CN114516926B - Preparation method of hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin - Google Patents
Preparation method of hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 90
- 239000011347 resin Substances 0.000 title claims abstract description 90
- 239000003208 petroleum Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 150000001993 dienes Chemical class 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 210000003918 fraction a Anatomy 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005977 Ethylene Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- -1 coatings Substances 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 238000000197 pyrolysis Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- 150000002815 nickel Chemical class 0.000 claims description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 claims description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 8
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 30
- 229920001971 elastomer Polymers 0.000 abstract description 19
- 239000000806 elastomer Substances 0.000 abstract description 16
- 238000005336 cracking Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000007865 diluting Methods 0.000 abstract description 3
- 230000009965 odorless effect Effects 0.000 abstract description 3
- 239000004831 Hot glue Substances 0.000 abstract description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- LRJOXARIJKBUFE-UHFFFAOYSA-N 1,2-diethyl-3-methylbenzene Chemical compound CCC1=CC=CC(C)=C1CC LRJOXARIJKBUFE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application relates to the field of petroleum resin, in particular to the technical field of C08F8/04, and more particularly relates to a preparation method of hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin. A process for the preparation of hydrogenated C9 petroleum resin comprising the steps of: (1) Ethylene is subjected to pyrolysis, carbon nine is rectified and cut to obtain a fraction A with a distillation range of 110-200 ℃ and C5 diolefin, the fraction A and the C5 diolefin are mixed to obtain a mixture B, and the mixture B reacts for 3-6 hours at 120-200 ℃ to obtain a polymerization solution; (2) Removing the solvent and the oligomer from the polymerization solution to obtain a resin solution; (3) Diluting resin liquid, and then adding the diluted resin liquid and H in a fixed bed hydrogenation reactor 2 Reacting to obtain hydrogenated resin liquid B; and (4) rectifying the hydrogenated resin liquid B and granulating to obtain the catalyst. The method has strong adaptability to different ethylene cracking carbon nine raw materials, few byproducts, and the obtained annular hydrogenated C9 petroleum resin is almost water white and odorless, has excellent compatibility with styrene elastomers such as SBS, SIS and the like, and is suitable for the fields of hot melt adhesives, coatings, rubber modification and the like.
Description
Technical Field
The application relates to the field of petroleum resin, in particular to the technical field of C08F8/04, and more particularly relates to a preparation method of hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin.
Background
Ethylene cracking carbon nine is a product of high-temperature condensation of raw materials and products of the ethylene cracking raw materials in steam cracking, the conventional distillation range is 90-230 ℃, and the fraction before 200 ℃ accounts for about 60-80%. The ethylene cracking carbon nine has a complex composition, and the components such as methyl styrene, trimethylbenzene, dicyclopentadiene, indene, methylindene, naphthalene and the like have higher content. Because of complex components and high separation difficulty, the catalyst is mainly used as a raw material for producing high-boiling solvent oil, can be used as boiler fuel and has low economic value.
At present, more than 70% of petroleum resin synthesis process and matching devices in China still stay in the stage of polymerization, rectification and molding, CN201010549195 dissolves crude carbon nine petroleum resin and then carries out hydrotreatment to obtain carbon nine petroleum resin, however, the produced petroleum resin has the problems of deep color, large smell, poor compatibility with styrene elastomers and the like, the styrene elastomers become the most important component parts of products such as global rubber, plastics and the like, the annual output of China is up to tens of millions of tons, the petroleum resin production process is optimized in China continuously, but the problems can not be solved radically, the downstream terminal application is seriously influenced, and the quality upgrading of related industries is hindered.
Therefore, it is necessary to provide a process for preparing hydrogenated C9 petroleum resin to obtain C9 petroleum resin which is almost water-white, odorless, and has excellent compatibility with styrene-based elastomers such as SBS, SIS, etc.
Disclosure of Invention
In view of the problems existing in the prior art, the first aspect of the present application provides a method for preparing hydrogenated C9 petroleum resin, comprising the steps of:
(1) Ethylene is subjected to pyrolysis, carbon nine is rectified and cut to obtain a fraction A with a distillation range of 110-200 ℃ and C5 diolefin, the fraction A and the C5 diolefin are mixed to obtain a mixture B, and the mixture B reacts for 3-6 hours at 120-200 ℃ to obtain a polymerization solution;
(2) Removing the solvent and the oligomer from the polymerization solution to obtain a resin solution;
(3) Diluting resin liquid, and then adding the diluted resin liquid and H in a fixed bed hydrogenation reactor 2 Reacting to obtain hydrogenated resin liquid B;
(4) And (3) rectifying the hydrogenated resin liquid B and granulating to obtain the catalyst.
In one embodiment, the fraction a comprises: 15-20wt% of methyl styrene, 40-50wt% of dicyclopentadiene, 10-20wt% of indene, 2-6wt% of methyl indene, 0.1-0.5wt% of naphthalene and the balance of inert components. Preferably, the fraction A comprises 18wt% of methylstyrene, 50wt% of dicyclopentadiene, 10wt% of indene, 5wt% of methylindene, 0.1wt% of naphthalene and the balance inert components.
Examples of inert components in fraction A include methylpropylene, diethylbenzene, methyldiethylbenzene, and trimethylbenzene.
In one embodiment, the C5 diolefin comprises: 15-18wt% of piperylene, 15-18wt% of isoprene, 15-18wt% of cyclopentadiene and the balance of inert components.
As the inert component in the C5 diolefin, n-pentane, isopentane, cyclopentane and the like can be exemplified.
In one embodiment, fraction a is ungelatinized with diatomaceous earth prior to mixing the fraction a and C5 diolefins. Preferably, fraction A after removal of the gum by diatomaceous earth, is such that the gum is less than or equal to 30ppm.
Preferably, in the step (1), the reaction temperature is 180 ℃ and the reaction time is 6 hours.
Preferably, in step (1), the C5 diolefin accounts for 5 to 35wt%, more preferably 15 to 33wt%, and there may be exemplified 15wt%, 16.7wt%, 20wt%, 25wt%, 30wt%, 33wt% and the like of the mixture.
Preferably, the mixture B comprises: 10 to 16.6 weight percent of methyl styrene, 26.6 to 33.3 weight percent of dicyclopentadiene, 6 to 10 weight percent of indene, 2.5 to 6 weight percent of piperylene, 2.5 to 6 weight percent of isoprene, 2.5 to 6 weight percent of cyclopentadiene, 1.4 to 4 weight percent of methylindene, 0.06 to 0.3 weight percent of naphthalene and the balance of inert components. More preferably, mix B comprises: 15wt% of methyl styrene, 30wt% of dicyclopentadiene, 6wt% of indene, 5wt% of piperylene, 5wt% of isoprene, 5wt% of cyclopentadiene, 2wt% of methylindene, 0.1wt% of naphthalene and the balance of inert components.
In one embodiment, step (2) comprises: vacuum rectifying the polymerization liquid to 60-100 deg.c in vacuum degree of-0.08 to-0.09 MPa to eliminate solvent; then continuously heating to 200-250 ℃ to remove the oligomer and obtain resin liquid; preferably, step (2) includes: vacuum rectifying the polymerization solution to 100 deg.c in vacuum degree of-0.09 MPa to eliminate solvent; and then continuously heating to 250 ℃ to remove the oligomer, thus obtaining the resin liquid.
In one embodiment, a two-stage hydrogenation fixed bed reactor is used in step (3) to allow the resin liquid to react with H 2 And (3) reacting.
Preferably, in the step (3), the resin solution is diluted with a solvent selected from one or more of cyclohexane, methylcyclohexane, toluene, xylene, trimethylbenzene, and C9 inert oil.
Preferably, in step (3), the weight ratio of the resin liquid to the solvent is 1: (2-5), more preferably 1:3.
In a preferred embodiment, step (3) comprises: the resin liquid is firstly fed into a first-stage fixed bed hydrogenation reactor after dilution, and is reacted with H under the action of nickel hydrogenation catalyst at the pressure of 8-12MPa and the temperature of 280-350 DEG C 2 Reacting to obtain hydrogenated resin liquid A; removing impurities from the hydrogenated resin liquid A, feeding the hydrogenated resin liquid A into a two-stage fixed bed hydrogenation reactor, and reacting with H under the action of a modified nickel hydrogenation catalyst at a pressure of 10-15 MPa and a temperature of 240-300 DEG C 2 And (3) reacting to obtain hydrogenated resin liquid B.
Preferably, the liquid hourly space velocity LSHV in the one-stage fixed bed hydrogenation reactor is 0.5-1.0h -1 。
Preferably, the liquid hourly space velocity LSHV in the two-stage fixed bed hydrogenation reactor is 0.25 to 1.0h -1 。
In a more preferred embodiment, step (3) comprises: the resin liquid is diluted and then is firstly fed into a first-stage fixed bed hydrogenation reactor, and is reacted with H under the action of nickel hydrogenation catalyst at the pressure of 8MPa and the temperature of 280-290 DEG C 2 Reacting to obtain hydrogenated resin liquid A; feeding the hydrogenated resin liquid A into an activated alumina filler tower, removing impurities at 120-180 ℃, feeding into a two-stage fixed bed hydrogenation reactor, and reacting with H under the action of a modified nickel hydrogenation catalyst at the pressure of 10MPa and the temperature of 280 DEG C 2 And (3) reacting to obtain hydrogenated resin liquid B.
Preferably, the average particle size of the alumina in the activated alumina packed column is from 6 to 13mm.
Preferably, the nickel-based hydrogenation catalyst has a nickel content of 25 to 40wt%, and examples thereof include 25wt%, 30wt%, 35wt% and 40wt%.
Preferably, the nickel hydrogenation catalyst is supported by Al 2 O 3 。
Preferably, the activated alumina has an average particle size of 13-25mm, e.g., 13mm, 15mm, 18mm, 20mm, 22mm, 25mm, etc.
Preferably, the modified nickel-based hydrogenation catalyst is a metallic platinum modified nickel-based hydrogenation catalyst.
It is further preferred that the platinum content of the metal platinum modified nickel-based hydrogenation catalyst is from 0.8 to 1.1wt%.
Preferably, the loading material of the modified nickel hydrogenation catalyst is Al 2 O 3 More preferably gamma-Al 2 O 3 。
Preferably, the modified nickel-based hydrogenation catalyst satisfies at least one of the following conditions:
(1) Specific surface area of 100-200m 2 Preferably 130-180m 2 /g；
(2) Pore volume of 0.2-0.8cm 3 Preferably 0.2-0.6 cm/g 3 /g；
(3) The average particle diameter is 2 to 10mm, preferably 5 to 10mm.
In one embodiment, in step (4), the conditions of the rectification include: vacuum degree is minus 0.090 to minus 0.095MPa, and temperature is 250-280 ℃.
Preferably, in step (4), the conditions for the rectification include: vacuum degree-0.095 MPa and temperature 250 ℃.
The second aspect of the application provides a hydrogenated C9 petroleum resin prepared by the method for preparing a hydrogenated C9 petroleum resin.
The hydrogenated C9 petroleum resin obtained by the preparation method has the softening point of 90-120 ℃, the Gardner color number of less than or equal to 1.0#, and the content of the annular structure of 85-95 wt%.
The applicant has found unexpectedly that by using a mixture of C5 diolefins and fraction A, and simultaneously adopting a specific two-stage hydrogenation reaction in the application, and controlling the temperature of the hydrogenation reaction to be 280-290 ℃, the prepared hydrogenated C9 petroleum resin has high cyclic structure content, low odor and good compatibility with styrene elastomers, and the applicant considers that the possible reasons are that the C5 diolefins in the specific content improve the flexibility of molecular chains, and at the same time, the content of the final cyclic structure is not influenced, and the compatibility with the styrene elastomers is improved. When the hydrogenation temperature is too high, the thermal cracking tendency of the resin becomes remarkable, the cyclic structure content and softening point are lowered, and the compatibility with styrene-based elastomers is deteriorated.
Compared with the prior art, the application has the following beneficial effects:
(1) The application takes the ethylene cracking carbon nine as the raw material to prepare the light-colored (almost water-white) odorless resin with higher added value, and the process has strong adaptability to different ethylene cracking carbon nine raw materials, less byproducts and high product quality, improves the economic utilization value and reduces the influence on the environment;
(2) The method has strong adaptability to different ethylene cracking carbon nine raw materials, few byproducts, and the prepared hydrogenated C9 petroleum resin with a high cyclic structure has the advantages of high cyclic structure, light color number, no smell, moderate softening point, narrow molecular weight distribution and the like, and has excellent compatibility with styrene elastomers such as SBS, SIS and the like; the method is suitable for the fields of hot melt adhesives, coatings, rubber modification and the like;
(3) The primary nickel hydrogenation catalyst adopted by the application has the characteristics of better colloid resistance, sulfur resistance, impurity resistance and the like, and is suitable for hydrogenation processes of complex components;
(4) The two-stage modified nickel hydrogenation catalyst adopted by the application has high activity, low degradation rate and long service life, and is suitable for the deep hydrogenation process of resin; the application adopts a two-stage fixed bed hydrogenation process, wherein the first stage adopts a poison-tolerant hydrogenation catalyst to pre-hydrogenate the resin and remove toxic impurities, and the second stage adopts a high-activity hydrogenation catalyst to further saturate unsaturated bonds in the resin molecules, so that the hydrogenation effect and the resin performance are improved.
Detailed Description
The present application is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Example 1
A preparation method of hydrogenated C9 petroleum resin comprises the following steps:
(1) And (3) rectifying and cutting ethylene pyrolysis carbon nine to obtain a fraction A with a distillation range of 110-190 ℃, and degumming by diatomite to reduce the colloid of the fraction A to 10ppm.
(2) Mixing the fraction A and C5 diolefin according to the mass ratio of 1:0.5 to obtain a mixture B, wherein the mixture B comprises the following components: 15.0wt% of methyl styrene, 30.0wt% of dicyclopentadiene, 6.0wt% of indene, 5.0wt% of piperylene, 5.0wt% of isoprene, 5.0wt% of cyclopentadiene, 2.0wt% of methylindene, 0.1wt% of naphthalene and the balance of inert components, adding a mixture B into a reaction kettle with stirring, and reacting for 6 hours at 180 ℃ to obtain a polymerization solution.
(3) Rectifying the polymerization solution in the step (2) to 100 ℃ under reduced pressure at the vacuum degree of-0.09 MPa, and removing the solvent; then continuously heating to 250 ℃ to remove the oligomer, thus obtaining resin liquid;
(4) Diluting the resin liquid and the solvent (methylcyclohexane) in the step (3) according to a mass ratio of 1:3, and feeding the diluted resin liquid and the solvent into a one-stage fixed bed hydrogenation reactor (liquid hourly space velocity LSHV is 0.8 h) -1 ) In the nickel hydrogenation catalyst (nickel content: 30%, support material: al 2 O 3 ) Under the action of pressure of 8MPa and temperature of 280 ℃ and H 2 Reacting to obtain hydrogenated resin liquid A;
(5) Feeding the hydrogenated resin liquid A obtained in the step (4) into an activated alumina packing tower (the average diameter of alumina porcelain balls is 10 mm), and removing impurities at 120 ℃; then the mixture is sent into a two-stage fixed bed hydrogenation reactor (the liquid hourly space velocity LSHV is 0.5 h) -1 ) In the modified nickel hydrogenation catalyst (the modified nickel hydrogenation catalyst adopts metal platinum as a modifier, wherein the platinum content is 1wt%, and the load material is gamma-Al) 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Specific surface area of the modified nickel hydrogenation catalyst is 130-180m 2 Per gram, pore volume of 0.4-0.6 cm 3 Per g, average particle size 5-10 mm), under the action of pressure 10MPa and temperature 280 ℃ and H 2 Reacting to obtain hydrogenated resin liquid B;
(6) And (3) feeding the hydrogenated resin liquid B obtained in the step (5) into a rectifying tower, rectifying at the temperature of 250 ℃ under the vacuum degree of-0.095 MPa, recovering the solvent at the tower top, and granulating the tower-mounted material to obtain hydrogenated C9 petroleum resin with the chromaticity of 0# and the softening point of 100 ℃ and the annular structure content of 95wt%, wherein the hydrogenated C9 petroleum resin has excellent compatibility with styrene elastomers.
Wherein the composition of fraction A is shown in Table 1 below.
TABLE 1
The composition of ethylene cracking carbon nine is shown in table 2 below.
TABLE 2
Examples 2 to 5, comparative example 1
A preparation method of hydrogenated C9 petroleum resin is the same as in example 1, except that the addition amount of C5 diolefin in step (2) is different, specifically shown in Table 3, wherein the addition amount of C5 diolefin is the mass percentage of C5 diolefin in the mixture B.
TABLE 3 Table 3
Among these, the method for determining compatibility with styrene-based elastomer in table 3 and the excellent, good, general criteria are: after the hydrogenated C9 resin and the styrene elastomer are mixed according to the weight ratio of 1:1, wax fog point detection analysis is carried out, the lower the wax fog point is, the better the compatibility is, the wax fog point is marked as excellent at 70-90 ℃, the 90-100 ℃ (excluding 90 ℃ and 100 ℃) is marked as excellent, and the temperature is marked as normal at 100 ℃ or higher.
As is clear from examples 2 to 5 and comparative example 1, as the total content of C5 diolefins in the mixture B increases, the content of the cyclic structure of the hydrogenated resin increases, the compatibility of the hydrogenated C9 resin with the styrene-based elastomer also increases significantly, and the molecular weight distribution Mw/Mn tends to increase; when no C5 diolefin is used as a modifier in the mixture, the hydrogenated resin has the minimum cyclic structure content, but the highest softening point and the smallest molecular weight distribution Mw/Mn. The hydrogenated resin has proper cyclic structure content and molecular weight distribution, can effectively enhance the compatibility with SBS, SIS and other elastomers, and improves the cohesive strength of products.
Examples 6 to 7
A process for preparing hydrogenated C9 petroleum resin having a highly cyclic structure, which differs from example 1 in the temperature in step (4), is shown in Table 4.
TABLE 4 Table 4
As is evident from examples 6 to 7 above, the hydrogenation temperature has a significant effect on the performance of the hydrogenated resin in the hydrogenation process. When the hydrogenation temperature exceeds 280 ℃, the thermal cracking tendency of the resin is remarkable, the cyclic structure content and softening point are reduced, and the compatibility with styrene elastomers is deteriorated.
Therefore, the ethylene cracking carbon nine is rectified and cut to the greatest extent, then the molecular structure of the resin is regulated and modified by using C5 diolefin, a proper amount of C5 diolefin can improve the flexibility of a molecular chain segment, the content of the annular structure in the resin is considered, the compatibility with styrene elastomer is not affected, and finally the color number and the smell of the resin are thoroughly improved by utilizing a two-section fixed bed hydrogenation process, so that the hydrogenation temperature is controlled to avoid the cracking of the resin due to deep hydrogenation. Compared with most of domestic petroleum resin production processes, the method has the main advantages that the annular hydrogenated C9 resin has lower color number, no smell and better compatibility with styrene elastomer, and is beneficial to promoting the upgrade of downstream industries.
Claims (6)
1. A process for the preparation of hydrogenated C9 petroleum resin comprising the steps of:
(1) Ethylene is subjected to pyrolysis, carbon nine is rectified and cut to obtain a fraction A with a distillation range of 110-200 ℃ and C5 diolefin, the fraction A and the C5 diolefin are mixed to obtain a mixture B, and the mixture B reacts for 3-6 hours at 120-200 ℃ to obtain a polymerization solution;
(2) Removing the solvent and the oligomer from the polymerization solution to obtain a resin solution;
(3) The resin liquid is diluted and then is firstly fed into a first-stage fixed bed hydrogenation reactor, and is reacted with H under the pressure of 8MPa and the temperature of 280 ℃ under the action of a nickel hydrogenation catalyst 2 Reacting to obtain hydrogenated resin liquid A; feeding the hydrogenated resin liquid A into an activated alumina filler tower, removing impurities at 120-180 ℃, feeding into a two-stage fixed bed hydrogenation reactor, and reacting with H under the action of a modified nickel hydrogenation catalyst at the pressure of 10MPa and the temperature of 280 DEG C 2 Reacting to obtain hydrogenated resin liquid B;
(4) Rectifying the hydrogenated resin liquid B and granulating to obtain the catalyst;
the fraction a comprises: 15-20wt% of methyl styrene, 40-50wt% of dicyclopentadiene, 10-20wt% of indene, 2-6wt% of methyl indene, 0.1-0.5wt% of naphthalene and the balance of inert components;
the C5 diolefins include: 15-18wt% of piperylene, 15-18wt% of isoprene, 15-18wt% of cyclopentadiene and the balance of inert components;
in the step (1), C5 diolefin accounts for 15-33wt% of the mixture;
the modified nickel hydrogenation catalyst is a metal platinum modified nickel hydrogenation catalyst; the platinum content of the metal platinum modified nickel hydrogenation catalyst is 0.8-1.1wt%.
2. The method for producing hydrogenated C9 petroleum resin according to claim 1, wherein the nickel content in the nickel-based hydrogenation catalyst is 25 to 40% by weight.
3. The process for producing hydrogenated C9 petroleum resin according to claim 2, wherein the modified nickel-based hydrogenation catalyst satisfies at least one of the following conditions:
(1) Specific surface area of 100-200m 2 /g，
(2) Pore volume of 0.2-0.8cm 3 /g，
(3) The average particle diameter is 2-10mm.
4. The process for producing a hydrogenated C9 petroleum resin according to claim 3, wherein the modified nickel-based hydrogenation catalyst satisfies at least one of the following conditions:
(1) The specific surface area is 130-180m 2 /g；
(2) Pore volume of 0.2-0.6cm 3 /g；
(3) The average particle size is 5-10mm.
5. The process for producing hydrogenated C9 petroleum resin according to claim 3 or 4, wherein the mixture B comprises: 10 to 16.6 weight percent of methyl styrene, 26.6 to 33.3 weight percent of dicyclopentadiene, 6 to 10 weight percent of indene, 2.5 to 6 weight percent of piperylene, 2.5 to 6 weight percent of isoprene, 2.5 to 6 weight percent of cyclopentadiene, 1.4 to 4 weight percent of methylindene, 0.06 to 0.3 weight percent of naphthalene and the balance of inert components.
6. A hydrogenated C9 petroleum resin produced according to the process for producing a hydrogenated C9 petroleum resin according to any one of claims 1 to 5.
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| CN102002130A (en) * | 2010-09-20 | 2011-04-06 | 中国海洋石油总公司 | Preparation method of hydrogenated C9 petroleum resin |
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| CN102002130A (en) * | 2010-09-20 | 2011-04-06 | 中国海洋石油总公司 | Preparation method of hydrogenated C9 petroleum resin |
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