CN1268433C - Prevulcanizing method for hydrogenating catalyst - Google Patents
Prevulcanizing method for hydrogenating catalyst Download PDFInfo
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- CN1268433C CN1268433C CN 200310104977 CN200310104977A CN1268433C CN 1268433 C CN1268433 C CN 1268433C CN 200310104977 CN200310104977 CN 200310104977 CN 200310104977 A CN200310104977 A CN 200310104977A CN 1268433 C CN1268433 C CN 1268433C
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- alkene
- hydrogenation catalyst
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- organic polysulfide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 135
- 238000000034 method Methods 0.000 title claims abstract description 72
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 44
- 239000005864 Sulphur Substances 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 23
- 150000008116 organic polysulfides Chemical class 0.000 claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 50
- 239000011593 sulfur Substances 0.000 claims description 50
- -1 Sulfur alkene Chemical class 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 34
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 13
- 239000005077 polysulfide Substances 0.000 claims description 11
- 229920001021 polysulfide Polymers 0.000 claims description 11
- 150000008117 polysulfides Polymers 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001924 cycloalkanes Chemical class 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- 239000003921 oil Substances 0.000 description 13
- 229910021536 Zeolite Inorganic materials 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 description 6
- 238000004517 catalytic hydrocracking Methods 0.000 description 5
- 238000003869 coulometry Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 150000002898 organic sulfur compounds Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- VHSBTBDMKDUVKG-UHFFFAOYSA-N (dimethylcarbamothioyltrisulfanyl) n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SSSSC(=S)N(C)C VHSBTBDMKDUVKG-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical class S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 1
- DLLMHEDYJQACRM-UHFFFAOYSA-N 2-(carboxymethyldisulfanyl)acetic acid Chemical compound OC(=O)CSSCC(O)=O DLLMHEDYJQACRM-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- JHZIJVAHARGFEC-UHFFFAOYSA-P N[S+]=C(CCC(S)=[S+]N)S Chemical class N[S+]=C(CCC(S)=[S+]N)S JHZIJVAHARGFEC-UHFFFAOYSA-P 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101100207342 Solanum lycopersicum TPS32 gene Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The present invention discloses a prevulcanization method of a hydrogenation catalyst, which comprises: firstly, the hydrogenation catalyst in an oxidation state is impregnated after an olefin-containing component, an organic polysulfide and an auxiliary agent are mixed and heated; secondly, the hydrogenation catalyst is impregnated with hydrocarbon oil, and the hydrocarbon oil is evaporated to dry to obtain the vulcanized hydrogenation catalyst. The method of the present invention has the advantages of simple and convenient operation, and easy implementation. A high sulphur retention level of the hydrogenation catalyst prevulcanized with the method of the present invention can be maintained in the reaction process, and simultaneously, the hydrogenation catalyst has high catalytic activity. The present invention especially suitable for use in a counter flow reactor can solve the practical problem of activity reduction caused by sulphur loss of a catalyst in the counter flow reactor.
Description
Technical field
The present invention relates to a kind of method for pre-sulphuration of hydrogenation catalyst, particularly relate to a kind of method for pre-sulphuration of catalyst used for hydrogenation of distilled oil fraction.
Background technology
Hydrogenation catalyst pre-curing method is divided into two big classes substantially, i.e. the outer presulfurization method of presulfurization method and device in the device.The presulfurization method is a kind of traditional method for pre-sulphuration in the device, and its shortcoming is cost height, cure time length, has used inflammable and poisonous sulfide, and environment is polluted.Presulfurization also brings catalyst long, problems such as running cost is many, dangerous height on-stream time in the device in addition.
The outer presulfurization method of device was meant before the reactor of packing into and earlier hydrogenation catalyst is combined with vulcanizing agent, reinstalled in the reactor, only need feed hydrogen when going into operation or feed hydrogen and oil product simultaneously, heated up subsequently and can finish the method for sulfuration activation.Because the outer method for pre-sulphuration of device has simple, efficient, free of contamination advantage and is widely used.The outer presulfurization method of device vulcanizing agent commonly used is elementary sulfur and/or organic polysulfide.
US5,215,954A discloses the method for two kinds of presulfurization containing metal oxide catalysts, first method comprises (1) method with distillation and/or fusing, described catalyst is contacted with elementary sulfur, the temperature of contact is sent in the hole of catalyst described elementary sulfur basically, (2) in the presence of liquid olefin, temperature approximately greater than 150 ℃ condition under the catalyst of heating introducing sulphur.Second method comprises the mixture of described catalyst with Powdered elementary sulfur and liquid olefin contacted, and more than the mixture to 150 that obtains of heating ℃.Can reduce the loss of sulphur to a certain extent with this method, improve the reservation degree of sulphur on the catalyst.But; used vulcanizing agent is an elementary sulfur in this patent; because elementary sulfur has easy distillation; dissolve in the raw material oil properties; when device goes into operation as there not being special safeguard measure; elementary sulfur on the catalyst very easily runs off, and makes catalyst vulcanization incomplete and active not enough, can contain too much sulphur in the product oil.Sometimes because of the loss of sulphur, elementary sulfur can condense in the pipeline in device downstream, thereby blocking pipeline causes the stopping production accident.
CN 1040071C discloses the catalyst method that a kind of processing contains at least a metal or nonmetal oxide and at least a reactive metal, this method is to handle catalyst with at least a vulcanizing agent, described vulcanizing agent is selected from elementary sulfur and has the organosulfur compound of R-S (n)-R ' chemical formula, n is 3-20 in the formula, R and R ' can be the same or different, the molecule of each group has 1-150 carbon atom, be selected from by saturated or unsaturated, straight or branched or alkane type alkyl, aryl, alkylaryl and aralkyl, R ' can also represent hydrogen atom.Can reduce the loss of sulphur to a certain extent with this method, improve the reservation degree of sulphur on the catalyst, but can also further improve the reservation degree of sulphur on the catalyst.
US 5,139,990A discloses a kind of Preparation of catalysts method that is used for the raw material of hydrocarbon-containifirst is carried out hydrotreatment, this method comprises that (1) obtains a kind of catalyst, this catalyst contains a kind of carrier material, and this carrier material deposits one or more raw materials to hydrocarbon-containifirst and carries out activated metal of hydrotreatment or metallic compound; (2) contact with the catalyst of step (1) with the liquid medium that contains organosulfur compound, in catalyst, introduce the organosulfur compound of effective dose, described organosulfur compound is selected from following one group: ethylenebis (aminodithioformic acid) salt, 2,5-dimercapto-1,3,4-thiadiazoles salt, thiocarbamide, ammonium sulfocyanate, dimethyl sulfoxide (DMSO), 3,4-dithia adipate, 2,2-dithio glycol.Though this method has improved the reservation degree of the sulphur on the catalyst to a certain extent, the amplitude that sulphur reservation degree improves is nowhere near.
CN 1417299A provides a kind of method for pre-sulphuration of hydrogenation catalyst, this method is earlier a kind of component, elementary sulfur and auxiliary agent that contains alkene to be mixed, again above-mentioned olefine sulfide mixture is mixed with another part elementary sulfur, the hydrogenation catalyst of oxide impregnation attitude heats this catalyst in the presence of nitrogen then.Used auxiliary agent is vulcanization of rubber organic additive commonly used such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, tetramethylthiuram tetrasulfide etc., and these auxiliary agents are poisonous, can pollute environment.The used vulcanizing agent of this method is an elementary sulfur, still has the shortcoming that easily runs off.In addition, this patent is to adopt the reservation degree of sulphur on the method detecting catalyst of acetone extracting, and this can only illustrate the process of static dissolution with solvents sulphur, and can not embody the true mistake sulphur situation of catalyst under the dynamic response state.
Summary of the invention
The purpose of this invention is to provide a kind of hydrogenation catalyst presulfurizing method new, that can further improve the reservation degree of sulphur on the catalyst.Catalyst after the presulfurization of employing this method is specially adapted to low-sulfur charging or the hydrogenation reaction in low-sulfur atmosphere, is particularly useful for the countercurrent reaction technological process of hydrogenation process.
The method for pre-sulphuration of hydrogenation catalyst provided by the invention may further comprise the steps:
A, a kind of component that contains alkene, organic polysulfide and auxiliary agent are mixed, the heating said mixture is 0.5～8 hour under 90～400 ℃ of conditions, preferably, be preferably in 120～180 ℃ of heating 0.5～2 hour, obtain the mixture of Containing Sulfur alkene 90～240 ℃ of heating 0.5～4 hour;
The hydrogenation catalyst of the impregnation mixture oxidation state of B, the Containing Sulfur alkene that obtains with steps A, and under 100～300 ℃ of conditions this solidliquid mixture of heating 0.5～8.0 hour, be preferably in 150～220 ℃ of heating 0.5～4.0 hour;
C, product that step B is obtained under 20～120 ℃ with the hydrocarbon ils dipping after 1～12 hour, the evaporate to dryness hydrocarbon ils makes the hydrogenation catalyst after the sulfuration.
The described component that contains alkene can be one or more in pure liquid monoene, diene and the polyenoid, and described monoene, diene and polyenoid can be straight chain, side chain or cyclic olefin, also can be the alkene of band aromatic ring.The described component that contains alkene is preferably the alkene that contains 5～30 carbon atoms.Can also contain in alkane, cycloalkane, the aromatic hydrocarbons one or more in the described component that contains alkene, wherein the content of alkene is 30wt%～100wt%.Describedly contain the distillate that olefin component can select to contain alkene, wherein the content of alkene is at least more than the 30wt%, preferably hypotoxic alkane of other key components in the distillate or cycloalkane.
It is R-S that described organic polysulfide is selected from general formula
nIn the organic polysulfide of-R ' one or more.General formula is R-S
nIn the organic polysulfide of-R ', n is an integer, and span is 4～8, is preferably 5～7; R and R ' can be identical or different, and expression carbon atoms number is 5～20 alkyl, and this alkyl can be preferably the straight or branched alkyl for alkyl, aryl, alkylaryl or the aryl alkyl of saturated or unsaturated, straight or branched or cycloalkanes type.Described organic polysulfide preferably is selected from one or more in two uncle's dodecyl polysulfides and the two uncle's nonyl polysulfides.
Described auxiliary agent is the mixture of two (propyloxy phenyl base) diphenylamines and propyloxy phenyl base diphenylamines, and wherein the part by weight that accounts for of two (propyloxy phenyl base) diphenylamines is 90wt%～98wt%.
The structural formula of two (propyloxy phenyl base) diphenylamines is:
The structural formula of propyloxy phenyl base diphenylamines is:
The molal quantity of sulphur is no less than the molal quantity of olefinic double bonds in the described organic polysulfide, and auxiliary dosage is the 5wt%～30wt% of sulfur content in the organic polysulfide, preferred 5wt%～20wt%.
The consumption of the mixture of the alkene of Containing Sulfur described in the step B in percent by volume, is 50%～85% of hydrogenation catalyst used therein pore volume.
Hydrocarbon ils described in the step C is one or more in gasoline, diesel oil and the decompressed wax oil, and the volume ratio of used hydrocarbon ils and catalyst is 2: 1～10: 1.
Described oxidation state hydrogenation catalyst comprises Hydrobon catalyst, hydrogenation protecting agent, hydrotreating catalyst and/or hydrocracking catalyst.Generally speaking, Hydrobon catalyst is to be purpose with desulfurization, denitrogenation; Hydrotreating catalyst be with desulfurization, denitrogenation, deolefination, to take off aromatic hydrocarbons be purpose; The hydrogenation protecting agent is to be purpose with demetalization, colloid and other impurity; With produce fuel oil be purpose be hydrocracking catalyst.These catalyst all contain a kind of catalyst carrier and the group vib hydrogenation active metals and the group VIII hydrogenation active metals that load on this carrier.Group vib hydrogenation active metals commonly used is molybdenum and/or tungsten, and group VIII hydrogenation active metals commonly used is nickel and/or cobalt.The catalyst carrier of Hydrobon catalyst, hydrogenation protecting catalyst generally is selected from heat-resistant inorganic oxide.The carrier of hydrocracking catalyst generally is selected from a kind of carrier that contains zeolite and heat-resistant inorganic oxide.The carrier of hydrotreating catalyst both can be a heat-resistant inorganic oxide, also can be the mixture of zeolite and heat-resistant inorganic oxide.
Described heat-resistant inorganic oxide is selected from one or more in the heat-resistant inorganic oxide that is commonly used for catalyst carrier for hydrgenating or matrix, as in aluminium oxide, silica, titanium oxide, zirconia and the boron oxide one or more, be preferably aluminium oxide and/or silica.
Zeolite in described hydrotreating catalyst or the hydrocracking catalyst is to be commonly used in the zeolite of hydrotreating catalyst or carrier of hydrocracking catalyst one or more, generally speaking, described zeolite is selected from one or more in mesopore and the large pore zeolite, as in y-type zeolite, Beta zeolite, the ZSM-5 zeolite one or more.
In described hydrogenation catalyst, can also contain adjuvant component, as fluorine, magnesium, phosphorus, zirconium, boron etc.
According to the reservation degree height of catalyst sulphur in course of reaction of method provided by the invention sulfuration, be specially adapted to the hydrogenation reaction of low-sulfur logistics or low-sulfur atmosphere, be particularly useful for the hydrogenation reaction of counter-current process.
According to method provided by the invention, catalyst is carried out the catalyst activated processing of need before use that presulfurization obtains, make the hydrogenation active metals oxygenate conversion on the catalyst become sulphided state.Be about to the sulfide type catalyst reactor of packing into, slowly be heated to the required temperature of hydrogenation reaction in the presence of hydrogen, this temperature is generally at 200～450 ℃.
The method for pre-sulphuration of hydrogenation catalyst provided by the invention has following characteristics:
(1) according to method provided by the invention catalyst is carried out presulfurization, catalyst can keep higher sulphur reservation degree in course of reaction.When especially this catalyst being applied to counter-current reactor, can solve the practical problem that catalyst reduces because of mistake sulphur activity in the counter-current reactor.
What (2) method provided by the invention adopted is organic polysulfide, rather than elementary sulfur, therefore can avoid the loss because of sulphur, and elementary sulfur condenses in the pipeline in device downstream, thereby blocking pipeline causes the stopping production accident.
What (3) method provided by the invention adopted is the environment-friendly type auxiliary agent, free from environmental pollution.And add the reservation degree that this auxiliary agent can obviously improve sulphur on the catalyst, can also improve activity of such catalysts simultaneously.
(4) adopt method provided by the invention catalyst to be handled with hydrocarbon ils, not only can further improve the reservation degree of sulphur on the catalyst, but also catalyst is vulcanized in pre-vulcanization process evenly, sintering of catalyst is avoided in the heat radiation when helping presulfiding of catalyst simultaneously.
(5) adopt method provided by the invention that catalyst is carried out presulfurization and have advantages of high catalytic activity, promptly its hydrodesulfurization, denitrification activity all are higher than the catalyst of method for pre-sulphuration presulfurization in the device.
(6) method of the present invention is easy and simple to handle, and is easy to implement.
The specific embodiment
The following examples will the present invention will be further described.
The oxidation state hydrogenation catalyst TF-1's that is adopted among the embodiment among the present invention is specifically composed as follows: NiO content is 4wt%, WO
3Content is 26wt%, and modified Y zeolite content is 25wt%, and all the other are aluminium oxide.The clover bar that is shaped as circumscribed circle diameter 1.2mm of this catalyst, the long 3～8mm of bar.The surface area of this catalyst is 221m
2/ g, pore volume are 0.31ml/g.
Used general formula is R-S in the embodiment of the invention
nThe organic polysulfide of-R ' has two kinds: a kind of is two uncle's nonyl polysulfides, n=5 wherein, and R is identical with R ', for uncle's nonyl, derives from ATOCHEM, and commodity are called TPS37, sulfur content 37wt%; Another kind is two uncle's dodecyl polysulfides, n=5 wherein, and R is identical with R ', for uncle's dodecyl, derives from ATOCHEM, and commodity are called TPS32, sulfur content 32wt%.
Embodiment 1
According to method provided by the invention catalyst is carried out presulfurization.
(1) with 87g laurylene (1-Dodecene, boiling point 213-215 ℃, d
4 20Be 0.758) and 22g two uncle's nonyl polysulfides (n=5), and the mixture of 1.5g two (propyloxy phenyl base) diphenylamines and propyloxy phenyl base diphenylamines (wherein the part by weight that accounts for of two (propyloxy phenyl base) diphenylamines is 95wt%) mixes, heat the product liquid that described mixtures obtained Containing Sulfur alkene in 2 hours at 180 ℃, sulfur content is 9.8wt% (a wherein sulfur content employing micro-coulometric determination) in the product;
(2) get the hydrogenation catalyst TF-1 of oxidation state of the product 180ml dipping 80g drying of the Containing Sulfur alkene that (1) obtain, and at 160 ℃ of heating these solidliquid mixtures 1 hour, dry in the shade;
(3) down be that the evaporate to dryness hydrocarbon ils made sulphurized catalyst LHX-1 after 235～335 ℃ light diesel fuel flooded 4 hours with above-mentioned product at 25 ℃ with the 200ml boiling range.
Embodiment 2
According to method provided by the invention catalyst is carried out presulfurization.
(1) with 128g laurylene (1-Dodecene, 213～215 ℃ of boiling points, d
4 20Be 0.758) mix with the mixture of 32.4g two uncle's dodecyl polysulfides (n=5) and 2g two (propyloxy phenyl base) diphenylamines and propyloxy phenyl base diphenylamines (wherein the part by weight that accounts for of two (propyloxy phenyl base) diphenylamines is 95wt%), heat the product liquid that said mixtures obtained Containing Sulfur alkene in 1.5 hours at 160 ℃, sulfur content is 10.95wt% (a wherein sulfur content employing micro-coulometric determination) in the product.
(2) get the oxidation state hydrogenation catalyst TF-1 of the product 200ml dipping 90g drying of the Containing Sulfur alkene that (1) obtain, and at 150 ℃ of heating these solidliquid mixtures 3 hours, dry in the shade;
(3) be 150～250 ℃ of exposure to gasoline after 6 hours with the 220ml boiling range with above-mentioned product down at 80 ℃, the evaporate to dryness hydrocarbon ils makes sulphurized catalyst LHX-2.
Embodiment 3
According to method provided by the invention catalyst is carried out presulfurization.
(1) the 100g decene (is contained α-C
10Alkene 98%) with 25.3g two uncle's nonyl polysulfides (n=5), and the mixture of 1.69g two (propyloxy phenyl base) diphenylamines and propyloxy phenyl base diphenylamines (wherein the part by weight that accounts for of two (propyloxy phenyl base) diphenylamines is 98%) mixes, heat the product liquid that described mixtures obtained Containing Sulfur alkene in 2 hours at 160 ℃, sulfur content is 12.2wt% (a wherein sulfur content employing micro-coulometric determination) in the product.
(2) get the oxidation state hydrogenation catalyst TF-1 of the product 150ml dipping 68g drying of the Containing Sulfur alkene that (1) obtain, and at 150 ℃ of heating these solidliquid mixtures 2 hours, dry in the shade;
(3) down be that the evaporate to dryness hydrocarbon ils made sulphurized catalyst LHX-3 after 235～335 ℃ light diesel fuel flooded 9 hours with above-mentioned product at 50 ℃ with the 186ml boiling range.
Comparative Examples 1
Not according to method provided by the invention catalyst is carried out presulfurization.Adding assistant not in this Comparative Examples.
(1), the 75g decene (is contained α-C
10Alkene 98%) mix with 18.9g two uncle's nonyl polysulfides (n=5), heat the product liquid that described mixtures obtained Containing Sulfur alkene in 1 hour at 200 ℃, sulfur content is 16.1wt% in the product, and wherein sulfur content adopts micro-coulometric determination.
(2), get the oxidation state hydrogenation catalyst TF-1 of the product 140ml dipping 63.5g drying of the Containing Sulfur alkene that (1) obtain, and at 150 ℃ of heating these solidliquid mixtures 3 hours, dry in the shade;
(3), be 235～335 ℃ light diesel fuel dipping after 3 hours with the 127ml boiling range at normal temperatures with above-mentioned product, the evaporate to dryness hydrocarbon ils makes sulphurized catalyst DHX-1.
Comparative Examples 2
Not according to method provided by the invention catalyst is carried out presulfurization.Do not carry out the hydrocarbon ils impregnation steps in this Comparative Examples.
(1) the 60g decene (is contained α-C
10Alkene 98%) with 15.18g two uncle's nonyl polysulfides (n=5), and the mixture of 1.014g two (propyloxy phenyl base) diphenylamines and propyloxy phenyl base diphenylamines (wherein the part by weight that accounts for of two (propyloxy phenyl base) diphenylamines is 95%) mixes, obtained the product liquid of Containing Sulfur alkene in 2 hours at 190 ℃ of described mixtures of heating, sulfur content is 10.68wt% in the product, and wherein sulfur content adopts micro-coulometric determination.
(2) get the oxidation state hydrogenation catalyst TF-1 of the product 135ml dipping 61.2g drying of the Containing Sulfur alkene that (1) obtain, and at 170 ℃ of heating these solidliquid mixtures 4 hours, drying in the shade makes sulphurized catalyst DHX-2.
Comparative Examples 3
Method according to embodiment 2, just the mixture with auxiliary agent two (propyloxy phenyl base) diphenylamines and propyloxy phenyl base diphenylamines changes the organic additive tetramethylthiuram disulfide 4g that does the vulcanization of rubber, other condition with embodiment 2 is identical, obtains sulfide type catalyst DHX-3.
Embodiment 4
The little anti-The effects of sulphur reservation degree situation on the catalyst.
10ml catalyst LHX-1 is loaded in little anti-(little anti-desk-top full-automatic miniature reaction system of Micro-BTRS900/PC of U.S. Autoclave Engineers company that is) device, hydrogen enters from reactor bottom, with the catalyst counter current contacting, reaction pressure 4.0MPa, reaction temperature is slowly risen to 330 ℃ with activating catalyst, hydrogen to oil volume ratio 800: 1, liquid hourly space velocity (LHSV) 2.0h
-1, the reaction time is 48 hours, and raw material is a toluene, and reaction result sees Table 1, and wherein sulfur content adopts ultraviolet fluorescence method to measure on the catalyst.
Embodiment 5-6
The little anti-The effects of sulphur reservation degree situation on the catalyst.
Carry out little anti-experiment by the method for embodiment 4, different just is changed to LHX-2, LHX-3 respectively with catalyst LHX-1, and reaction result sees Table 1.
Comparative Examples 4-6
The little anti-The effects of sulphur reservation degree situation on the catalyst.
Carry out little anti-experiment by the method for embodiment 5, different just is changed to DHX-1, DHX-2, DHX-3 respectively with catalyst LHX-1, and reaction result sees Table 1.
The little anti-experimental result of table 1
| Example number | The catalyst numbering | The relative conversion ratio of toluene, wt% | Relative sulphur reservation degree, wt% |
| 4 | LHX-1 | 100 | 100 |
| 5 | LHX-2 | 108 | 121 |
| 6 | LHX-3 | 106 | 115 |
| Comparative Examples 4 | DHX-1 | 96 | 86 |
| Comparative Examples 5 | DHX-2 | 98 | 89 |
| Comparative Examples 6 | DHX-3 | 97 | 84 |
The result of table 1 shows, hydrogen and feedstock oil adverse current be during through beds, adopt method presulfurization provided by the invention catalyst have a very high sulphur reservation degree.
Embodiment 7
The reactivity worth of the catalyst of the following examples explanation after method presulfurization provided by the invention.
The catalyst LHX-2100ml of embodiment 2 preparation is packed in the reactor of small-sized reaction unit of 100ml, feed hydrogen temperature is slowly risen to 320 ℃ with the activation sulphurized catalyst.Reaction pressure 6.5MPa, 350 ℃ of reaction temperatures, hydrogen to oil volume ratio 800: 1, liquid hourly space velocity (LHSV) 1.5h
-1Feedstock oil character and reaction result see Table 2 and table 3 respectively.
Comparative Examples 7
The explanation of this Comparative Examples adopts the interior method for pre-sulphuration of existing device catalyst to be carried out the catalytic performance of the catalyst of presulfurization.
Embodiment 1 described catalyst TF-1100ml is packed in the reactor of small-sized reaction unit of 100ml, feed the virgin kerosene that contains carbon disulfide 2wt%, reaction pressure 6.5MPa, hydrogen to oil volume ratio 800: 1, liquid hourly space velocity (LHSV) 1.5h
-1, temperature slowly rises to 150 ℃ of constant temperature 1 hour, rises to 230 ℃ of constant temperature 6 hours again catalyst is carried out presulfurization.Under the condition identical, the catalytic activity of catalyst is estimated, be the results are shown in table 3 with identical feedstock oil with embodiment 7.
Comparative Examples 8-10
The explanation of this Comparative Examples adopts Comparative Examples 1,2 and 3 method for pre-sulphuration that catalyst is carried out catalyst DHX-1, the DHX-2 of presulfurization, the catalytic performance of DHX-3.
According to the method evaluate catalysts of embodiment 7, just change catalyst LHX-2 into DHX-1, DHX-2, DHX-3.Feedstock oil character and reaction result see Table 2 and table 3 respectively.
Table 2 feedstock oil character
| Feedstock property | |
| Density (20 ℃), g.cm -3 | 0.9123 |
| Boiling range (ATSM D-86), ℃ 10% 50% 90% | 245 283 344 |
| Nitrogen, μ g.g -1 | 833 |
| Sulphur, μ g.g -1 | 3564 |
| Cetane number | 25.0 |
Table 3 product property
| Numbering | Embodiment 7 | Comparative Examples 7 | Comparative Examples 8 | Comparative Examples 9 | Comparative Examples 10 |
| The catalyst numbering | LHX-2 | TF-1 | DHX-1 | DHX-2 | DHX-3 |
| Product property | |||||
| Density (20 ℃), g.cm -3 | 0.8808 | 0.8864 | 0.8829 | 0.8824 | 0.8853 |
| Nitrogen, μ g.g -1 | 63 | 96 | 84 | 82 | 79 |
| Sulphur, μ g.g -1 | 100 | 180 | 153 | 126 | 147 |
| Cetane number | 35.2 | 33 | 34.1 | 34.4 | 34.9 |
| Cetane number amplification | 10.2 | 8 | 9.1 | 9.4 | 9.9 |
| Desulfurization degree, wt% | 97.1 | 94.9 | 95.7 | 96.5 | 95.9 |
| Denitrification percent, wt% | 92.4 | 88.4 | 89.9 | 90.2 | 90.5 |
The result of table 3 shows, adopt the catalyst of the inventive method presulfurization desulfurization, denitrogenation, take off the catalyst that fragrant activity is better than the vulcanization process sulfuration of adopting in the Comparative Examples, more be better than the catalyst that adopts presulfurization method sulfuration in the device.
Claims (11)
1, a kind of method for pre-sulphuration of hydrogenation catalyst comprises:
A, a kind of component that contains alkene, organic polysulfide and auxiliary agent are mixed, the heating said mixture is 0.5～8.0 hour under 90～400 ℃ of conditions, obtains the mixture of Containing Sulfur alkene;
The hydrogenation catalyst of the impregnation mixture oxidation state of B, Containing Sulfur alkene that steps A is obtained, and under 100～300 ℃ of temperature this solidliquid mixture of heating 0.5～8.0 hour;
C, product that step B is obtained under 20～120 ℃ with the hydrocarbon ils dipping after 1～12 hour, the evaporate to dryness hydrocarbon ils makes the hydrogenation catalyst after the sulfuration;
Olefin(e) centent is 30wt%～100wt% in the described component that contains alkene; It is R-S that described organic polysulfide is selected from general formula
nIn the organic polysulfide of-R ' one or more; Wherein n is an integer, and span is 4～8; R and R ' are identical or different, and expression carbon atoms number is 5～20 alkyl, and this alkyl is alkyl, aryl, alkylaryl or the aryl alkyl of saturated or unsaturated, straight or branched or cycloalkanes type; Described auxiliary agent is the mixture of two (propyloxy phenyl base) diphenylamines and propyloxy phenyl base diphenylamines, and wherein the part by weight that accounts for of two (propyloxy phenyl base) diphenylamines is 90wt%～98wt%; The molal quantity of sulphur is no less than the molal quantity of olefinic double bonds in the described organic polysulfide, and auxiliary dosage is the 5wt%～30wt% of sulfur content in the organic polysulfide.
2, method according to claim 1, it is characterized in that the described component that contains alkene is one or more in pure liquid monoene, diene and the polyenoid, described monoene, diene and polyenoid are one or more in the alkene of straight chain, side chain, ring-type or band aromatic ring.
3, method according to claim 1 and 2 is characterized in that the described component that contains alkene is the alkene that contains 5～30 carbon atoms.
4, method according to claim 1 is characterized in that also containing in the described component that contains alkene in alkane, cycloalkane, the aromatic hydrocarbons one or more.
5, method according to claim 1 is characterized in that described general formula is R-S
nIn the organic polysulfide of-R ', n is an integer, and span is 5～7; R and R ' are identical or different, expression straight or branched alkyl.
6, method according to claim 1 is characterized in that described organic polysulfide is selected from one or more in two uncle's dodecyl polysulfides and the two uncle's nonyl polysulfides.
7, method according to claim 1, the consumption that it is characterized in that described auxiliary agent is the 5wt%～20wt% of sulfur content in the organic polysulfide.
8, method according to claim 1 is characterized in that the consumption of the product of described Containing Sulfur alkene in percent by volume, being 50%～85% of hydrogenation catalyst used therein pore volume.
9, method according to claim 1, the heating-up temperature that it is characterized in that the described mixture of steps A is 90～240 ℃, be 0.5～4 hour heat time heating time; The heating-up temperature of the described mixture of step B is 150～220 ℃, and be 0.5～4 hour heat time heating time.
10, method according to claim 1, the volume ratio that it is characterized in that hydrocarbon ils described in the step C and catalyst is 2: 1～10: 1.
11, method according to claim 1 is characterized in that described hydrocarbon ils is one or more in gasoline, diesel oil and the decompressed wax oil.
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| CN100360237C (en) * | 2005-05-12 | 2008-01-09 | 中国石油化工股份有限公司 | Sulfurized hydrogenation catalyst, prepn. method |
| CN100432191C (en) * | 2005-10-19 | 2008-11-12 | 中国石油化工股份有限公司 | Method for FCC gasoline proceeding hydrodesulphurization and olefin removal |
| JP5086344B2 (en) * | 2006-07-21 | 2012-11-28 | 中國石油化工股▲フン▼有限公司 | Hydrogenation catalyst composition and method for its preparation and use thereof |
| CN102309948A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for charging boiling bed catalyst on line |
| CN103801335B (en) * | 2012-11-08 | 2016-01-20 | 中国石油化工股份有限公司 | The preparation method of sulfurized hydrogenation catalyst |
| CN107446616B (en) * | 2016-05-30 | 2019-08-06 | 中国石油化工股份有限公司 | One kind being hydrocracked start-up method |
| CN109174207B (en) * | 2018-07-11 | 2019-10-29 | 上海英保能源化工科技有限公司 | A kind of activity of hydrocatalyst restores and vulcanization process |
| CN111068794B (en) * | 2018-10-22 | 2023-02-03 | 中国石油化工股份有限公司 | External presulfurization method of hydrogenation catalyst |
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