CN117567227A - Preparation method of high-purity dicyclopentadiene and derivatives - Google Patents
Preparation method of high-purity dicyclopentadiene and derivatives Download PDFInfo
- Publication number
- CN117567227A CN117567227A CN202311522849.0A CN202311522849A CN117567227A CN 117567227 A CN117567227 A CN 117567227A CN 202311522849 A CN202311522849 A CN 202311522849A CN 117567227 A CN117567227 A CN 117567227A
- Authority
- CN
- China
- Prior art keywords
- dicyclopentadiene
- purity
- molecular sieve
- cyclopentadiene
- reaction
- 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.)
- Pending
Links
- 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 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000002808 molecular sieve Substances 0.000 claims abstract description 65
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 65
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000011941 photocatalyst Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 12
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 239000011949 solid catalyst Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 230000003213 activating effect Effects 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 10
- 238000004451 qualitative analysis Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- NDTCXABJQNJPCF-UHFFFAOYSA-N chlorocyclopentane Chemical compound ClC1CCCC1 NDTCXABJQNJPCF-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
- C07C2/40—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes of conjugated dienes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of dicyclopentadiene, and discloses a preparation method of high-purity dicyclopentadiene and derivatives. Then, high-purity cyclopentadiene is utilized for polymerization reaction, and the dicyclopentadiene with high purity is obtained by regulating and optimizing the reaction conditions. The nano Ru-supported molecular sieve is used as a photocatalyst, hydrazine hydrate is used as a hydrogen source under the action of ultraviolet light to catalyze cyclopentadiene to carry out hydrogenation reaction to generate cyclopentene, and the method has the advantages of high cyclopentadiene conversion rate and good cyclopentene selectivity, and is mild in photocatalytic reaction condition, environment-friendly and simple and convenient to operate.
Description
Technical Field
The invention relates to the technical field of dicyclopentadiene, in particular to a preparation method of high-purity dicyclopentadiene and derivatives.
Background
Dicyclopentadiene and its derivatives cyclopentadiene, cyclopentene and other chemical products with high added value are widely used as intermediate compounds for preparing chemical medicine, complex and other products; the purity of the prior industrial dicyclopentadiene is lower and is only about 70-85%, so that the preparation of the dicyclopentadiene, cyclopentadiene and cyclopentene with high purity and high yield has important significance.
At present, cyclopentadiene is mainly obtained by separating and purifying raw materials such as an ethylene cracking byproduct C9 and the like, but the problems of complex preparation process and lower cyclopentadiene yield and purity exist. The depolymerization is an effective method for preparing cyclopentadiene by taking dicyclopentadiene as a raw material, but the self-polymerization phenomenon of cyclopentadiene exists in the high-temperature depolymerization process, so that the yield and purity of cyclopentadiene are affected.
Cyclopentene is a downstream product of cyclopentadiene, can be further used for preparing medical intermediates with high added value such as cyclopentanol, chlorocyclopentane and the like, and is prepared by a catalytic hydrogenation method of cyclopentene at present, wherein common catalysts mainly comprise Pd/C catalyst and Ni/Al catalyst 2 O 3 A catalyst, etc.
The molecular sieve is a hydrated aluminosilicate substance with molecular screening function, has good ion exchange property, catalysis and other performances, can be used as a catalyst and a carrier, and has wide application prospect in the field of organic synthesis; the photocatalysis reaction is a green and efficient synthesis reaction, can convert light energy into chemical energy under the action of a photocatalyst, promotes the reaction, and has the advantages of green and environment-friendly performance, mild reaction conditions and the like; the invention aims to prepare a Ru-supported molecular sieve photocatalyst, and adopts a photocatalytic reaction to realize the catalytic hydrogenation of cyclopentadiene to prepare cyclopentene.
Disclosure of Invention
The invention solves the technical problems that: provides a preparation method of high-purity dicyclopentadiene, cyclopentadiene derivatives and cyclopentene, and solves the problems of complex preparation method and low yield of the traditional dicyclopentadiene, cyclopentadiene and cyclopentene.
The technical scheme provided by the invention is as follows:
the preparation process of high purity dicyclopentadiene, which is prepared through depolymerizing and polymerizing industrial dicyclopentadiene or with ethylene side product cracking carbon nine fraction as material; the preparation method comprises the following steps:
(1) Adding industrial dicyclopentadiene and a polymerization inhibitor diethyl hydroxylamine into a reactor of a continuous reaction-rectification device, heating and refluxing until no condensate is dropped, heating and depolymerizing, and collecting a fraction at 41-43 ℃ until no fraction is distilled to obtain a dicyclopentadiene derivative: high purity cyclopentadiene;
(2) Adding high-purity cyclopentadiene into a polymerization reaction kettle, introducing nitrogen, discharging air in the reaction kettle, and heating to perform polymerization reaction to obtain high-purity dicyclopentadiene.
Further, in the step (1), dicyclopentadiene diethyl hydroxylamine=1 g (2-4). Times.10 -4 g。
Further, the temperature of heating reflux in the step (1) is 120-130 ℃; the depolymerization temperature is 170-175 ℃.
Further, the temperature of the polymerization reaction in the step (2) is 75-85 ℃ and the time is 6-12 h.
Further, the high-purity dicyclopentadiene can be prepared from a carbon nine fraction obtained by cracking an ethylene byproduct: mixing the pyrolysis carbon nine component and the extractant N-methyl pyrrolidone, heating to azeotropy dicyclopentadiene and the extractant in the pyrolysis carbon nine component, enabling the mixture of dicyclopentadiene and the extractant to flow out from the top of a rectifying tower, controlling the optimal temperature at 100-110 ℃ at the top of the rectifying tower, controlling the reflux ratio of the rectifying tower to be 1-2.5, and collecting the product after condensation.
Further, adding ethanol, high-purity cyclopentadiene and hydrazine hydrate into a flask, stirring, adding Ru-loaded molecular sieve photocatalyst, placing the flask into a water bath, radiating and reacting for 6-24-h under a lamp source, controlling the reaction temperature to be 20-30 ℃, filtering and recovering a solid catalyst after the reaction, distilling filtrate, and collecting a fraction at 44-46 ℃ to obtain cyclopentene.
Further, ethanol, high-purity cyclopentadiene, hydrazine hydrate, ru-loaded molecular sieve photocatalyst= (20-50) mL, 1g (20-50) mL and 0.1-0.18 g.
Further, the lamp source is an ultraviolet lamp, comprising a high-pressure mercury lamp or a xenon lamp, the power is 300-600W, and the distance between the lamp source and the flask is 10-20cm.
Further, the preparation method of the Ru-loaded molecular sieve photocatalyst comprises the following steps:
(1) Adding (0.8-3) g of water, ethylenediamine tetraacetic acid and ZSM-5 molecular sieve with the proportion of (30-50) into a flask, stirring and dispersing, then placing the flask into a water bath kettle, stirring at 40-70 ℃ for etching for 3-8h, and filtering to obtain an activated ZSM-5 molecular sieve;
(2) Adding ethanol, an activated ZSM-5 molecular sieve and ruthenium trichloride into a flask, stirring and dispersing, adding sodium borohydride, reacting at room temperature for 3-6 h, filtering and washing to obtain the Ru-loaded molecular sieve photocatalyst.
Further, in the step (4), ethanol, activated ZSM-5 molecular sieve, ruthenium trichloride, sodium borohydride= (30-60) mL, 1g (0.01-0.1 g) and 0.12-1.5 g.
The invention has the technical effects that:
according to the invention, diethyl hydroxylamine is used as a polymerization inhibitor, and cyclopentadiene self-polymerization is inhibited in the industrial dicyclopentadiene depolymerization process, so that cyclopentadiene with high purity and high yield is obtained. Then, high-purity cyclopentadiene is utilized for polymerization reaction, and the dicyclopentadiene with high purity is obtained by regulating and optimizing the reaction conditions.
According to the invention, nano Ru-supported molecular sieve light is used as a photocatalyst, hydrazine hydrate is used as a hydrogen source under the action of ultraviolet light to catalyze cyclopentadiene to carry out hydrogenation reaction to generate cyclopentene, and the method has the advantages of high cyclopentadiene conversion rate and good cyclopentene selectivity, and the photocatalysis reaction condition is mild, green and environment-friendly, and is simple to operate.
According to the invention, the ZSM-5 molecular sieve is subjected to acidification etching by using ethylenediamine tetraacetic acid, non-framework aluminum in the molecular sieve is removed by etching, so that the crystallinity of the ZSM-5 molecular sieve can be improved, and meanwhile, a uniform micropore structure is formed in the ZSM-5 molecular sieve after etching, thereby being beneficial to improving the pore volume and specific surface area of the ZSM-5 molecular sieve.
The invention adopts an activated ZSM-5 molecular sieve as a catalyst carrier, and uses ethylenediamine tetraacetic acid in a framework as a complexing agent to perform Ru 3+ Complexing Ru 3+ Uniformly loading the Ru nanoparticles into a molecular sieve, and finally reducing the Ru nanoparticles by sodium borohydride to obtain the Ru-loaded molecular sieve photocatalyst, so that the Ru nanoparticles are uniformly dispersed in the ZSM-5 molecular sieve, the aggregation of the Ru nanoparticles is reduced, and the catalyst has more active catalytic sites.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
Preparing high-purity cyclopentadiene: adding 20g of industrial dicyclopentadiene and 4-8mg of polymerization inhibitor diethyl hydroxylamine into a reactor of a continuous reaction-rectification device, heating to 120-130 ℃ for reflux until no condensate drops, heating to 170-175 ℃ for depolymerization, and collecting fractions at 41-43 ℃ until no fractions are distilled, thus obtaining dicyclopentadiene derivatives: high purity cyclopentadiene;
preparing high-purity dicyclopentadiene: adding high-purity cyclopentadiene into a polymerization reaction kettle, introducing nitrogen, discharging air in the reaction kettle, heating to perform polymerization reaction, controlling the temperature to be 75-85 ℃ and the time to be 6-12 h, and obtaining the high-purity dicyclopentadiene.
Preparing a Ru-loaded molecular sieve photocatalyst: (1) Adding 6-10mL of water, 0.16-0.6g of ethylenediamine tetraacetic acid and 0.2g of ZSM-5 molecular sieve into a flask, stirring for dispersion, then placing the flask into a water bath kettle, stirring at 40-70 ℃ for etching for 3-8h, and filtering to obtain an activated ZSM-5 molecular sieve;
(2) Adding 6-12mL of ethanol, 0.2g of activated ZSM-5 molecular sieve and 2-20mg of ruthenium trichloride into a flask, stirring and dispersing, adding 24-300mg of sodium borohydride, reacting at room temperature for 3-6 h, filtering and washing to obtain the Ru-loaded molecular sieve photocatalyst.
Preparing cyclopentene: adding 40-100) mL of ethanol, 2g of high-purity cyclopentadiene and 20-50mL of hydrazine hydrate into a flask, stirring, adding 0.2-0.36g of Ru-loaded molecular sieve photocatalyst, placing the flask into a water bath, taking a high-pressure mercury lamp or a xenon lamp as an ultraviolet lamp source, carrying out irradiation reaction under the lamp source at the power of 300-600W and the distance between the lamp source and the flask of 10-20cm for 6-24 h, controlling the reaction temperature to 20-30 ℃, filtering after the reaction, recovering a solid catalyst, distilling filtrate, and collecting a fraction at the temperature of 44-46 ℃ to obtain cyclopentene.
As one embodiment, the high purity dicyclopentadiene may also be produced from a carbon nine fraction obtained by cracking an ethylene byproduct. Mixing the pyrolysis carbon nine component and the extractant N-methyl pyrrolidone, heating to azeotropy dicyclopentadiene and the extractant in the pyrolysis carbon nine component, flowing the mixture of dicyclopentadiene and the extractant out through the top of a rectifying tower, controlling the optimal temperature at 100-110 ℃ at the top of the rectifying tower, controlling the reflux ratio of the rectifying tower to be 1-2.5, and collecting the product after condensation.
Example 1
20g of industrial-grade dicyclopentadiene (purity 75%) and 4 mg inhibitor diethyl hydroxylamine are added into a reactor of a continuous reaction-rectification device, the mixture is heated to 125 ℃ for reflux, and then depolymerization is carried out at 170 ℃, and fractions at 42 ℃ are collected, so that high-purity cyclopentadiene is obtained.
Example 2
20g of industrial dicyclopentadiene and 6mg inhibitor diethyl hydroxylamine are added into a reactor of a continuous reaction-rectification device, the mixture is heated to 125 ℃ for reflux, then depolymerization is carried out at 175 ℃, and fractions at 42 ℃ are collected, so that high-purity cyclopentadiene is obtained.
Example 3
20g of industrial dicyclopentadiene and 8mg inhibitor diethyl hydroxylamine are added into a reactor of a continuous reaction-rectification device, the mixture is heated to 125 ℃ for reflux, then depolymerization is carried out at 170 ℃, and fractions at 42 ℃ are collected, so that high-purity cyclopentadiene is obtained.
Example 4
20g of industrial dicyclopentadiene and 6mg inhibitor diethyl hydroxylamine are added into a reactor of a continuous reaction-rectification device, the mixture is heated to 125 ℃ for reflux, then depolymerization is carried out at 170 ℃, and fractions at 42 ℃ are collected, so that high-purity cyclopentadiene is obtained.
And carrying out qualitative analysis on the high-purity cyclopentadiene by adopting a gas chromatograph-mass spectrometer.
Comparative example 1
20g of industrial dicyclopentadiene is added into a reactor of a continuous reaction-rectification device, the mixture is heated to 125 ℃ for reflux, then depolymerization is carried out at 175 ℃, and fractions at 42 ℃ are collected to obtain high-purity cyclopentadiene.
Table 1 qualitative analysis of high purity cyclopentadiene.
| Cyclopentadiene content (%) | Dicyclopentadiene content (%) | |
| Example 1 | 97.21 | 2.01 |
| Example 2 | 99.29 | 0.64 |
| Example 3 | 98.21 | 1.12 |
| Example 4 | 99.10 | 0.75 |
| Comparative example 1 | 95.12 | 2.79 |
As is clear from Table 1, in example 2, when the amount of the polymerization inhibitor diethyl hydroxylamine was 6mg, the cyclopentadiene content of the high-purity cyclopentadiene reached 99.29% and the dicyclopentadiene content was only 0.64%. Comparative example 1 was free of addition of a polymerization inhibitor of diethylhydroxylamine and had a cyclopentadiene content of only 95.12%.
Example 5
Adding high-purity cyclopentadiene into a polymerization reaction kettle, introducing nitrogen, discharging air in the reaction kettle, heating to 75 ℃, and carrying out polymerization reaction for 12 h to obtain high-purity dicyclopentadiene.
Example 6
Adding high-purity cyclopentadiene into a polymerization reaction kettle, introducing nitrogen, discharging air in the reaction kettle, heating to 80 ℃, and performing polymerization reaction 8-h to obtain high-purity dicyclopentadiene.
Example 7
Adding high-purity cyclopentadiene into a polymerization reaction kettle, introducing nitrogen, discharging air in the reaction kettle, heating to 85 ℃, and carrying out polymerization reaction for 8 hours to obtain high-purity dicyclopentadiene.
Example 8
Adding high-purity cyclopentadiene into a polymerization reaction kettle, introducing nitrogen, discharging air in the reaction kettle, heating to 80 ℃, and carrying out polymerization reaction for 12 h to obtain high-purity dicyclopentadiene.
Qualitative analysis of high-purity dicyclopentadiene using gas chromatograph-mass spectrometer
Table 2 qualitative analysis of high purity dicyclopentadiene.
| Dicyclopentadiene yield (%) | Dicyclopentadiene purity (%) | |
| Example 5 | 72.3 | 95.6 |
| Example 6 | 93.5 | 97.9 |
| Example 7 | 90.1 | 99.3 |
| Example 8 | 86.9 | 98.6 |
As is clear from Table 2, in example 6, the polymerization temperature was 80℃and the time was 8h, and the dicyclopentadiene yield was 93.5%.
Example 9
(1) 8mL of water, 0.35g of ethylenediamine tetraacetic acid and 0.2g of ZSM-5 molecular sieve are added into a flask, the mixture is stirred and dispersed, then the flask is placed into a water bath kettle for stirring and etching, the temperature of the etching process is 50 ℃, the time is 6 h, and the activated ZSM-5 molecular sieve is obtained after filtering.
(2) 10mL of water, 0.2g of activated ZSM-5 molecular sieve and 2mg of ruthenium trichloride are added into a flask, stirred for 6 h to disperse, 25 mg sodium borohydride is added, reaction is carried out at room temperature for 5 h, and filtration and water washing are carried out to obtain the Ru-loaded molecular sieve photocatalyst.
(3) Adding 80mL of ethanol, 2g of high-purity cyclopentadiene (prepared in example 2) and 80mL of hydrazine hydrate into a flask, stirring, adding 0.2g of Ru-supported molecular sieve photocatalyst, placing the flask into a water bath, carrying out irradiation reaction under a 400W high-pressure mercury lamp, controlling the distance between a lamp source and the flask to be 15cm, reacting at 25 ℃ for 12 h ℃, filtering after the reaction to recover a solid catalyst, distilling filtrate, collecting fractions at 45 ℃ to obtain cyclopentene, and carrying out qualitative analysis by using a gas chromatography-mass spectrometer.
Example 10
This embodiment differs from embodiment 9 in that:
the amount of ruthenium trichloride in step (2) was 6mg and the amount of sodium borohydride was 75mg. The remaining steps are the same.
Example 11
This embodiment differs from embodiment 9 in that:
the amount of ruthenium trichloride in step (2) was 10mg and the amount of sodium borohydride was 130mg. The remaining steps are the same.
Example 12
This embodiment differs from embodiment 9 in that:
the amount of ruthenium trichloride in the step (2) was 15mg, and the amount of sodium borohydride was 210mg. The remaining steps are the same.
Example 13
This embodiment differs from embodiment 9 in that:
the amount of ruthenium trichloride in step (2) was 20mg and the amount of sodium borohydride was 300mg. The remaining steps are the same.
Comparative example 2
The difference between this comparative example and example 9 is that: and the ZSM-5 molecular sieve is not etched and activated by using ethylenediamine tetraacetic acid.
The method comprises the following steps: 10mL of water, 0.2g of ZSM-5 molecular sieve and 2mg of ruthenium trichloride are added into a flask, stirred for 6 h to disperse, 25 mg sodium borohydride is added, reaction is carried out at room temperature for 5 h, and filtration and water washing are carried out to obtain the Ru-loaded molecular sieve photocatalyst.
Adding 80mL of ethanol, 2g of high-purity cyclopentadiene and 80mL of hydrazine hydrate into a flask, stirring, adding 0.2g of Ru-supported molecular sieve photocatalyst, placing the flask into a water bath kettle, carrying out irradiation reaction under a 400W high-pressure mercury lamp, controlling the distance between a lamp source and the flask to be 15cm, reacting at 20 ℃ for 10 h, filtering after the reaction, recovering a solid catalyst, distilling filtrate, collecting fractions at 45 ℃, and carrying out qualitative analysis by adopting a gas chromatography-mass spectrometer.
Comparative example 3
The difference between this comparative example and example 9 is that: the activated ZSM-5 molecular sieve is used for replacing the Ru-loaded molecular sieve photocatalyst.
The method comprises the following steps: 8mL of water, 0.35g of ethylenediamine tetraacetic acid and 0.2g of ZSM-5 molecular sieve are added into a flask, the mixture is stirred and dispersed, then the flask is placed into a water bath kettle for stirring and etching, the temperature of the etching process is 40 ℃, the time is 8h, and the activated ZSM-5 molecular sieve is obtained after filtering.
Adding 80mL of ethanol, 2g of high-purity cyclopentadiene and 80mL of hydrazine hydrate into a flask, stirring, adding 0.2g of activated ZSM-5 molecular sieve, placing the flask into a water bath kettle, carrying out irradiation reaction under a 400W high-pressure mercury lamp, controlling the distance between a lamp source and the flask to be 15cm, reacting at 20 ℃ for 10 h, filtering after the reaction, recovering a solid catalyst, distilling filtrate, collecting fractions at 45 ℃, and carrying out qualitative analysis by adopting a gas chromatography-mass spectrometer.
The activated ZSM-5 molecular sieve was vacuum degassed at 120℃for 12 h and the specific surface area was measured using a specific surface area and pore size analyzer.
Table 3 specific surface area test table for activated ZSM-5 molecular sieves.
| Specific surface area (m) 2 /g） | Pore volume (cm) 3 /g） | |
| Example 9 | 1210.8 | 1.01 |
| Comparative example 2 (ZSM-5 molecular sieve) | 856.2 | 0.76 |
As can be seen from Table 3, in comparative example 2The ZSM-5 molecular sieve is not etched and activated by ethylenediamine tetraacetic acid, and the specific surface area and the pore volume are only 856.2m 2 /g、0.76 cm 3 /g。
In example 9, ZSM-5 molecular sieve was activated by etching with ethylenediamine tetraacetic acid to a specific surface area and pore volume of 1210.8m 2 /g、1.01 cm 3 /g。
Table 4 qualitative analysis of fractions test table.
| Cyclopentadiene conversion (%) | Cyclopentene Selectivity (%) | |
| Example 9 | 82.0 | 74.0 |
| Example 10 | 87.6 | 79.5 |
| Example 11 | 92.4 | 85.9 |
| Example 12 | 92.1 | 85.0 |
| Example 13 | 90.8 | 84.1 |
| Comparative example 2 | 72.4 | 55.0 |
| Comparative example 3 | 58.9 | 2.9 |
As is clear from Table 4, in example 11, when the amount of ruthenium trichloride was 10mg and the amount of sodium borohydride was 130mg, the Ru-supported molecular sieve photocatalyst had the best effect on the photocatalytic hydrogenation of cyclopentadiene, the cyclopentadiene conversion was 92.4%, and the cyclopentene selectivity was 85.9%.
Comparative example 2 etching activation of ZSM-5 molecular sieves without ethylenediamine tetraacetic acid, ZSM-5 molecular sieves have a small specific surface area, and Ru cannot be reacted 3+ Complexing Ru is difficult to perform 3+ And the reduced Ru nano particles are uniformly dispersed in the ZSM-5 molecular sieve, so that the effect of photocatalytic hydrogenation of cyclopentadiene is poor.
In comparative example 3, the activated ZSM-5 molecular sieve is used for replacing Ru-supported molecular sieve photocatalyst, so that the effect of photocatalytic hydrogenation of cyclopentadiene is the worst, and cyclopentene cannot be effectively generated.
Example 14
This embodiment differs from embodiment 11 in that:
the dosage of the Ru-supported molecular sieve photocatalyst in the step (3) is 0.24g.
Example 15
This embodiment differs from embodiment 11 in that:
the dosage of the Ru-supported molecular sieve photocatalyst in the step (3) is 0.28g.
Example 16
This embodiment differs from embodiment 11 in that:
the dosage of the Ru-supported molecular sieve photocatalyst in the step (3) is 0.32g.
Example 17
This embodiment differs from embodiment 11 in that:
the dosage of the Ru-supported molecular sieve photocatalyst in the step (3) is 0.36g.
Table 5 qualitative analysis of fractions test table.
| Cyclopentadiene conversion (%) | Cyclopentene Selectivity (%) | |
| Example 7 | 92.4 | 85.9 |
| Example 14 | 95.0 | 90.1 |
| Example 15 | 97.2 | 90.1 |
| Example 16 | 98.0 | 92.2 |
| Example 17 | 96.3 | 89.0 |
As is clear from Table 4, in example 16, when the amount of the Ru-supported molecular sieve photocatalyst used was 0.32g, the effect of photocatalytic hydrogenation on cyclopentadiene was best, and the selectivity of cyclopentene was 92.2%.
Finally, it is noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be understood that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The high-purity dicyclopentadiene can be prepared by depolymerizing and polymerizing industrial-grade dicyclopentadiene or by using ethylene byproduct cracking carbon nine fraction as raw material; the preparation method is characterized by comprising the following steps:
(1) Adding industrial dicyclopentadiene and a polymerization inhibitor diethyl hydroxylamine into a reactor of a continuous reaction-rectification device, heating and refluxing until no condensate is dropped, heating and depolymerizing, and collecting a fraction at 41-43 ℃ until no fraction is distilled to obtain a dicyclopentadiene derivative: high purity cyclopentadiene;
(2) Adding high-purity cyclopentadiene into a polymerization reaction kettle, introducing nitrogen, discharging air in the reaction kettle, and heating to perform polymerization reaction to obtain high-purity dicyclopentadiene.
2. The method for producing high-purity dicyclopentadiene according to claim 1, wherein in step (1), dicyclopentadiene diethyl hydroxylamine=1 g (2 to 4). Times.10 -4 g。
3. The method for producing high-purity dicyclopentadiene according to claim 1, wherein the temperature of the heating reflux in step (1) is 120 to 130 ℃; the depolymerization temperature is 170-175 ℃.
4. The method for preparing high purity dicyclopentadiene according to claim 1, wherein the polymerization reaction in step (2) is carried out at a temperature of 75 to 85 ℃ for a period of 6 to 12 h.
5. The method for producing high-purity dicyclopentadiene according to claim 1, wherein: the method is characterized in that the high-purity dicyclopentadiene can be prepared by taking ethylene byproduct cracking carbon nine fraction as a raw material: mixing the pyrolysis carbon nine component and the extractant N-methyl pyrrolidone, heating to azeotropy dicyclopentadiene and the extractant in the pyrolysis carbon nine component, enabling the mixture of dicyclopentadiene and the extractant to flow out from the top of a rectifying tower, controlling the optimal temperature at 100-110 ℃ at the top of the rectifying tower, controlling the reflux ratio of the rectifying tower to be 1-2.5, and collecting the product after condensation.
6. A process for preparing cyclopentene using the high-purity cyclopentadiene prepared in claim 1: the preparation method is characterized in that ethanol, high-purity cyclopentadiene and hydrazine hydrate are added into a flask, ru-loaded molecular sieve photocatalyst is added after stirring, the flask is placed into a water bath kettle, the reaction is carried out under the irradiation of a lamp source for 6-24-h, the reaction temperature is controlled to be 20-30 ℃, solid catalyst is recovered after the reaction, filtrate is distilled, and fraction at 44-46 ℃ is collected, so that cyclopentene is obtained.
7. The method for producing cyclopentene according to claim 6: the method is characterized in that ethanol, high-purity cyclopentadiene, hydrazine hydrate and Ru-loaded molecular sieve photocatalyst are used for preparing the photocatalyst with the concentration of= (20-50) mL, 1g (20-50) mL and 0.1-0.18 g.
8. The method for producing cyclopentene according to claim 6: the device is characterized in that the lamp source is an ultraviolet lamp and comprises a high-pressure mercury lamp or a xenon lamp, the power is 300-600W, and the distance between the lamp source and the flask is 10-20cm.
9. The method for producing cyclopentene according to claim 6: the preparation method of the Ru-loaded molecular sieve photocatalyst is characterized by comprising the following steps of:
(1) Adding (0.8-3) g of water, ethylenediamine tetraacetic acid and ZSM-5 molecular sieve with the proportion of (30-50) into a flask, stirring and dispersing, then placing the flask into a water bath kettle, stirring at 40-70 ℃ for etching for 3-8h, and filtering to obtain an activated ZSM-5 molecular sieve;
(2) Adding ethanol, an activated ZSM-5 molecular sieve and ruthenium trichloride into a flask, stirring and dispersing, adding sodium borohydride, reacting at room temperature for 3-6 h, filtering and washing to obtain the Ru-loaded molecular sieve photocatalyst.
10. The method for producing cyclopentene according to claim 9: the method is characterized in that in the step (4), ethanol is used for activating ZSM-5 molecular sieve, ruthenium trichloride is used for sodium borohydride= (30-60) mL, 1g is used for (0.01-0.1) g, and 0.12-1.5 g is used for preparing the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311522849.0A CN117567227A (en) | 2023-11-16 | 2023-11-16 | Preparation method of high-purity dicyclopentadiene and derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311522849.0A CN117567227A (en) | 2023-11-16 | 2023-11-16 | Preparation method of high-purity dicyclopentadiene and derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117567227A true CN117567227A (en) | 2024-02-20 |
Family
ID=89861845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311522849.0A Pending CN117567227A (en) | 2023-11-16 | 2023-11-16 | Preparation method of high-purity dicyclopentadiene and derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117567227A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3949011A (en) * | 1974-07-01 | 1976-04-06 | Viktor Sergeevich Smirnov | Method of preparing cycloolefines |
| JPS62167733A (en) * | 1986-01-18 | 1987-07-24 | Sumitomo Chem Co Ltd | Method for preventing formation of polymeric by-product |
| WO2002036529A1 (en) * | 2000-10-30 | 2002-05-10 | Samsung General Chemicals Co., Ltd. | Production method of dicyclopentadiene from c5-fraction of hydrocarbon pyrolysis |
| CN103058815A (en) * | 2013-01-25 | 2013-04-24 | 山东元利科技股份有限公司 | Method for continuously extracting dicyclopentadiene from coked crude benzene |
| CN103664472A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing high-purity dicyclopentadiene |
| CN104058917A (en) * | 2013-03-20 | 2014-09-24 | 赢创工业集团股份有限公司 | Process And Composition For Inhibiting The Polymerization Of Cyclopentadiene Compounds |
| CN105585415A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | A method of preparing high-purity dicyclopentadiene through reactive distillation |
| CN109745985A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | Catalyst and its preparation method and application for cyclopentadiene preparing cyclopentene |
| CN109865519A (en) * | 2017-12-01 | 2019-06-11 | 中国石化扬子石油化工有限公司 | A kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application |
| CN114931945A (en) * | 2022-05-31 | 2022-08-23 | 武汉理工大学 | Novel way for selective catalytic hydrogenation of unsaturated eneyne without participation of gaseous hydrogen and catalyst thereof |
-
2023
- 2023-11-16 CN CN202311522849.0A patent/CN117567227A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3949011A (en) * | 1974-07-01 | 1976-04-06 | Viktor Sergeevich Smirnov | Method of preparing cycloolefines |
| JPS62167733A (en) * | 1986-01-18 | 1987-07-24 | Sumitomo Chem Co Ltd | Method for preventing formation of polymeric by-product |
| WO2002036529A1 (en) * | 2000-10-30 | 2002-05-10 | Samsung General Chemicals Co., Ltd. | Production method of dicyclopentadiene from c5-fraction of hydrocarbon pyrolysis |
| CN103664472A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing high-purity dicyclopentadiene |
| CN103058815A (en) * | 2013-01-25 | 2013-04-24 | 山东元利科技股份有限公司 | Method for continuously extracting dicyclopentadiene from coked crude benzene |
| CN104058917A (en) * | 2013-03-20 | 2014-09-24 | 赢创工业集团股份有限公司 | Process And Composition For Inhibiting The Polymerization Of Cyclopentadiene Compounds |
| CN105585415A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | A method of preparing high-purity dicyclopentadiene through reactive distillation |
| CN109745985A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | Catalyst and its preparation method and application for cyclopentadiene preparing cyclopentene |
| CN109865519A (en) * | 2017-12-01 | 2019-06-11 | 中国石化扬子石油化工有限公司 | A kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application |
| CN114931945A (en) * | 2022-05-31 | 2022-08-23 | 武汉理工大学 | Novel way for selective catalytic hydrogenation of unsaturated eneyne without participation of gaseous hydrogen and catalyst thereof |
Non-Patent Citations (3)
| Title |
|---|
| MITAMURA, TAKENORI等: "Novel photoinduced reduction of conjugate dienes by the combination of benzenethiol and diphenyl diselenide", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》, vol. 80, no. 12, 13 December 2007 (2007-12-13), pages 2443 - 2445 * |
| ZHI CAI等，: "Liquid-Phase Cracking of Dicyclopentadiene by Reactive Distillation", 《ENERGY & FUELS》, vol. 23, 9 July 2009 (2009-07-09), pages 4077 - 4081 * |
| 刘威廉 等: "抑制双环戊二烯解聚过程聚合物的产生", 石化技术与应用, vol. 27, no. 03, 10 May 2009 (2009-05-10), pages 238 - 241 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109174085B (en) | Atomic-level dispersed palladium-based nano-diamond/graphene composite material catalyst and preparation method and application thereof | |
| CN107721843B (en) | Method for synthesizing succinic acid by catalytic hydrogenation of acetylene dicarbonylation product | |
| CN112341312B (en) | Method for preparing cyclohexanol and derivative thereof by selective hydrogenolysis of lignin | |
| CN113731441B (en) | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof | |
| CN109759109B (en) | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of nitrobenzene compounds | |
| CN112058313B (en) | Composite catalyst, preparation method thereof and application thereof in citral synthesis | |
| CN109701574B (en) | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of pyridine ring compounds | |
| CN117567227A (en) | Preparation method of high-purity dicyclopentadiene and derivatives | |
| CN114849753B (en) | Preparation method and application of palladium metal cluster catalyst | |
| CN115650829B (en) | Method for preparing cyclohexanone compounds by photocatalysis of biomass phenolic compounds | |
| CN112717987B (en) | Metal supported composite catalyst Me/TiO2-HZSM-5, and preparation method and application thereof | |
| CN113398968B (en) | MOF-derived TiO 2 Porous g-C 3 N 4 Composite photocatalyst, preparation method and application thereof | |
| CN1594278A (en) | Method for producing p-p-phenylene diamine by p-nitroaniline hydrogenation | |
| CN1085186C (en) | Method for prodn. of hydrogen from methyl alcohol | |
| CN101195600A (en) | Method for producing 4-hydroxyindole | |
| Jeong et al. | Synthesis of high-energy-density fuel through the dimerization of bicyclo [2.2. 1] hepta-2, 5-diene over a nanoporous catalyst | |
| CN112237913B (en) | Preparation method of palladium supported hydrogenation catalyst and catalyst thereof | |
| WO2023077285A1 (en) | Defect-rich covalent organic framework material, preparation method therefor, and application thereof in photocatalytic hydrogen evolution | |
| CN113896851A (en) | Defect-rich covalent organic framework material, preparation method thereof and application thereof in photocatalytic hydrogen evolution | |
| CN102773102A (en) | Catalyst for low-temperature synthesis of methanol and preparation method | |
| CN112495440A (en) | MOF-based composite catalyst and preparation method thereof | |
| CN111871441A (en) | Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof | |
| CN115611735A (en) | Method for preparing p-hydroxy-benzene propionate by depolymerizing lignin under catalysis of nickel loaded on layered hierarchical pore molecular sieve | |
| CN115646495B (en) | High-activity NiCu/Al 2 O 3 Preparation of catalyst and application of catalyst in catalytic hydrogen transfer cracking of aryl ether C-O bond | |
| CN116444367B (en) | Process for producing high-purity methyl acetate by reactive distillation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |