TWI826986B - Method for measuring catalyst concentration in slurry solution and continuous preparation method of hydrogenated petroleum resin using the same - Google Patents
Method for measuring catalyst concentration in slurry solution and continuous preparation method of hydrogenated petroleum resin using the same Download PDFInfo
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- TWI826986B TWI826986B TW111111982A TW111111982A TWI826986B TW I826986 B TWI826986 B TW I826986B TW 111111982 A TW111111982 A TW 111111982A TW 111111982 A TW111111982 A TW 111111982A TW I826986 B TWI826986 B TW I826986B
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- Prior art keywords
- catalyst
- slurry solution
- concentration
- petroleum resin
- hydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 205
- 239000002002 slurry Substances 0.000 title claims abstract description 155
- 238000000034 method Methods 0.000 title claims abstract description 80
- 239000003208 petroleum Substances 0.000 title claims abstract description 70
- 239000011347 resin Substances 0.000 title claims abstract description 64
- 229920005989 resin Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 103
- 238000004140 cleaning Methods 0.000 claims description 59
- 239000002904 solvent Substances 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
- 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 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 18
- 238000010438 heat treatment Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- -1 nickel peroxide Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Specific substances contained in the oils or fuels
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Food Science & Technology (AREA)
- Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本發明關於一種用於測量漿料溶液的催化劑濃度的方法,係藉由無穩定性問題的簡單製程,以及使用該方法之氫化石油樹脂的連續製備方法。 相關申請案之交互參照 The present invention relates to a method for measuring the catalyst concentration of a slurry solution through a simple process without stability problems, and a continuous preparation method of hydrogenated petroleum resin using this method. Cross-references to related applications
本申請案主張2021年4月13日向韓國智慧財產局申請的韓國專利申請案第10-2021-0047646號的權益,其全部內容以引用方式納入本文。This application claims the rights and interests of Korean Patent Application No. 10-2021-0047646 filed with the Korean Intellectual Property Office on April 13, 2021, the entire content of which is incorporated herein by reference.
石油樹脂氫化反應器的操作方式是使用高溫高壓泵將催化劑漿料溶液在反應器中攪拌,但如果漿料溶液中所含固體催化劑含量超過標準值,由於流化床的強應力,可能使泵損壞或故障,因此應停止氫化反應器作業。The operation method of the petroleum resin hydrogenation reactor is to use a high-temperature and high-pressure pump to stir the catalyst slurry solution in the reactor. However, if the solid catalyst content in the slurry solution exceeds the standard value, the pump may be damaged due to the strong stress of the fluidized bed. Damage or malfunction, so the hydrogenation reactor operation should be stopped.
特定而言,如果催化劑濃度低,則氫化性能可能會降低,如果催化劑濃度高,則可能會導致泵故障,因此可能會因頻繁停止作業而降低生產率。因此,將漿液溶液中的固體催化劑濃度在一定範圍內操作,以確保氫化反應器的操作穩定性,被認為是重要製程技術之一。Specifically, if the catalyst concentration is low, the hydrogenation performance may be reduced, and if the catalyst concentration is high, it may cause pump failure, so productivity may be reduced due to frequent shutdowns of operations. Therefore, operating the solid catalyst concentration in the slurry solution within a certain range to ensure the operational stability of the hydrogenation reactor is considered to be one of the important process technologies.
測量固體催化劑濃度的常用分析器僅可以在含水條件下使用,因此需要開發一種用於測量包括有機溶劑的氫化反應器中催化劑濃度的新穎方法。Common analyzers for measuring solid catalyst concentration can only be used under aqueous conditions, so there was a need to develop a novel method for measuring catalyst concentration in hydrogenation reactors including organic solvents.
同時,如果氫化反應器中所用鎳系催化劑經由真空過濾回收,由於催化劑的自熱性質(self-heating property),可能會產生熱和火焰(flame),從而降低穩定性。At the same time, if the nickel-based catalyst used in the hydrogenation reactor is recovered through vacuum filtration, heat and flame may be generated due to the self-heating property of the catalyst, thereby reducing stability.
因此,需要研究一種藉由更安全及更簡單製程以測量反應器中固體催化劑濃度的新穎方法。Therefore, there is a need to develop a novel method for measuring the solid catalyst concentration in the reactor through a safer and simpler process.
技術問題technical issues
本發明目的為提供一種測量漿料溶液的催化劑濃度的方法,係藉由無穩定性問題的簡單製程。The object of the present invention is to provide a method for measuring the catalyst concentration of a slurry solution through a simple process without stability problems.
本發明另一目的為提供一種氫化石油樹脂的連續製備方法,係使用測量漿料溶液的催化劑濃度的方法。 技術方案 Another object of the present invention is to provide a continuous preparation method of hydrogenated petroleum resin, which uses a method of measuring the catalyst concentration of the slurry solution. Technical solution
根據本發明一個具體實例,提供一種測量漿料溶液中催化劑濃度的方法,其包含以下步驟: 第一次清洗使用飽和烴系溶劑清洗包含氫化催化劑的石油樹脂漿料溶液; 第二次清洗使用醇清洗第一次經清洗的漿料溶液; 第三次清洗使用去離子水(DI water)清洗第二次經清洗的漿料溶液; 在50℃至70℃乾燥第三次經清洗的漿料溶液,以得到催化劑固體內容物(content);及 測量包含氫化催化劑的石油樹脂漿料溶液的催化劑濃度,該濃度定義為乾燥後得到的催化劑固體內容物的重量比。 According to a specific example of the present invention, a method for measuring catalyst concentration in a slurry solution is provided, which includes the following steps: The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; The second cleaning uses alcohol to clean the first cleaned slurry solution; For the third cleaning, use deionized water (DI water) to clean the second cleaned slurry solution; Dry the third cleaned slurry solution at 50°C to 70°C to obtain the catalyst solid content; and The catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst is measured and is defined as the weight ratio of the catalyst solid content obtained after drying.
根據本發明另一個具體實例,提供一種氫化石油樹脂的連續製備方法,包含以下步驟: 將包含石油樹脂、氫化催化劑及溶劑的漿料溶液及氫氧引入連續漿料反應器,以進行連續氫化反應, 在氫化反應期間回收部分漿料溶液以及測量漿料溶液中氫化催化劑的濃度;以 週期性或非週期性引入及排出氫化催化劑,使得氫化催化劑濃度維持在以漿料溶液總重量計2wt%至20wt%, 其中測量氫化催化劑濃度的步驟包含以下步驟: a) 第一次清洗使用飽和烴系溶劑清洗包含氫化催化劑的石油樹脂漿料溶液; b) 第二次清洗使用醇清洗第一次經清洗的漿料溶液; c) 第三次清洗使用去離子水(DI water)清洗第二次經清洗的漿料溶液; d) 在50℃至70℃乾燥第三次經清洗的漿料溶液以得到催化劑固體內容物;及 e) 測量包含氫化催化劑的石油樹脂漿料溶液的催化劑濃度,該濃度定義為乾燥後得到的催化劑固體內容物的重量比。 有利效果 According to another specific example of the present invention, a continuous preparation method of hydrogenated petroleum resin is provided, including the following steps: introducing a slurry solution containing petroleum resin, a hydrogenation catalyst and a solvent and hydrogen and oxygen into a continuous slurry reactor to perform a continuous hydrogenation reaction , during the hydrogenation reaction, recover part of the slurry solution and measure the concentration of the hydrogenation catalyst in the slurry solution; introduce and discharge the hydrogenation catalyst periodically or non-periodically, so that the hydrogenation catalyst concentration is maintained at 2wt% to 2wt% based on the total weight of the slurry solution. 20wt%, in which the step of measuring the hydrogenation catalyst concentration includes the following steps: a) The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; b) The second cleaning uses alcohol to clean the first cleaning c) Use deionized water (DI water) to clean the second cleaned slurry solution for the third time; d) Dry the third cleaned slurry solution at 50°C to 70°C to obtain Catalyst solid content; and e) measuring the catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst, which concentration is defined as the weight ratio of the catalyst solid content obtained after drying. beneficial effect
根據本發明測量漿料溶液中催化劑濃度的方法,在經過使用特定溶劑的漿料溶液的多步驟清洗製程後,能以既安全又簡單的方法測量漿料溶液中的催化劑濃度。特別的是,可以準確地測量漿料溶液中的催化劑濃度而無需單獨校正製程。According to the method of measuring the catalyst concentration in the slurry solution of the present invention, the catalyst concentration in the slurry solution can be measured in a safe and simple method after a multi-step cleaning process of the slurry solution using a specific solvent. In particular, the catalyst concentration in the slurry solution can be accurately measured without the need for separate calibration of the process.
並且,根據本發明氫化石油樹脂的連續製備方法,藉由使用測量漿料溶液中催化劑濃度的方法,可以有效控制催化劑濃度,顯著改良反應器的作業效率。Moreover, according to the continuous preparation method of hydrogenated petroleum resin of the present invention, by using the method of measuring the catalyst concentration in the slurry solution, the catalyst concentration can be effectively controlled and the operating efficiency of the reactor can be significantly improved.
儘管可以對本發明進行各種修改,並且本發明可以具有各種形式,但是下面將詳細說明和解釋特定實施例。然而,應當理解,這些並不旨在將本發明限制於特定揭露,並且本發明包括不脫離本發明的精神和技術範圍的所有修改、等同物或其替代物。While the invention is susceptible to various modifications and the invention may be taken in various forms, specific embodiments are described and explained in detail below. However, it should be understood that these are not intended to limit the present invention to the specific disclosure, and the present invention includes all modifications, equivalents, or substitutes thereof that do not depart from the spirit and technical scope of the present invention.
此外,本文使用的術語僅僅是為了解釋特定的具體實例,而不是為了限制本發明。單數表達包括其複數表達,除非是從上下文中明確陳述或顯而易見其非意旨的。如本文所用,術語「包括」、「配備」或「具有」等旨在指示所使用的特徵、數量、步驟、結構元件或其組合的存在,並且它們不旨在排除一個或多個其他特徵、數量、步驟、結構元件或其組合的存在或添加的可能性。Furthermore, the terminology used herein is for the purpose of explaining particular embodiments only and is not intended to limit the invention. A singular expression includes its plural expression unless this is expressly stated from the context or it is obvious that this is not intended. As used herein, the terms "comprising", "equipped with" or "having" are intended to indicate the presence of a feature, number, step, structural element or combination thereof, and they are not intended to exclude one or more other features, The presence or possibility of addition of quantities, steps, structural elements or combinations thereof.
此外,如果提到每一層或每個元件形成在每一層或每個元件的「之上」或「上方」,這意味著每一層或每個元件直接形成在每一層或每個元件上,或者其他層或元件可以另外形成在層與層之間或在一主體或一基底上。In addition, when reference is made to each layer or element being formed "on" or "over" each layer or element, this means that each layer or element is formed directly on each layer or element, or Other layers or elements may be additionally formed between layers or on a body or a substrate.
石油樹脂氫化反應器的操作方式是使用高溫高壓泵將催化劑漿料溶液在反應器中攪拌,但如果漿料溶液中所含固體催化劑含量超過標準值,由於流化床的強應力,可能使泵損壞或故障,因此應停止氫化反應器作業。The operation method of the petroleum resin hydrogenation reactor is to use a high-temperature and high-pressure pump to stir the catalyst slurry solution in the reactor. However, if the solid catalyst content in the slurry solution exceeds the standard value, the pump may be damaged due to the strong stress of the fluidized bed. Damage or malfunction, so the hydrogenation reactor operation should be stopped.
因此,需要將漿料溶液中的催化劑濃度控制在一定範圍內,為了測量催化劑濃度,以往在反應器內使用超聲波,或者藉由真空過濾從反應器中回收漿料溶液。然而,如果使用超聲波,是在水性條件下進行,並不適用在有機溶劑條件下進行的漿料,並且需要對測量濃度進行校正製程,因此需要單獨的測量方法進行校正。並且,在真空過濾的情況下,如果使用鎳系催化劑,由於自熱性質可能會燃燒(ignition),因此穩定性可能會顯著降低。Therefore, the catalyst concentration in the slurry solution needs to be controlled within a certain range. In order to measure the catalyst concentration, ultrasonic waves have been used in the reactor or the slurry solution has been recovered from the reactor through vacuum filtration. However, if ultrasonic wave is used, it is carried out under aqueous conditions and is not suitable for slurries carried out under organic solvent conditions, and a calibration process is required to measure the concentration, so a separate measurement method is required for calibration. In addition, in the case of vacuum filtration, if a nickel-based catalyst is used, ignition may occur due to self-heating properties, so the stability may be significantly reduced.
為了解決這些問題,本發明人發現,藉由使用三種不同的溶劑分階段清洗漿料溶液,接著在特定條件下乾燥並測量濃度的製程,漿料溶液中的催化劑濃度可以藉由簡單製程準確測量而完成本發明,沒有諸如燃燒穩定性問題。 測量漿料溶液 中 催化劑濃度 的 方法 In order to solve these problems, the inventors found that by using three different solvents to clean the slurry solution in stages, drying it under specific conditions and measuring the concentration, the catalyst concentration in the slurry solution can be accurately measured through a simple process. With the completion of the present invention, there are no problems such as combustion stability. Method for measuring catalyst concentration in slurry solutions
根據本發明的一個具體實例,測量漿料溶液中催化劑濃度的方法包含以下步驟: 第一次清洗使用飽和烴系溶劑清洗包含氫化催化劑的石油樹脂漿料溶液; 第二次清洗使用醇清洗第一次經清洗的漿料溶液; 第三次清洗使用去離子水(DI water)清洗第二次經清洗的漿料溶液; 在50℃至70℃乾燥第三次經清洗的漿料溶液以得到催化劑固體內容物;及 測量包含氫化催化劑的石油樹脂漿料溶液的催化劑濃度,該濃度定義為乾燥後得到的催化劑固體內容物的重量比。 According to a specific example of the present invention, the method for measuring the catalyst concentration in the slurry solution includes the following steps: The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; The second cleaning uses alcohol to clean the first cleaned slurry solution; For the third cleaning, use deionized water (DI water) to clean the second cleaned slurry solution; Dry the third cleaned slurry solution at 50°C to 70°C to obtain the catalyst solid content; and The catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst is measured and is defined as the weight ratio of the catalyst solid content obtained after drying.
下文將對每一步驟詳細說明。Each step is explained in detail below.
首先,石油樹脂漿料溶液可包含石油樹脂、氫化催化劑及溶劑。First, the petroleum resin slurry solution may include petroleum resin, hydrogenation catalyst and solvent.
石油樹脂需要氫化,種類沒有特定限定,例如可包括二環戊二烯(DCPD)、C5餾分、C8餾分、C9餾分或其聚合產物。Petroleum resin needs to be hydrogenated, and the type is not particularly limited. For example, it may include dicyclopentadiene (DCPD), C5 fraction, C8 fraction, C9 fraction or polymerization products thereof.
C5餾分包括石油餾分、副產物及其組合,是對石油進行預處理、蒸餾和聚合得到的,是指C5不飽和烴,諸如環戊二烯、異戊二烯、間戊二烯及類似物;C8餾分包括石油餾分、副產物及其組合,是對石油進行預處理、蒸餾和聚合得到的,是指C8不飽和烴,諸如苯乙烯、辛烯及類似物;C9餾分包括石油餾分、副產物及其組合,是對石油進行預處理、蒸餾和聚合得到的,是指C9不飽和烴,諸如乙烯基甲苯、茚及類似物。C5 fraction includes petroleum fractions, by-products and their combinations. It is obtained by pretreatment, distillation and polymerization of petroleum. It refers to C5 unsaturated hydrocarbons, such as cyclopentadiene, isoprene, piperylene and the like. ;C8 fraction includes petroleum fractions, by-products and their combinations. It is obtained by pretreatment, distillation and polymerization of petroleum. It refers to C8 unsaturated hydrocarbons, such as styrene, octene and the like; C9 fraction includes petroleum fractions, by-products and their combinations. The products and their combinations are obtained by preprocessing, distilling and polymerizing petroleum, and refer to C9 unsaturated hydrocarbons, such as vinyl toluene, indene and the like.
氫化催化劑可使用包含鎳(Ni)作為活性金屬的催化劑,特定而言,氫化催化劑可以是載體上載持有鎳(Ni)的催化劑,但不受限於此。The hydrogenation catalyst may be a catalyst containing nickel (Ni) as an active metal. Specifically, the hydrogenation catalyst may be a catalyst carrying nickel (Ni) on a carrier, but is not limited thereto.
載持催化劑(supported catalyst)可包含,以100重量份催化劑計,40至90重量份的一或多種選自由鎳(Ni)、氧化鎳(NiO,Ni 2O 3)及過氧化鎳(NiO 2)組成之群的活性材枓,以及10至60重量份的載體。 The supported catalyst may include, based on 100 parts by weight of the catalyst, 40 to 90 parts by weight of one or more materials selected from the group consisting of nickel (Ni), nickel oxide (NiO, Ni 2 O 3 ) and nickel peroxide (NiO 2 ), and a carrier consisting of 10 to 60 parts by weight.
活性材料可源自原料前驅物,諸如硝酸鎳(Ni(NO 3) 2)、氯化鎳(NiCl 2)、硫酸鎳(NiSO 4)、乙酸鎳(Ni(Acetate) 2),較佳可使用硝酸鎳。 The active material can be derived from raw material precursors, such as nickel nitrate (Ni(NO 3 ) 2 ), nickel chloride (NiCl 2 ), nickel sulfate (NiSO 4 ), nickel acetate (Ni(Acetate) 2 ), preferably using Nickel nitrate.
只要載體是本領域常用的化合物就沒有特定限制,例如可以是選自二氧化矽(SiO 2)、矽藻土、氧化鋁(Al 2O 3)和氧化鎂中的一或多種,在此種載體載持的情況下,由於催化劑結構穩定性的改良,可以表現更優異的催化活性。 There is no specific limitation as long as the carrier is a compound commonly used in the art. For example, it can be one or more selected from silica (SiO 2 ), diatomaceous earth, aluminum oxide (Al 2 O 3 ) and magnesium oxide. In this case When supported by a carrier, the catalyst can exhibit better catalytic activity due to the improved structural stability of the catalyst.
氫化催化劑可視需要進一步包含助催化劑、其他添加劑及類似物,沒有特定限制。The hydrogenation catalyst may further contain cocatalysts, other additives and the like as necessary, without specific limitations.
活性材料的平均尺寸沒有特定限制,例如可為1 nm至10 nm,較佳為1 nm或更大,或3 nm或更大,或5 nm或更大,10 nm或更小,或8 nm或更小,或7 nm或更小。當活性材料的平均尺寸在上述範圍內時,可以表現更優異的催化活性。The average size of the active material is not particularly limited, for example, it may be 1 nm to 10 nm, preferably 1 nm or greater, or 3 nm or greater, or 5 nm or greater, 10 nm or less, or 8 nm or less, or 7 nm or less. When the average size of the active material is within the above range, more excellent catalytic activity can be exhibited.
可以使用飽和烴系溶劑,諸如戊烷、己烷、庚烷、壬烷、癸烷、十一烷、十二烷、環己烷、甲基環己烷及類似物作為溶劑,但本發明不限於此。Saturated hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane and the like can be used as solvents, but the present invention does not Limited to this.
溶劑的用量以100重量份的石油樹脂計可為40至80重量份。如果溶劑的用量小於40重量份,黏度可能會增加,因此反應性和製程穩定性可能會降低,如果大於80重量份,則生產率可能會降低,溶劑回收能量可能會增加。較佳地,溶劑的用量以100重量份的石油樹脂計可為40重量份或更多、或50重量份或更多、或60重量份或更多、和80重量份或更少、或75重量份或更少或70重量份或更少。The amount of solvent may be 40 to 80 parts by weight based on 100 parts by weight of petroleum resin. If the amount of solvent is less than 40 parts by weight, the viscosity may increase, so reactivity and process stability may decrease. If it is more than 80 parts by weight, productivity may decrease and solvent recovery energy may increase. Preferably, the amount of solvent can be 40 parts by weight or more, or 50 parts by weight or more, or 60 parts by weight or more, and 80 parts by weight or less, or 75 based on 100 parts by weight of petroleum resin. parts by weight or less or 70 parts by weight or less.
石油樹脂和溶劑的混合可以藉由常用方法進行。The mixing of petroleum resin and solvent can be carried out by common methods.
根據本發明一個具體實例,方法包含使用飽和烴系溶劑第一次清洗包含氫化催化劑的石油樹脂漿料溶液的步驟。According to a specific example of the present invention, the method includes the step of using a saturated hydrocarbon solvent to first clean the petroleum resin slurry solution containing the hydrogenation catalyst.
此步驟移除回收的催化劑表面上殘留的石油樹脂,從而提高後續第二和第三清洗步驟中催化劑穩定製程的效率,藉此在測量漿料溶液濃度的製程中減少乾燥後最終回收的催化劑固體內容物的誤差。This step removes residual petroleum resin on the surface of the recovered catalyst, thereby improving the efficiency of the catalyst stabilization process in the subsequent second and third cleaning steps, thereby reducing the final recovered catalyst solids after drying in the process of measuring the concentration of the slurry solution. Errors in contents.
第一次清洗步驟所用烴系溶劑可特定地選自戊烷、己烷、庚烷、壬烷、癸烷、十一烷、十二烷、環己烷和甲基環己烷組成之群中的一或多種,較佳使用環己烷。The hydrocarbon solvent used in the first cleaning step can be specifically selected from the group consisting of pentane, hexane, heptane, nonane, decane, undecane, dodecane, cyclohexane and methylcyclohexane. One or more of them, preferably cyclohexane.
烴系溶劑的用量沒有特定限定,用量可為待測量的漿料溶液重量的2-3倍。The amount of hydrocarbon solvent is not specifically limited, and the amount can be 2-3 times the weight of the slurry solution to be measured.
清洗步驟藉由常用方法進行,例如,可以藉由將待測量的漿料溶液引入包括濾紙的容器中,將清洗溶劑引入該容器中,將漿料溶液引入容器中來進行,從而使漿液溶液被清洗。清洗步驟可以進行1-3次,較佳2-3次,在這種情況下,藉由相同方法重複進行。The cleaning step is performed by a common method. For example, it can be performed by introducing the slurry solution to be measured into a container including filter paper, introducing the cleaning solvent into the container, and introducing the slurry solution into the container, so that the slurry solution is Clean. The cleaning step can be performed 1-3 times, preferably 2-3 times. In this case, it is repeated by the same method.
只要濾紙能夠過濾催化劑固體內容物,沒有特定限定,例如可以使用孔徑為0.3 ㎛-5.0 ㎛的PTFE濾紙,但不限於此。As long as the filter paper can filter the catalyst solid content, there is no specific limit. For example, PTFE filter paper with a pore size of 0.3㎛-5.0㎛ can be used, but is not limited to this.
接下來,該方法包含使用醇對第一次經清洗的漿料溶液進行第二次清洗的步驟。Next, the method includes the step of washing the first washed slurry solution a second time with alcohol.
在第一次經清洗的漿料溶液中,殘留作為清洗液的飽和烴系溶劑,在第二次清洗步驟中,藉由使用醇進行第二次清洗,移除相應的溶劑成分,從而在隨後的第三次清洗步驟中使用去離子水以提高催化劑穩定製程的效率。In the first cleaned slurry solution, the saturated hydrocarbon solvent used as the cleaning liquid remains. In the second cleaning step, the corresponding solvent component is removed by using alcohol for the second cleaning, so that the subsequent Deionized water is used in the third cleaning step to improve the efficiency of the catalyst stabilization process.
如果省略使用醇的第二次清洗步驟,即使在殘留有機溶劑的情況下使用去離子水進行清洗,由於溶劑的性質,去離子水可能不會接觸催化劑表面,因此難以達成催化劑穩定。If the second cleaning step using alcohol is omitted, even if deionized water is used for cleaning with residual organic solvent, the deionized water may not contact the catalyst surface due to the nature of the solvent, making it difficult to achieve catalyst stabilization.
第二清洗步驟中使用的醇可以是選自C1-10一級醇、C1-10二級醇和C1-10三級醇組成之群中的一或多種,例如可使用甲醇、乙醇、丙醇、丁醇、己醇及類似物,較佳可以使用乙醇、2-丙醇、1-己醇、2-甲基-2-丙醇及類似物。The alcohol used in the second cleaning step can be one or more selected from the group consisting of C1-10 primary alcohol, C1-10 secondary alcohol and C1-10 tertiary alcohol. For example, methanol, ethanol, propanol, butyl alcohol can be used. Alcohol, hexanol and the like, preferably ethanol, 2-propanol, 1-hexanol, 2-methyl-2-propanol and the like can be used.
醇的用量沒有特定限定,溶劑的用量可以為待測量漿料溶液重量的2-3倍。The amount of alcohol used is not specifically limited, and the amount of solvent used can be 2-3 times the weight of the slurry solution to be measured.
清洗步驟藉由與第一次清洗步驟相同的方法進行,特定而言,可以藉由將第二次清洗步驟用的醇引入包括第一次經清洗的漿料溶液的容器中,讓漿料溶液被清洗。清洗步驟可進行1至3次,較佳2至3次,在此情況下,藉由相同方法重覆進行。The cleaning step is performed by the same method as the first cleaning step. Specifically, the alcohol used in the second cleaning step can be introduced into the container containing the first cleaned slurry solution, so that the slurry solution Be cleansed. The cleaning step can be performed 1 to 3 times, preferably 2 to 3 times. In this case, the same method is repeated.
接著,該方法包含使用去離子水(DI water)步驟對第二次經清洗的漿料溶液進行第三次清洗。Next, the method includes washing the second washed slurry solution a third time using a deionized water (DI water) step.
在第三次清洗步驟中,藉由去離子水進行第三次清洗,活性材料(例如鎳)可能與水接觸,因此,活性材料的表面可能以水合物的形式去活化,從而在乾燥製程中可以防止由於活性材料自熱性質的燃燒,從而能夠穩定測量催化劑重量。經由該製程,最終可以更準確且更穩定地測量催化劑濃度。In the third cleaning step, by performing the third cleaning with deionized water, the active material (such as nickel) may come into contact with water. Therefore, the surface of the active material may be deactivated in the form of hydrates, thereby causing the drying process to fail. Combustion due to the self-heating properties of the active material can be prevented, enabling stable measurement of the catalyst weight. Through this process, the catalyst concentration can ultimately be measured more accurately and more stably.
去離子水的用量沒有特定限定,用量可以為待測量漿料溶液重量的2-3倍。There is no specific limit on the amount of deionized water used, and the amount used can be 2-3 times the weight of the slurry solution to be measured.
清洗步驟藉由與第一次和第二次清洗步驟相同的方法進行,特定而言,可以藉由將第三次清洗用的去離子水引入包括第二次經清洗的漿料溶液的容器中,讓漿料溶液被清洗。清洗步驟可進行1至3次,較佳2至3次,在此情況下,藉由相同方法重覆進行。The cleaning step is performed by the same method as the first and second cleaning steps. Specifically, the deionized water for the third cleaning can be introduced into the container containing the second cleaned slurry solution. , let the slurry solution be cleaned. The cleaning step can be performed 1 to 3 times, preferably 2 to 3 times. In this case, the same method is repeated.
然後,該方法包含將第三次經清洗的漿料溶液在50℃至70℃下乾燥以得到催化劑固內容物的步驟。Then, the method includes the step of drying the third washed slurry solution at 50°C to 70°C to obtain the catalyst solid content.
經由50℃至70℃的乾燥製程,可以有效地移除漿料溶液中殘留的有機溶劑和過量的水分,而無需對催化劑進行改質,更佳的乾燥溫度為55℃至65℃。Through the drying process of 50°C to 70°C, the residual organic solvent and excess moisture in the slurry solution can be effectively removed without modifying the catalyst. The better drying temperature is 55°C to 65°C.
乾燥時間沒有特定限制,可以在上述溫度範圍內進行10~120分鐘,以充分移除殘留的有機溶劑和過量的水分,較佳進行30至60分鐘。There is no specific limit to the drying time. It can be carried out within the above temperature range for 10 to 120 minutes to fully remove the residual organic solvent and excess moisture. It is preferably carried out for 30 to 60 minutes.
乾燥製程的方法沒有特定限制,可以藉由本領域常用的方法進行,例如可以在對流烘箱中進行。The method of the drying process is not particularly limited and can be carried out by methods commonly used in the art, for example, it can be carried out in a convection oven.
經由乾燥製程,可以有效移除漿料溶液中的有機溶劑和過量水分。Through the drying process, the organic solvent and excess moisture in the slurry solution can be effectively removed.
接著,該方法包含測量包含氫化催化劑的石油樹脂漿料溶液的催化劑濃度的步驟,該濃度定義為乾燥後得到的催化劑固體內容物的重量比。Next, the method includes the step of measuring the catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst, the concentration being defined as the weight ratio of the catalyst solid content obtained after drying.
特定而言,漿料溶液中的催化劑濃度可以根據以下數學公式1測量。Specifically, the catalyst concentration in the slurry solution can be measured according to the following mathematical formula 1.
[數學公式1] 漿料溶液中的催化劑濃度(wt%) = (C-B)/A x 100 A:用於測量的石油樹脂漿料溶液的重量 B:使用前濾紙和乾燥皿的重量 C:乾燥後濾紙和包括回收的催化劑固體內容物的乾燥皿的重量 [Mathematical formula 1] Catalyst concentration in slurry solution (wt%) = (C-B)/A x 100 A: Weight of petroleum resin slurry solution used for measurement B: Weight of filter paper and drying dish before use C: Weight of dried filter paper and drying dish including recovered catalyst solid content
如上所述,如果在特定溶劑和特定條件下經由第一次、第二次和第三次清洗步驟測量漿料溶液中的催化劑濃度,可以有效移除石油樹脂漿料殘留物,同時可以使活性材料以水合物形式穩定,因此,可以藉由非常簡單的方法準確地測量漿料溶液中的催化劑濃度。As mentioned above, if the catalyst concentration in the slurry solution is measured through the first, second and third cleaning steps under specific solvents and specific conditions, the petroleum resin slurry residues can be effectively removed while the activity can be The material is stable in hydrate form, so the catalyst concentration in the slurry solution can be accurately measured by a very simple method.
同時,如果將測量漿料溶液中催化劑濃度的方法應用於使用漿料反應器的氫化石油樹脂的連續製備方法,可以有效控制反應器的催化劑濃度,從而穩定地維持反應器的作業。 氫化石油樹脂 的 連續製備方法 At the same time, if the method of measuring the catalyst concentration in the slurry solution is applied to the continuous production method of hydrogenated petroleum resin using a slurry reactor, the catalyst concentration of the reactor can be effectively controlled, thereby stably maintaining the operation of the reactor. Continuous preparation method of hydrogenated petroleum resin
根據本發明另一個具體實例,提供一種氫化石油樹脂的連續製備方法,其使用測量漿料溶液中催化劑濃度的方法。According to another specific example of the present invention, a continuous preparation method of hydrogenated petroleum resin is provided, which uses a method of measuring the catalyst concentration in the slurry solution.
特定而言,該方法包含以下步驟: 將包含石油樹脂、氫化催化劑及溶劑的漿料溶液以及氫氧引入連續漿料反應器,以進行連續氫化反應, 在氫化反應期間回收部分漿料溶液以及測量漿料溶液中氫化催化劑的濃度;及 週期性或非週期性引入及排出氫化催化劑,使得氫化催化劑濃度維持在以漿料溶液總重量計2wt%至20wt%, 其中測量氫化催化劑濃度的步驟包含以下步驟: a) 第一次清洗使用飽和烴系溶劑清洗包含氫化催化劑的石油樹脂漿料溶液; b) 第二次清洗使用醇清洗第一次經清洗的漿料溶液; c) 第三次清洗使用去離子水(DI water)清洗第二次經清洗的漿料溶液; d) 在50℃至70℃乾燥第三次經清洗的漿料溶液以得到催化劑固體內容物;及 e) 測量包含氫化催化劑的石油樹脂漿料溶液的催化劑濃度,該濃度定義為乾燥後得到的催化劑固體內容物的重量比。 Specifically, the method consists of the following steps: The slurry solution containing petroleum resin, hydrogenation catalyst and solvent, and hydrogen and oxygen are introduced into the continuous slurry reactor to perform continuous hydrogenation reaction, Recovering a portion of the slurry solution during the hydrogenation reaction and measuring the concentration of the hydrogenation catalyst in the slurry solution; and Periodically or non-periodically introduce and discharge the hydrogenation catalyst so that the concentration of the hydrogenation catalyst is maintained at 2wt% to 20wt% based on the total weight of the slurry solution, The steps for measuring the hydrogenation catalyst concentration include the following steps: a) The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; b) Use alcohol to clean the first cleaned slurry solution for the second cleaning; c) For the third cleaning, use deionized water (DI water) to clean the second cleaned slurry solution; d) Dry the third cleaned slurry solution at 50°C to 70°C to obtain the catalyst solid content; and e) Measure the catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst, which concentration is defined as the weight ratio of the catalyst solid content obtained after drying.
首先,該方法包含將包含石油樹脂、氫化催化劑及溶劑的漿料溶液以及氫氧引入連續漿料反應器的步驟,以進行連續氫化反應,First, the method includes the step of introducing a slurry solution containing petroleum resin, a hydrogenation catalyst and a solvent, and hydrogen and oxygen into a continuous slurry reactor to perform a continuous hydrogenation reaction,
漿料溶液中石油樹脂、氫化催化劑及溶劑的種類及含量如以上所述,因此不再贅述。The types and contents of the petroleum resin, hydrogenation catalyst and solvent in the slurry solution are as mentioned above, so they will not be described again.
氫化催化劑可以與溶劑或石油樹脂混合並引入。Hydrogenation catalysts can be mixed with solvents or petroleum resins and introduced.
藉由使用漿料反應器將催化劑顆粒分散於反應溶液中並使其連續反應,可以在反應期間週期性或非週期性額外引入一定量的新鮮催化劑,同時可排出催化劑,因此容易控制反應器中催化劑的含量。結果,催化劑的活性可以一直保持恆定。當額外引入新鮮催化劑時,催化劑和溶劑可以在單獨反應器中混合並引入。By using a slurry reactor to disperse catalyst particles in the reaction solution and allow it to react continuously, a certain amount of fresh catalyst can be introduced periodically or non-periodicly during the reaction, and the catalyst can be discharged at the same time, so it is easy to control the reactor Catalyst content. As a result, the activity of the catalyst can be kept constant. When additional fresh catalyst is introduced, the catalyst and solvent can be mixed and introduced in separate reactors.
至於反應器,特定而言,根據混合的方法,可以使用配備攪拌器的高壓釜型反應器或在循環的同時混合反應流體的迴路式反應器。As for the reactor, specifically, depending on the mixing method, an autoclave type reactor equipped with a stirrer or a loop type reactor that mixes the reaction fluid while circulating may be used.
隨後,將氫氧引入連續漿料反應器的同時,進行氫化反應。Subsequently, hydrogenation reaction is performed while introducing hydrogen and oxygen into the continuous slurry reactor.
氫化反應期間的溫度可以為150℃至350℃,較佳為150℃或更高,或200℃或更高及300℃或更低。並且,壓力可以是20巴至100巴,較佳是20巴或更高,或50巴或更高,和100巴或更低。如果氫化反應溫度低於150℃,或壓力低於20巴,則可能無法進行充分反應,又如果反應溫度高於350℃,或壓力高於100巴,則擔憂過度反應和副產物的產生。並且,可以連續引入氫氣,使氫化反應期間可以恆定地保持反應壓力。The temperature during the hydrogenation reaction may be 150°C to 350°C, preferably 150°C or higher, or 200°C or higher and 300°C or lower. And, the pressure may be 20 bar to 100 bar, preferably 20 bar or higher, or 50 bar or higher, and 100 bar or lower. If the hydrogenation reaction temperature is lower than 150°C or the pressure is lower than 20 bar, sufficient reaction may not occur. If the reaction temperature is higher than 350°C or the pressure is higher than 100 bar, there is concern about excessive reaction and the production of by-products. Furthermore, hydrogen can be introduced continuously so that the reaction pressure can be constantly maintained during the hydrogenation reaction.
並且,在加入氫氣之前用惰性氣體(諸如氮氣、氬氣及類似物)或還原氣體(諸如氫氣)吹洗(purging)包括氫化催化劑和石油樹脂的混合物的漿料反應器內部的步驟。較佳地,可以進行用惰性氣體(諸如氮氣)吹洗,然後再用氫氣吹洗的製程。其中,可以根據常用方法進行吹洗製程,並且可以重複進行一次或兩次。And, a step of purging the inside of the slurry reactor including the mixture of the hydrogenation catalyst and the petroleum resin with an inert gas (such as nitrogen, argon and the like) or a reducing gas (such as hydrogen) before adding the hydrogen gas. Preferably, a process of purging with an inert gas (such as nitrogen) and then purging with hydrogen can be performed. Among them, the purging process can be carried out according to common methods, and can be repeated once or twice.
並且,在混合期間,可以額外引入溶劑,其中,可以使用如上所述的烴系溶劑作為溶劑。Also, during mixing, a solvent may be additionally introduced, wherein a hydrocarbon-based solvent as described above may be used as the solvent.
接著,該方法包含在氫化反應期間回收部分漿料溶液並測量漿料溶液中氫化催化劑的濃度的步驟。Next, the method includes the steps of recovering a portion of the slurry solution during the hydrogenation reaction and measuring the concentration of the hydrogenation catalyst in the slurry solution.
特定而言,在氫化反應期間,回收反應器中部分漿料溶液,並經由以下步驟a)、b)、c)、d)及e)測量漿料溶液中的催化劑濃度。 a) 第一次清洗使用飽和烴系溶劑清洗包含氫化催化劑的石油樹脂漿料溶液; b) 第二次清洗使用醇清洗第一次經清洗的漿料溶液; c) 第三次清洗使用去離子水(DI water)清洗第二次經清洗的漿料溶液; d) 在50℃至70℃乾燥第三次經清洗的漿料溶液以得到催化劑固體內容物;及 e) 測量包含氫化催化劑的石油樹脂漿料溶液的催化劑濃度,該濃度定義為乾燥後得到的催化劑固體內容物的重量比。 Specifically, during the hydrogenation reaction, a portion of the slurry solution in the reactor is recovered, and the catalyst concentration in the slurry solution is measured through the following steps a), b), c), d) and e). a) The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; b) Use alcohol to clean the first cleaned slurry solution for the second cleaning; c) For the third cleaning, use deionized water (DI water) to clean the second cleaned slurry solution; d) Dry the third cleaned slurry solution at 50°C to 70°C to obtain the catalyst solid content; and e) Measure the catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst, which concentration is defined as the weight ratio of the catalyst solid content obtained after drying.
步驟a)、b)、c)、d)及e)與測量漿料溶液中催化劑濃度的方法中所述者相同,而因此不再贅述。Steps a), b), c), d) and e) are the same as those described in the method of measuring the catalyst concentration in the slurry solution, and therefore will not be described again.
接著,該方法包含週期性或非週期性引入及排出氫化催化劑以使氫化催化劑的濃度維持在以漿料溶液總重量計2wt%至20wt%的步驟。Next, the method includes the steps of periodically or non-periodically introducing and discharging the hydrogenation catalyst to maintain the concentration of the hydrogenation catalyst at 2 to 20 wt% based on the total weight of the slurry solution.
根據上述測量氫化催化劑濃度的方法導出的濃度可被視為漿料溶液中的總濃度,根據導出的濃度,可以週期性或非週期性引入和排出氫化催化劑以控制濃度。The concentration derived according to the above method of measuring the concentration of the hydrogenation catalyst can be regarded as the total concentration in the slurry solution. According to the derived concentration, the hydrogenation catalyst can be introduced and discharged periodically or non-periodically to control the concentration.
由於連續漿料反應器以使用高溫高壓泵將催化劑漿料在反應器中攪拌的方式操作,因此在具有平衡作業穩定和反應效率的製程條件下操作是重要的。在這方面,如果催化劑的濃度低於2 wt%,氫反應效率可能會降低,而如果催化劑的濃度大於20 wt%,流化催化劑床的強應力可能會導致泵損壞或故障。因此作業可能變得困難並且生產率可能降低。Since the continuous slurry reactor is operated by using a high-temperature and high-pressure pump to stir the catalyst slurry in the reactor, it is important to operate under process conditions that balance operational stability and reaction efficiency. In this regard, if the catalyst concentration is lower than 2 wt%, the hydrogen reaction efficiency may be reduced, while if the catalyst concentration is greater than 20 wt%, the strong stress on the fluidized catalyst bed may cause pump damage or failure. Therefore the work may become difficult and productivity may decrease.
並且,將氫化催化劑多次引入連續漿料反應器中以維持上述濃度,並且週期性或非週期性將其引入和排出。Also, the hydrogenation catalyst is introduced into the continuous slurry reactor multiple times to maintain the above concentration, and is introduced and discharged periodically or non-periodically.
術語「週期性引入」是指第一次引入氫化催化劑的時間(T1)、第二次引入氫化催化劑的時間(T2)、第三次引入氫化催化劑的時間(T3)之間的時間間隔、第n-1次引入氫化催化劑的時間(Tn-1)和第n次引入氫化催化劑的時間(Tn)之間的時間間隔,即T1到T2之間的時間、T2到T3之間的時間和Tn-1到Tn之間的時間都相同。The term "periodic introduction" refers to the time interval between the time when the hydrogenation catalyst is introduced for the first time (T1), the time when the hydrogenation catalyst is introduced for the second time (T2), the time when the hydrogenation catalyst is introduced for the third time (T3), and the time when the hydrogenation catalyst is introduced for the third time (T3). The time interval between the time when the hydrogenation catalyst is introduced for the n-1 time (Tn-1) and the time when the hydrogenation catalyst is introduced for the nth time (Tn), that is, the time between T1 and T2, the time between T2 and T3 and Tn The times between -1 and Tn are all the same.
術語「非週期性引入」是指第一次引入氫化催化劑的時間(T1)、第二次引入氫化催化劑的時間(T2)、第三次引入氫化催化劑的時間(T3)之間的時間間隔、第n-1次引入氫化催化劑的時間(Tn-1)和第n次引入氫化催化劑的時間(Tn)之間的時間間隔,即T1到T2之間的時間、T2到T3之間的時間和Tn-1到Tn之間的時間彼此不相同。The term "aperiodic introduction" refers to the time interval between the time when the hydrogenation catalyst is introduced for the first time (T1), the time when the hydrogenation catalyst is introduced for the second time (T2), and the time when the hydrogenation catalyst is introduced for the third time (T3). The time interval between the time when the hydrogenation catalyst is introduced for the n-1th time (Tn-1) and the time when the hydrogenation catalyst is introduced for the nth time (Tn), that is, the time between T1 and T2, the time between T2 and T3 and The times between Tn-1 and Tn are different from each other.
術語「排出」是指將氫化催化劑的漿料溶液從反應器轉移到能夠藉由操作閥門進行單獨減壓和冷卻的取樣容器中。在取樣容器中,第一漿料溶液和氫氣共存,藉由在冷卻皿管中引入冷卻劑冷卻反應溶液,然後操作取樣容器的閥門排出氫氣,得到在常溫常壓下的測量樣品。The term "discharge" refers to the transfer of the slurry solution of the hydrogenation catalyst from the reactor into a sampling vessel that can be individually depressurized and cooled by operating a valve. In the sampling container, the first slurry solution and hydrogen gas coexist. By introducing a coolant into the cooling dish tube to cool the reaction solution, and then operating the valve of the sampling container to discharge the hydrogen gas, a measurement sample at normal temperature and pressure is obtained.
根據本發明一個具體實例,在第一次引入氫化催化劑後,可以1至24小時的間隔週期性或非週期性引入氫化催化劑。According to a specific example of the present invention, after the hydrogenation catalyst is introduced for the first time, the hydrogenation catalyst may be introduced periodically or non-periodically at intervals of 1 to 24 hours.
並且,第一次引入的氫化催化劑以及之後在反應進行期間引入的氫化催化劑在滿足上述性質的範圍內可以具有相同或不同的鎳和載體含量(wt%)。Also, the hydrogenation catalyst introduced for the first time and the hydrogenation catalyst introduced later during the reaction may have the same or different nickel and support contents (wt%) within the range that satisfies the above properties.
在周期性引入和非週期性引入中,氫化催化劑的引入次數(n)沒有特定限制,只要為2次或2次以上即可,可以根據生產需要多次引入氫化催化劑以進行加氫反應。In periodic introduction and non-periodic introduction, there is no specific limit on the number of introductions (n) of the hydrogenation catalyst, as long as it is 2 or more times, the hydrogenation catalyst can be introduced multiple times according to production needs to perform the hydrogenation reaction.
並且,氫化催化劑的引入時間間隔沒有限制,例如可以根據需要控制在1至24小時以內。Moreover, the time interval for introducing the hydrogenation catalyst is not limited, and can be controlled within 1 to 24 hours as needed, for example.
如上所述,根據本發明一個具體實例的製備方法,在特定溶劑及特定條件下測量經過第一次、第二次及第三次清洗步驟後漿料溶液中的催化劑濃度,因為不會產生催化劑自燃(natural ignition),因此是安全的,並且可以藉由非常簡單的方法準確測量漿料溶液的催化劑濃度。並且,由於藉由引入氫化催化劑進行氫化反應,使得氫化催化劑濃度在連續漿料反應器中維持恆定,因此即使根據氫化反應進行過程需要更換或添加催化劑以控制催化活性時,亦無需停止反應,可以改變中間引入的催化劑,從而使反應連續進行,並恆定維持催化活性,從而顯著改良氫化反應的效率。As mentioned above, according to the preparation method of a specific example of the present invention, the catalyst concentration in the slurry solution after the first, second and third cleaning steps is measured in a specific solvent and under specific conditions, because no catalyst will be produced It is safe due to natural ignition, and the catalyst concentration of the slurry solution can be accurately measured by a very simple method. Moreover, since the hydrogenation reaction is carried out by introducing the hydrogenation catalyst, the concentration of the hydrogenation catalyst is maintained constant in the continuous slurry reactor. Therefore, even if the catalyst needs to be replaced or added according to the progress of the hydrogenation reaction to control the catalytic activity, there is no need to stop the reaction. Changing the catalyst introduced in the middle allows the reaction to proceed continuously and maintain the catalytic activity constantly, thereby significantly improving the efficiency of the hydrogenation reaction.
下文將經由本發明的特定實施例來詳細說明本發明的作用和效果。然而,這些實施例僅作為對本發明的說明,並不由此確定本發明的權利範圍。 [ 實施例 及 比較實施例 ] The functions and effects of the present invention will be explained in detail below through specific embodiments of the present invention. However, these embodiments are only used to illustrate the present invention and do not determine the scope of rights of the present invention thereby. [ Examples and Comparative Examples ]
合成實施例Synthesis Example 11 :氫化催化劑: Hydrogenation catalyst 的of 合成synthesis
將37.5 g多孔二氧化矽粉和硝酸鎳(297.3 g/L)在蒸餾水中的1.875 mL溶液放入沉澱容器中,邊攪拌邊升溫至80℃。達到80℃後,用注射泵在1小時內將1.500 mL碳酸鈉(174.6 g/L)溶液引入沉澱容器中。完成沉澱後,溶液pH為7.5,用約5L蒸餾水洗滌並過濾,然後在120℃的烘箱中乾燥8小時以上。將其細分,然後在氫氣氣氛下於400℃還原活化。使用含有1%氧氣的氮氣混合氣體將活化的催化劑鈍化,從而製備氫化催化劑。Place a 1.875 mL solution of 37.5 g porous silica powder and nickel nitrate (297.3 g/L) in distilled water into a precipitation vessel, and raise the temperature to 80°C while stirring. After reaching 80°C, use a syringe pump to introduce 1.500 mL of sodium carbonate (174.6 g/L) solution into the precipitation vessel within 1 hour. After completing the precipitation, the solution pH is 7.5, wash and filter with about 5L distilled water, and then dry in an oven at 120°C for more than 8 hours. It is subdivided and then reduced and activated at 400°C in a hydrogen atmosphere. The activated catalyst was passivated using a nitrogen gas mixture containing 1% oxygen, thereby preparing a hydrogenation catalyst.
實施例Example 11
98.0 g藉由以60:40的比例混合石油樹脂(藉由Hanwha Solutions製備)和環己烷製備的石油樹脂溶液和2.0 g氫化催化劑混合,以製備石油樹脂漿料溶液,將其引入能以1,600 RPM攪拌的500 mL CSTR(連續攪拌槽反應器)型連續漿料反應器作為原料。固定反應器後,用5 kg/cm 2的N 2吹洗3次,用H 2吹洗3次。 98.0 g of a petroleum resin solution prepared by mixing petroleum resin (prepared by Hanwha Solutions) and cyclohexane in a ratio of 60:40 was mixed with 2.0 g of a hydrogenation catalyst to prepare a petroleum resin slurry solution, which was introduced into the slurry solution at 1,600 A 500 mL CSTR (Continuous Stirred Tank Reactor) type continuous slurry reactor stirred by RPM was used as the raw material. After fixing the reactor, purge it 3 times with 5 kg/cm 2 N and 3 times with H 2 .
將反應器內的溫度升至230℃,然後將反應器加壓至80巴的反應壓力,進行氫化反應1小時。並且,為了將氫化反應期間的反應壓力維持在80巴,連續供應氫氣。The temperature in the reactor was raised to 230°C, and then the reactor was pressurized to a reaction pressure of 80 bar, and the hydrogenation reaction was carried out for 1 hour. Also, in order to maintain the reaction pressure at 80 bar during the hydrogenation reaction, hydrogen gas was continuously supplied.
反應進行1小時後,將石油樹脂漿料溶液從反應器轉移到單獨的取樣容器中,然後冷卻至室溫(約25℃)並減壓至大氣壓(約1atm),得到12 g石油樹脂漿料溶液樣品。將得到的樣品放入上面置有真空過濾機的濾紙(PTFE濾紙)的乾燥皿中,開始過濾。在乾燥皿上,將每次30 g環己烷引入3次以進行第一次清洗步驟。接著,將每次30 g乙醇引入3次以進行第二次清洗步驟。接下來,每次30g去離子水引入3次以進行第三次清洗步驟,從而穩定催化劑活性。完成第一次、第二次和第三次清洗步驟後,取出乾燥的乾燥皿,放入對流烘箱(Ajeon Heating Industries, Convection oven(G2D)),在60℃乾燥30分鐘,從而得到催化劑固體內容物。After the reaction for 1 hour, the petroleum resin slurry solution was transferred from the reactor to a separate sampling container, then cooled to room temperature (about 25°C) and reduced to atmospheric pressure (about 1 atm) to obtain 12 g of petroleum resin slurry. Solution sample. The obtained sample was placed in a drying dish with filter paper (PTFE filter paper) of a vacuum filter placed on it, and filtration was started. On a drying dish, introduce 30 g of cyclohexane 3 times each time for the first cleaning step. Next, 30 g of ethanol each time was introduced 3 times for the second cleaning step. Next, 30 g of deionized water was introduced three times each time for the third cleaning step to stabilize the catalyst activity. After completing the first, second and third cleaning steps, take out the dry drying dish, place it in a convection oven (Ajeon Heating Industries, Convection oven (G2D)), and dry it at 60°C for 30 minutes to obtain the solid content of the catalyst things.
漿料溶液中的催化劑濃度可以根據以下數學公式1測量。 [數學公式1] 漿料溶液中的催化劑濃度(wt%) = (C-B)/A x 100 A:用於測量的石油樹脂漿料溶液的重量 B:使用前濾紙和乾燥皿的重量 C:乾燥後濾紙和包括回收的催化劑固體內容物的乾燥皿的重量 The catalyst concentration in the slurry solution can be measured according to the following mathematical formula 1. [Mathematical formula 1] Catalyst concentration in slurry solution (wt%) = (C-B)/A x 100 A: Weight of petroleum resin slurry solution used for measurement B: Weight of filter paper and drying dish before use C: Weight of dried filter paper and drying dish including recovered catalyst solid content
實施例Example 22
藉由與實施例1相同的方法測量漿料溶液中的催化劑濃度,不同之處在於96.0 g藉由以60:40的比例混合石油樹脂(藉由Hanwha Solutions製備)和環己烷而製備的石油樹脂溶液和4.0 g氫化催化劑混合,以製備石油樹脂漿料溶液。The catalyst concentration in the slurry solution was measured by the same method as Example 1, except that 96.0 g of petroleum prepared by mixing petroleum resin (prepared by Hanwha Solutions) and cyclohexane in a ratio of 60:40 The resin solution and 4.0 g of hydrogenation catalyst were mixed to prepare a petroleum resin slurry solution.
實施例Example 33
藉由與實施例1相同的方法測量漿料溶液中的催化劑濃度,不同之處在於92.0g藉由以60:40的比例混合石油樹脂(藉由Hanwha Solutions製備)和環己烷而製備的石油樹脂溶液和8.0g氫化催化劑混合,以製備石油樹脂漿料溶液。The catalyst concentration in the slurry solution was measured by the same method as Example 1, except that 92.0 g of petroleum prepared by mixing petroleum resin (prepared by Hanwha Solutions) and cyclohexane in a ratio of 60:40 The resin solution and 8.0 g of hydrogenation catalyst were mixed to prepare a petroleum resin slurry solution.
實施例Example 44
藉由與實施例1相同的方法測量漿料溶液中的催化劑濃度,不同之處在於85.0g藉由以60:40的比例混合石油樹脂(藉由Hanwha Solutions製備)和環己烷而製備的石油樹脂溶液和15.0g氫化催化劑混合,以製備石油樹脂漿料溶液。The catalyst concentration in the slurry solution was measured by the same method as Example 1, except that 85.0 g of petroleum prepared by mixing petroleum resin (prepared by Hanwha Solutions) and cyclohexane in a ratio of 60:40 The resin solution and 15.0 g of hydrogenation catalyst were mixed to prepare a petroleum resin slurry solution.
實施例Example 55
藉由與實施例1相同的方法測量漿料溶液中的催化劑濃度,不同之處在於在第二清洗步驟中使用相同含量的1-己基醇取代乙醇。The catalyst concentration in the slurry solution was measured by the same method as in Example 1, except that the same content of 1-hexyl alcohol was used instead of ethanol in the second cleaning step.
實施例Example 66
藉由與實施例1相同的方法測量漿料溶液中的催化劑濃度,不同之處在於在第二清洗步驟中使用相同含量的2-丙醇取代乙醇。The catalyst concentration in the slurry solution was measured by the same method as in Example 1, except that the same content of 2-propanol was used instead of ethanol in the second cleaning step.
實施例Example 77
藉由與實施例1相同的方法測量漿料溶液中的催化劑濃度,不同之處在於在第二清洗步驟中使用相同含量的2-甲基-2-丙醇取代乙醇。The catalyst concentration in the slurry solution was measured by the same method as in Example 1, except that the same content of 2-methyl-2-propanol was used instead of ethanol in the second cleaning step.
比較實施例Comparative Example 11
將12g實施例1的石油樹脂漿料溶液引入上面放置真空過濾機的濾紙(PTFE濾紙)的乾燥皿中,開始過濾。在乾燥皿上,將每次30g環己烷引入3次以進行第一次清洗步驟。然後,取出乾燥皿,放入對流烘箱(Ajeon Heating Industries, Convection oven(G2D)),在60℃下乾燥30分鐘,其中乾燥期間發生快速加熱,因此催化劑不能被回收。12 g of the petroleum resin slurry solution of Example 1 was introduced into a drying dish on which the filter paper (PTFE filter paper) of the vacuum filter was placed, and filtration was started. On the drying dish, introduce 30 g of cyclohexane 3 times each time for the first cleaning step. Then, the drying dish was taken out, placed in a convection oven (Ajeon Heating Industries, Convection oven (G2D)), and dried at 60° C. for 30 minutes, in which rapid heating occurred during the drying period, so the catalyst could not be recovered.
比較實施例Comparative Example 22
將12g實施例1的石油樹脂漿料溶液引入上面放置真空過濾機的濾紙(PTFE濾紙)的乾燥皿中,開始過濾。在乾燥皿上,將每次30g環己烷引入3次以進行第一次清洗步驟。接著,將每次30 g乙醇引入3次以進行第二次清洗步驟。然後,取出乾燥皿,放入對流烘箱(Ajeon Heating Industries, Convection oven(G2D)),在60℃下乾燥30分鐘,其中乾燥期間發生快速加熱,因此催化劑不能被回收。12 g of the petroleum resin slurry solution of Example 1 was introduced into a drying dish on which the filter paper (PTFE filter paper) of the vacuum filter was placed, and filtration was started. On the drying dish, introduce 30 g of cyclohexane 3 times each time for the first cleaning step. Next, 30 g of ethanol each time was introduced three times for the second cleaning step. Then, the drying dish was taken out, placed in a convection oven (Ajeon Heating Industries, Convection oven (G2D)), and dried at 60° C. for 30 minutes, in which rapid heating occurred during the drying period, so the catalyst could not be recovered.
比較實施例Comparative Example 33
將12g實施例1的石油樹脂漿料溶液引入上面放置真空過濾機的濾紙(PTFE濾紙)的乾燥皿中,開始過濾。在乾燥皿上,將每次30g環己烷引入3次以進行第一次清洗步驟。接著,將每次30g去離子水引入3次以進行第二次清洗步驟。然後,取出乾燥皿,放入對流烘箱(Ajeon Heating Industries, Convection oven(G2D)),在60℃下乾燥30分鐘,其中乾燥期間發生快速加熱,因此催化劑不能被回收。 12 g of the petroleum resin slurry solution of Example 1 was introduced into a drying dish on which the filter paper (PTFE filter paper) of the vacuum filter was placed, and filtration was started. On the drying dish, introduce 30 g of cyclohexane 3 times each time for the first cleaning step. Next, 30 g of deionized water was introduced three times each time to perform the second cleaning step. Then, the drying dish was taken out, placed in a convection oven (Ajeon Heating Industries, Convection oven (G2D)), and dried at 60° C. for 30 minutes, in which rapid heating occurred during the drying period, so the catalyst could not be recovered.
實驗實施例Experimental examples 11
根據實施例和比較實施例測量的漿料溶液中的催化劑濃度和誤差顯示於以下表1中。The measured catalyst concentrations and errors in the slurry solutions according to the Examples and Comparative Examples are shown in Table 1 below.
【表1】
如表1的數據所確認的,根據本發明測量漿料溶液中催化劑濃度的方法,可藉由簡單方法測量漿料溶液中催化劑濃度。特別的是,以漿液溶液中的實際催化劑含量計,誤差範圍小於10%,因此證實當該方法應用於連續漿液反應器時,催化劑濃度的測量方法準確性高,因此,不需要單獨的校正製程。As confirmed by the data in Table 1, according to the method of measuring the catalyst concentration in the slurry solution of the present invention, the catalyst concentration in the slurry solution can be measured by a simple method. In particular, based on the actual catalyst content in the slurry solution, the error range is less than 10%, thus confirming that when this method is applied to a continuous slurry reactor, the measurement method of catalyst concentration is highly accurate and, therefore, does not require a separate calibration process. .
同時,如果比較實施例中未完全進行本發明的第一次、第二次和第三次清洗步驟,由於乾燥製程期間受熱,無法測量催化劑濃度。Meanwhile, if the first, second and third cleaning steps of the present invention are not completely performed in the comparative example, the catalyst concentration cannot be measured due to heat during the drying process.
實驗實施例Experimental examples 22
在能夠以1,600 RPM攪拌的500 mL CSTR(連續攪拌槽反應器)型連續漿料反應器中,將以60:40的重量比的石油樹脂原料和環己烷溶劑引入反應器,然後將氫化催化劑引入反應器,將反應器固定,然後用5 kg/cm 2的N 2吹洗3次,H 2吹洗3次。其中,氫化催化劑的引入量以石油樹脂和溶劑的總和(重量)計為4.0wt%。 In a 500 mL CSTR (Continuous Stirred Tank Reactor) type continuous slurry reactor capable of stirring at 1,600 RPM, petroleum resin feedstock and cyclohexane solvent in a weight ratio of 60:40 are introduced into the reactor, and then the hydrogenation catalyst is Introduce the reactor, fix the reactor, and then flush with 5 kg/ cm of N 3 times and H 3 times. Among them, the introduction amount of the hydrogenation catalyst is 4.0wt% based on the total weight of the petroleum resin and solvent.
將反應器內升溫至230℃後,加壓至80巴的反應壓力,進行氫化反應1小時。並且,為了將氫化反應期間的反應壓力維持在80巴,連續供應氫氣。After the temperature in the reactor was raised to 230°C, the pressure was increased to a reaction pressure of 80 bar, and the hydrogenation reaction was carried out for 1 hour. Also, in order to maintain the reaction pressure at 80 bar during the hydrogenation reaction, hydrogen gas was continuously supplied.
對於12g石油樹脂漿料溶液樣品,根據實驗實施例1實施例1的方法測量催化劑濃度。For a 12 g petroleum resin slurry solution sample, the catalyst concentration was measured according to the method of Experimental Example 1 Example 1.
接著,判斷所測量的催化劑濃度的變化程度,在連續氫化反應開始後將催化劑引入/排出反應器,使得催化劑濃度維持在初始催化劑濃度的±0.5wt%。Next, the degree of change in the measured catalyst concentration is judged, and the catalyst is introduced/discharged from the reactor after the continuous hydrogenation reaction is started so that the catalyst concentration is maintained at ±0.5 wt% of the initial catalyst concentration.
然後,為了間隔3小時測量來自上述反應器的漿料溶液中的催化劑濃度,回收漿料溶液樣品,導出催化劑濃度變化,據此將催化劑引入/排出反應器,使得催化劑濃度維持在初始催化劑濃度的±0.5wt%。Then, in order to measure the catalyst concentration in the slurry solution from the above reactor at intervals of 3 hours, recover the slurry solution sample to derive the catalyst concentration change, and accordingly introduce/discharge the catalyst into the reactor so that the catalyst concentration is maintained at the initial catalyst concentration. ±0.5wt%.
催化劑總共引入/排出5次,反應總共進行15小時。The catalyst was introduced/discharged 5 times in total, and the reaction was carried out for a total of 15 hours.
實驗實施例2證實,將本發明的漿料溶液中催化劑濃度的測定方法應用於連續漿料反應器,在共計15小時的反應期間可以有效控制催化劑濃度,從而有效地進行反應。Experimental Example 2 demonstrates that by applying the method for measuring the catalyst concentration in the slurry solution of the present invention to a continuous slurry reactor, the catalyst concentration can be effectively controlled during a total reaction period of 15 hours, thereby effectively performing the reaction.
【表2】
無without
無without
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