013-03-06 | 中国石油化工股份有限公司 | Method for separation of C5 fraction and preparation of cyclopentadiene |
| US9988324B2 (en) | 2015-11-04 | 2018-06-05 | Exxonmobil Chemical Patents Inc. | Process and system for making cyclopentadiene and/or dicyclopentadiene |
| CN111097525A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Solid acid catalyst for olefin epoxidation reaction, preparation method and application |
| CN111569457A (en) * | 2019-02-15 | 2020-08-25 | 中国石油化工股份有限公司 | NMP solvent recovery method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248996C (en) * | 2003-06-19 | 2006-04-05 | 中国石化上海石油化工股份有限公司 | Process for refining crude dicyclopentadiene |
-
2005
- 2005-09-21 CN CNB2005100608412A patent/CN1304341C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399123A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene and dimethylcyclopentadiene |
| CN102442875A (en) * | 2010-10-25 | 2012-05-09 | 南通派斯第农药化工有限公司 | Preparation process for cyclopentadiene |
| CN102951985A (en) * | 2011-08-17 | 2013-03-06 | 中国石油化工股份有限公司 | Method for separation of C5 fraction and preparation of cyclopentadiene |
| US9988324B2 (en) | 2015-11-04 | 2018-06-05 | Exxonmobil Chemical Patents Inc. | Process and system for making cyclopentadiene and/or dicyclopentadiene |
| CN111097525A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Solid acid catalyst for olefin epoxidation reaction, preparation method and application |
| CN111569457A (en) * | 2019-02-15 | 2020-08-25 | 中国石油化工股份有限公司 | NMP solvent recovery method |
| CN111569457B (en) * | 2019-02-15 | 2022-08-12 | 中国石油化工股份有限公司 | NMP solvent recovery method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1304341C (en) | 2007-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1304341C (en) | Process for producing high purity dicyclo pentylene | |
| CN1088095C (en) | C4Method and device for converting olefinic cuts into polyisobutene and propylene | |
| Meylemans et al. | Solvent‐free conversion of linalool to methylcyclopentadiene dimers: a route to renewable high‐density fuels | |
| CN1708466A (en) | Method for producing oligomers derived from butenes | |
| CN1511126A (en) | Olefin isomerization process | |
| CN1361756A (en) | Process for the separation of isobutene from normal butenes | |
| CN103030515B (en) | Alkylbenzene production method | |
| CN1309691C (en) | Method for working up crude 1,3-butadiene | |
| CN111548246A (en) | Method for preparing high-purity dicyclopentadiene from cracking carbon nine fraction | |
| CN1095703A (en) | The method for transformation of a kind of alkene or alkene mixture | |
| CN101238083B (en) | Improved drying process for linear alpha-olefins | |
| CN1095826C (en) | Esterification of (meth) acrylic acid with alkanol | |
| CN100430353C (en) | Method of separating butane-1 from C4 fraction | |
| CN1886394A (en) | Process for the preparation of propylene carbonate | |
| CN108586201B (en) | Method for improving pinene conversion rate in terpineol synthesis | |
| CN113754539A (en) | Purification and decoloration method of dimethyl oxalate | |
| CN1793133A (en) | Process for catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid | |
| CN107915565B (en) | Method for preparing exo-dicyclopentadiene through bridge-type dicyclopentadiene isomerization | |
| CN114621046B (en) | Method for preparing high-purity dicyclopentadiene through ionic liquid catalysis | |
| CN107573239B (en) | Synthetic method of tert-amyl acetate | |
| CN1292370A (en) | Preparation method of high-purity endocyclic type cyclopentadiene | |
| CN1085644C (en) | Catalytic distillation method for production of alkylbenzene | |
| KR100523601B1 (en) | Method of purification of dicyclopentadiene from C5 and C9+ fractions | |
| RU2177930C1 (en) | Alkene oligomers production process | |
| CN118652157B (en) | Process for producing norbornene and tetracyclododecene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070314 Termination date: 20100921 |