CN114516926A - 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 100
- 239000011347 resin Substances 0.000 title claims abstract description 100
- 239000003208 petroleum Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 150000001993 dienes Chemical class 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 210000003918 fraction a Anatomy 0.000 claims abstract description 17
- 238000005336 cracking Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 238000007865 diluting Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- 150000002815 nickel Chemical class 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- -1 platinum metal modified nickel Chemical class 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 26
- 229920001971 elastomer Polymers 0.000 abstract description 19
- 239000000806 elastomer Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000009965 odorless effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004831 Hot glue Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product 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
- 239000000463 material Substances 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 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
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 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
- 230000015572 biosynthetic process 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
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 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
- YQZBFMJOASEONC-UHFFFAOYSA-N 1-Methyl-2-propylbenzene Chemical compound CCCC1=CC=CC=C1C YQZBFMJOASEONC-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
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation 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
- 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
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer 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
- 238000000926 separation method Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
Abstract
The invention 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. The preparation method of the hydrogenated C9 petroleum resin comprises the following steps: (1) the ethylene cracking carbon nine is rectified and cut to obtain a fraction A with the 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 at the temperature of 120-200 ℃ for 3-6 hours to obtain a polymerization solution; (2) removing the solvent and the oligomer from the polymerization solution to obtain a resin solution; (3) diluting the resin liquid and reacting with H in a fixed bed hydrogenation reactor2Reacting to obtain hydrogenated resin liquid B; (4) 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, almost water white and odorless annular hydrogenated C9 petroleum resin obtained by the method, has excellent compatibility with styrene elastomers such as SBS, SIS and the like, and is suitable for hot melt adhesives, coatings and rubber modificationSex, etc.
Description
Technical Field
The invention 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
The ethylene cracking carbon nine is a product of high-temperature condensation of the raw material and the product of the ethylene cracking raw material 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 complex composition, wherein the content of the components is higher, such as methyl styrene, trimethylbenzene, dicyclopentadiene, indene, methyl indene, naphthalene and the like. Because the components are complex and the separation difficulty is high, the catalyst is mainly used as a raw material for producing high-boiling-point solvent oil and can also be used as boiler fuel, and the economic value is low.
At present, over 70% of petroleum resin synthesis processes and matching devices in China still stay at the stage of polymerization-rectification-molding, CN201010549195 dissolves crude carbon-nine petroleum resin and then carries out hydrotreating to obtain the carbon-nine petroleum resin, however, the produced petroleum resin generally has the problems of deep color, large smell, poor compatibility with styrene elastomers and the like, while styrene elastomers become the most important components of products such as global rubber, plastics and the like, the yield of the products reaches up to tens of millions of tons every year in China only, although the petroleum resin production process is continuously optimized in China, the petroleum resin synthesis processes only can play a role in improvement, the problems cannot be radically solved, the downstream terminal application is seriously influenced, and the related quality upgrading is hindered.
Therefore, it is necessary to provide a method for producing a hydrogenated C9 petroleum resin to obtain a C9 petroleum resin which is almost water white, odorless and excellent in compatibility with styrene-based elastomers such as SBS and SIS.
Disclosure of Invention
In view of the problems of the prior art, the first aspect of the present invention provides a method for preparing hydrogenated C9 petroleum resin, comprising the following steps:
(1) the ethylene cracking carbon nine is rectified and cut to obtain a fraction A with the 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 at the temperature of 120-200 ℃ for 3-6 hours to obtain a polymerization solution;
(2) removing the solvent and the oligomer from the polymerization liquid to obtain resin liquid;
(3) diluting the resin liquid and reacting with H in a fixed bed hydrogenation reactor2Reacting to obtain hydrogenated resin liquid B;
(4) and (4) rectifying the hydrogenated resin liquid B and granulating to obtain the catalyst.
In one embodiment, the fraction a comprises: 15-20 wt% of methyl styrene, 40-50 wt% of dicyclopentadiene, 10-20 wt% of indene, 2-6 wt% of methyl indene, 0.1-0.5 wt% of naphthalene and the balance of inert components. Preferably, the fraction A comprises 18 wt% of methyl styrene, 50 wt% of dicyclopentadiene, 10 wt% of indene, 5 wt% of methyl indene, 0.1 wt% of naphthalene and the balance inert components.
Examples of the inert component in fraction A include methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.
In one embodiment, the C5 diolefins include: 15-18 wt% of piperylene, 15-18 wt% of isoprene, 15-18 wt% of cyclopentadiene and the balance inert components.
As inert components in the C5 diolefin, n-pentane, isopentane, cyclopentane and the like can be cited.
In one embodiment, fraction a is degelled with diatomaceous earth prior to combining fraction a with C5 diolefin. Preferably, fraction A is degelled with diatomaceous earth to a gel content of 30ppm or less.
Preferably, in the step (1), the reaction temperature is 180 ℃ and the reaction time is 6 h.
Preferably, in step (1), the C5 diolefin constitutes 5 to 35 wt%, more preferably 15 to 33 wt%, of the blend, and examples thereof include 15 wt%, 16.7 wt%, 20 wt%, 25 wt%, 30 wt%, 33 wt%.
Preferably, mix B comprises: 10-16.6 wt% of methyl styrene, 26.6-33.3 wt% of dicyclopentadiene, 6-10 wt% of indene, 2.5-6 wt% of piperylene, 2.5-6 wt% of isoprene, 2.5-6 wt% of cyclopentadiene, 1.4-4 wt% of methyl indene, 0.06-0.3 wt% of naphthalene and the balance of inert components. More preferably, mix B comprises: 15 wt% of methyl styrene, 30 wt% of dicyclopentadiene, 6 wt% of indene, 5 wt% of piperylene, 5 wt% of isoprene, 5 wt% of cyclopentadiene, 2 wt% of methyl indene, 0.1 wt% of naphthalene and the balance of inert components.
In one embodiment, step (2) comprises: rectifying the polymerization liquid to 60-100 ℃ under reduced pressure at the vacuum degree of-0.08-0.09 MPa, and removing the solvent; then, continuously heating to 200-250 ℃, and removing the oligomer to obtain resin liquid; preferably, step (2) comprises: vacuum rectifying the polymerized liquid to 100 deg.c at vacuum degree of-0.09 MPa and eliminating solvent; then, the temperature is continuously increased to 250 ℃, and oligomer is removed to obtain resin liquid.
In one embodiment, two-stage hydrogenation fixed bed reactor is adopted in the step (3) to ensure that the resin liquid and H are mixed2And (4) 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 the 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 diluted and then firstly sent into a first-stage fixed bed hydrogenation reactor, and is reacted with H under the pressure of 8-12MPa and the temperature of 280-2Reacting to obtain hydrogenated resin liquid A; removing impurities from the hydrogenated resin liquid A, sending the hydrogenated resin liquid A into a two-stage fixed bed hydrogenation reactor, and reacting the hydrogenated resin liquid A with H under the action of a modified nickel hydrogenation catalyst at the pressure of 10-15 MPa and the temperature of 240-300 DEG C 2Reacting to obtain hydrogenated resin liquid B.
Preferably, the liquid hourly space velocity LSHV in the first-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 0.25-1.0 h-1。
In a more preferred embodiment, step (3) comprises: after being diluted, the resin liquid is firstly sent into a fixed bed hydrogenation reactor and is subjected to pressure under the action of a nickel hydrogenation catalyst8MPa, a temperature of 280 ℃ and 290 ℃ and H2Reacting to obtain hydrogenated resin liquid A; the hydrogenated resin liquid A is sent into an activated alumina packing tower, after impurities are removed at the temperature of 180 ℃ with 120 plus materials, the hydrogenated resin liquid A is sent into a two-stage fixed bed hydrogenation reactor, and under the action of a modified nickel hydrogenation catalyst, the hydrogenated resin liquid A is reacted with H under the pressure of 10MPa and the temperature of 280 DEG C2Reacting to obtain hydrogenated resin liquid B.
Preferably, the average particle size of the alumina in the activated alumina packed column is 6 to 13 mm.
The nickel-based hydrogenation catalyst preferably contains 25 to 40 wt% of nickel, and examples thereof include 25 wt%, 30 wt%, 35 wt%, and 40 wt%.
Preferably, the supporting material of the nickel-based hydrogenation catalyst is Al2O3。
Preferably, the activated alumina has an average particle size of 13 to 25mm, such as 13mm, 15mm, 18mm, 20mm, 22mm, 25mm, and the like.
Preferably, the modified nickel-based hydrogenation catalyst is a platinum metal modified nickel-based hydrogenation catalyst.
More preferably, the platinum content in the metallic platinum modified nickel-based hydrogenation catalyst is 0.8-1.1 wt%.
Preferably, the load material of the modified nickel-based hydrogenation catalyst is Al2O3More preferably gamma-Al2O3。
Preferably, the modified nickel-based hydrogenation catalyst at least satisfies one of the following conditions:
(1) the specific surface area is 100-200m2/g, preferably 130-180m2/g；
(2) Pore volume of 0.2-0.8cm3In g, preferably 0.2 to 0.6cm3/g；
(3) The average particle size is 2 to 10mm, preferably 5 to 10 mm.
In one embodiment, in step (4), the rectification conditions include: the vacuum degree is-0.090 to-0.095 MPa, and the temperature is 250-280 ℃.
Preferably, in the step (4), the rectification conditions include: the vacuum degree is-0.095 MPa, and the temperature is 250 ℃.
The second aspect of the invention provides a hydrogenated C9 petroleum resin prepared by the preparation method of the hydrogenated C9 petroleum resin.
The hydrogenated C9 petroleum resin prepared 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 a ring structure of 85-95 wt%.
The applicant has surprisingly found that the hydrogenated C9 petroleum resin prepared by using C5 diolefin in combination with fraction a and using the two-stage hydrogenation reaction specified in the present application and controlling the hydrogenation reaction temperature at 280-290 ℃ has a high cyclic structure content, low odor and good compatibility with styrenic elastomers, and the applicant believes that the possible reason is that the flexibility of the molecular chain is improved by the specified content of C5 diolefin, while the final cyclic structure content is not affected and the compatibility with styrenic elastomers is improved. If the hydrogenation temperature is too high, the thermal cracking tendency of the resin is remarkable, the content of the cyclic structure and the softening point are reduced, and the compatibility with the styrene elastomer is poor.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method 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, few byproducts and high product quality, improves the economic utilization value of the product, 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 ring structure has the advantages of high ring structure, light color number, no odor, 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 nickel-based hydrogenation catalyst adopted by the invention has the characteristics of better colloid resistance, sulfur resistance, impurity resistance and the like, and is suitable for a hydrogenation process of complex components;
(4) the two-stage modified nickel hydrogenation catalyst adopted by the invention has high activity, low degradation rate and long service life, and is suitable for the deep hydrogenation process of resin; the invention adopts a two-stage fixed bed hydrogenation process, wherein a poison-resistant hydrogenation catalyst is adopted in the first stage to pre-hydrogenate the resin and remove toxic impurities, and a high-activity hydrogenation catalyst is adopted in the second stage to further saturate unsaturated bonds in the resin molecules, so that the hydrogenation effect and the resin performance are improved.
Detailed Description
The present invention will be described below by way of 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) the ethylene cracking carbon nine is rectified and cut to obtain a fraction A with the distillation range of 110-190 ℃, and the fraction A is degummed by diatomite to reduce the colloid to 10 ppm.
(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: 15.0 wt% of methyl styrene, 30.0 wt% of dicyclopentadiene, 6.0 wt% of indene, 5.0 wt% of piperylene, 5.0 wt% of isoprene, 5.0 wt% of cyclopentadiene, 2.0 wt% of methyl indene, 0.1 wt% of naphthalene and the balance of inert components, adding the mixture B into a reaction kettle with a stirrer, and reacting at 180 ℃ for 6 hours to obtain a polymerization solution.
(3) Rectifying the polymerization liquid obtained in the step (2) to 100 ℃ under the vacuum degree of-0.09 MPa, and removing the solvent; then, continuously heating to 250 ℃, and removing the oligomer to obtain resin liquid;
(4) diluting the resin liquid in the step (3) and a solvent (methyl cyclohexane) according to the mass ratio of 1: 3, and then feeding the diluted resin liquid and the solvent (methyl cyclohexane) into a first-section fixed bed hydrogenation reactor (the liquid hourly space velocity LSHV is 0.8h-1) In the nickel hydrogenation catalyst (nickel content is 30%, and load material is Al) 2O3) Under the action of (1), reacting with H under the pressure of 8MPa and the temperature of 280 DEG C2Reacting to obtain hydrogenated resin liquid A;
(5) feeding the hydrogenated resin liquid A obtained in the step (4) into an activated alumina packed tower (the average diameter of alumina porcelain balls is 10mm), 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 series hydrogenation catalyst (the modified nickel series hydrogenation catalyst adopts metal platinum as)Is a modified substance, wherein the platinum content is 1wt percent, and the load material is gamma-Al2O3(ii) a The specific surface area of the modified nickel hydrogenation catalyst is 130-180 m2Per gram, pore volume 0.4-0.6 cm3G, average particle diameter of 5-10mm) under the pressure of 10MPa and the temperature of 280 ℃ with H2Reacting 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 vacuum degree of-0.095 MPa and the temperature of 250 ℃, recovering the solvent from the tower top, and granulating the tower kettle material to obtain the hydrogenated C9 petroleum resin with the chroma of 0#, no odor, the softening point of 100 ℃ and the cyclic structure content of 95 wt%, wherein the hydrogenated C9 petroleum resin has excellent compatibility with the styrene elastomer.
The composition of fraction a is shown in table 1 below.
TABLE 1
The composition of the 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 that of example 1, except that the addition amount of C5 diolefin in step (2) is different, and concretely, see Table 3, wherein the addition amount of C5 diolefin is the mass percent of C5 diolefin in the mixture B.
TABLE 3
Among them, the determination method of compatibility with styrene-based elastomer in table 3 and the excellent, good, and general criteria for determination are: the hydrogenated C9 resin and styrene elastomer are mixed according to the weight ratio of 1: 1, and wax haze point detection and analysis are carried out, the lower the wax haze point is, the better the compatibility is, the wax haze point is marked as excellent at 70-90 ℃, the better the wax haze point is marked as good at 90-100 ℃ (excluding 90 ℃ and 100 ℃), and the normal wax haze point is marked as normal at more than or equal to 100 ℃.
As can be seen from the above examples 2-5 and comparative example 1, with the increase of the total content of C5 diolefin in the mixture B, the content of the cyclic structure of the hydrogenated resin increases, the compatibility of the hydrogenated C9 resin with the styrene elastomer also increases significantly, and the molecular weight distribution Mw/Mn tends to increase; when no C5 diolefin is used as modifier in the mixture, the hydrogenated resin has the smallest content of cyclic structure, but has 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 elastomers such as SBS, SIS and the like, and improves the cohesive strength of products.
Examples 6 to 7
A method for preparing hydrogenated C9 petroleum resin with high cyclic structure is the same as example 1 except for the difference of temperature in step (4), see Table 4.
TABLE 4
From the above examples 6-7, it can be seen that the hydrogenation temperature has a significant effect on the properties of the hydrogenated resin in the hydrogenation process. When the hydrogenation temperature exceeds 280 ℃, the thermal cracking tendency of the resin is obvious, the content of a cyclic structure and the softening point are reduced, and the compatibility with the styrene elastomer is poor.
Therefore, the ethylene cracking carbon nine is subjected to rectification cutting to retain a ring structure to the maximum extent, the molecular structure of the resin is adjusted and modified by using C5 diolefin, the appropriate amount of C5 diolefin can improve the flexibility of a polymer chain segment, the content of the ring structure in the resin is considered, the compatibility of the resin and a styrene elastomer is not influenced, finally, the color number and the smell of the resin are thoroughly improved by using a two-section fixed bed hydrogenation process, and 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 cyclic hydrogenated C9 resin has lower color number and no odor, has better compatibility with styrene elastomers, and is beneficial to promoting the upgrading of downstream industries.
Claims (10)
1. A preparation method of hydrogenated C9 petroleum resin is characterized by comprising the following steps:
(1) the ethylene cracking carbon nine is rectified and cut to obtain a fraction A with the 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 at the temperature of 120-200 ℃ for 3-6 hours to obtain a polymerization solution;
(2) removing the solvent and the oligomer from the polymerization solution to obtain a resin solution;
(3) diluting the resin liquid and reacting with H in a fixed bed hydrogenation reactor2Reacting to obtain hydrogenated resin liquid B;
(4) and (4) rectifying the hydrogenated resin liquid B and granulating to obtain the catalyst.
2. The method for preparing hydrogenated C9 petroleum resin according to claim 1, wherein in step (1), the C5 diolefin constitutes 5-35 wt% of the blend.
3. The method for preparing hydrogenated C9 petroleum resin according to claim 2, wherein step (3) comprises using a two-stage hydrogenation fixed bed reactor to mix the resin solution with H2And (4) reacting.
4. The method for producing a hydrogenated C9 petroleum resin according to claim 3, wherein the step (3) comprises: the resin liquid is diluted and then firstly sent into a first-stage fixed bed hydrogenation reactor, and is reacted with H under the pressure of 8-12MPa and the temperature of 280-2Reacting to obtain hydrogenated resin liquid A; removing impurities from the hydrogenated resin liquid A, sending the hydrogenated resin liquid A into a two-stage fixed bed hydrogenation reactor, and carrying out pressure hydrogenation on the hydrogenated resin liquid A under the action of a modified nickel hydrogenation catalyst Force 10-15MPa, temperature 240-2Reacting to obtain hydrogenated resin liquid B.
5. The method of claim 4, wherein the nickel content of the hydrogenation catalyst is 25-40 wt%.
6. The method for preparing hydrogenated C9 petroleum resin according to claim 4 or 5, wherein the modified nickel hydrogenation catalyst is a platinum metal modified nickel hydrogenation catalyst.
7. The method of claim 6, wherein the content of Pt in the Pt-modified Ni-based hydrogenation catalyst is 0.8-1.1 wt%.
8. The method for preparing hydrogenated C9 petroleum resin according to claim 7, wherein the modified nickel-based hydrogenation catalyst satisfies at least one of the following conditions:
(1) the specific surface area is 100-200m2G, preferably 130-180m2/g；
(2) Pore volume of 0.2-0.8cm3In g, preferably 0.2 to 0.6cm3/g；
(3) The average particle size is 2 to 10mm, preferably 5 to 10 mm.
9. The method for preparing hydrogenated C9 petroleum resin according to claim 7 or 8, wherein mix B comprises: 10-16.6 wt% of methyl styrene, 26.6-33.3 wt% of dicyclopentadiene, 6-10 wt% of indene, 2.5-6 wt% of piperylene, 2.5-6 wt% of isoprene, 2.5-6 wt% of cyclopentadiene, 1.4-4 wt% of methyl indene, 0.06-0.3 wt% of naphthalene and the balance of inert components.
10. A hydrogenated C9 petroleum resin produced by the method of producing a hydrogenated C9 petroleum resin according to any one of claims 1 to 9.
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