CN101914387B - Catalysis upgrading method for cracking ethylene by-product carbon-9 - Google Patents
Catalysis upgrading method for cracking ethylene by-product carbon-9 Download PDFInfo
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- 238000005336 cracking Methods 0.000 title claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000005977 Ethylene Substances 0.000 title claims abstract description 27
- 239000006227 byproduct Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007670 refining Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 229910003294 NiMo Inorganic materials 0.000 claims description 2
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003502 gasoline Substances 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 9
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- 230000023556 desulfurization Effects 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 229910000510 noble metal Inorganic materials 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 230000009965 odorless effect Effects 0.000 abstract 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- -1 dienes compound Chemical class 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009967 tasteless effect Effects 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 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 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229940065278 sulfur compound Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
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Abstract
The invention discloses a catalysis upgrading method for cracking ethylene by-product carbon-9, belonging to the field of heterogeneous catalysis. The catalysis upgrading method is characterized by comprising the following steps of: firstly, carrying out selective hydrogenation reaction on a metal (noble metal or non-noble metal) catalyst under the mild condition and eliminating dialkene and styrene derivatives, carrying out hydrogenation refining reaction on a sulfide catalyst, and eliminating monoene, nitrogen-containing compounds and sulfur-containing compounds through monoolefine hydrogenation saturation, hydrogen desulfurization and hydrogenation denitrogenation reaction to obtain a water-white and odorless carbon-9 product with favorable stability. The carbon-9 product can be used as a high-octane gasoline ingredient and higher aromatics solvent oil. The metal catalyst and the sulfide catalyst used in the invention are prepared by selecting a proper carrier according to the component and the performance of the cracking ethylene by-product carbon-9 through liquid phase and gaseous phase deposition methods. The invention has the advantages of simple process, high catalyst activity and selectivity, and favorable economic benefit and industrial application potentials.
Description
Technical field
The invention belongs to heterogeneous catalysis field, relate to a kind of cracking ethylene by-product carbon nine catalysis upgradings and produce stop bracket gasoline composition or higher aromatics solvent oil technology.
Background technology
Along with developing rapidly of China's oil chemical industry, ethylene production capacity increases year by year.C 9 fraction of cracking is one of Main By product of cracking ethylene, accounts for the 10-20% of ethene ultimate production.It is expected that, the output of China's C 9 fraction of cracking in 2010 will reach more than 1,000,000 ton/years.Therefore, utilize rationally and effectively the by product C 9 fraction of cracking ethylene just more and more to receive publicity.C 9 fraction of cracking forms complicated, and main component has Styrene and its derivatives, indenes and derivative thereof, dienes compound and Nitrogen or sulfur-compounds, and its chemical constitution changes with the difference of cracking stock, cracking severity and technique.In the C 9 fraction of cracking utilization Main Problems be that the color that causes of its chemical constitution is dark, peculiar smell is large, unstable etc.
Because the olefin(e) centent of C 9 fraction of cracking is high, C 9 fraction of cracking polymerization production petroleum resin, modified petroleum resin, the hydrogenated petroleum resins of adopting, disclose the hydrogenated petroleum resin that utilizes C 9 fraction production performance excellence more as US Patent No. 6458902 at present.Utilize the high characteristics of C 9 fraction of cracking aromaticity content, many families have developed famous oil company the technology that the dealkylation technology is produced benzene, as Hydeal, Detol and Litol technology etc., the catalyzer of use comprises metal catalyst, metal oxide catalyst, zeolite catalyst and dual-function catalyst etc.C 9 fraction of cracking also is used to increase production BTX aromatic hydrocarbons technology, just effectively utilizes carbon nine benzene such as volume increase such as cut such as grade, the aromatic hydrocarbons such as toluene and dimethylbenzene as the APU technology.The catalyzer that adopts be metal load on zeolite, catalyzer need not regeneration.In C 9 fraction of cracking, Multiple components can be as important organic chemical industry and fine chemistry industry chemical simultaneously.US Patent No. 4522688 has been introduced a kind of method of dines separation, can separate basic organic chemical industry raw materials such as obtaining cyclopentadiene, methyl cyclopentadiene.
Chinese patent CN1948441A relates to a kind of cracking carbon nine bubbling bed hydrogenation techniques.Rectifying carbon nine after flash oil after the employing hot polymerization and continuous negative pressure distillation mixes, and obtains a kind of mixing carbon nine raw materials.The adiabatic bubbling bed reactor of cocurrent flow type is adopted in hydrotreatment.This technique weak point is to be only applicable to flash oil and rectifying carbon nine mixing raw materials of low alkene, is unsuitable for cut carbon nine, and does not remove wherein sulfur-bearing and nitrogenous compound, can not produce high-quality gasoline.
Chinese patent CN200710043945 relates to a kind of method for cracking carbon nine and above hydrocarbon hydrogenation thereof, mainly solves the technical problem that the hydrogenation activity that exists in prior art is low, olefin conversion is low, the diolefin hydrogenation rate is low.Take carbon nine and above hydrocarbon feed thereof oil and hydrogen as raw material, be 30-100 ℃ in temperature of reaction, reaction pressure is 2.0-3.5MPa, the stock oil air speed is 1.0-2.5h
-1, hydrogen/oil volume is than being 100-400: under 11 condition, make the unsaturated components such as diolefin in stock oil, alkenyl aromatic hydrocarbon, indenes, dicyclopentadiene change into stable hydrocarbon or alkylaromatic hydrocarbon on nickel on alumina catalyst.The method weak point is not remove sulfur-bearing and nitrogenous compound wherein, can not produce high-quality gasoline.
Chinese patent CN200810151911 relates to extraction agent and the removal methods that removes the C 9 fuel oil medium sulphide content.Extraction agent used can be taken into account yield and the desulfurization degree of C 9 fuel oil, and desulfurization degree can reach 58%, and yield improves the pressure that can alleviate follow-up solvent recuperation.The method weak point is that desulfurization degree is low, complex process, and economy is relatively poor.
Summary of the invention
The technical problem to be solved in the present invention be for cracking ethylene by-product carbon nine utilize that color in process is dark, peculiar smell is large, the problem such as unstable, realize cracking ethylene by-product carbon nine catalysis upgradings take stop bracket gasoline cut or higher aromatics solvent oil as target product.Specifically, the present invention is at first with cracking ethylene by-product carbon nine one-stage hydrogenations, at hydrogen partial pressure 1-6MPa, and volume space velocity 0.5-4.0h
-1, temperature of reaction 30-120 ℃ is 100-1000 with hydrogen to oil volume ratio: carry out hydrogenation reaction under 1 condition and remove diolefine and styrene derivatives on metal catalyst; And then carry out the secondary hydrogenation reaction, and at hydrogen partial pressure 1-6MPa, volume space velocity 0.5-4.0h
-1, temperature of reaction 200-350 ℃ and hydrogen to oil volume ratio are 100-1000: under 1 condition on sulfide catalyst hydrofining remove monoene, sulfur-bearing and the compound such as nitrogenous, produce carbon nine products that obtain water-white, tasteless, good security; Carbon nine products can be used as the stop bracket gasoline composition, also can be used as the higher aromatics solvent oil.
Technical scheme of the present invention is as follows:
Processing raw material in the present invention is cracking ethylene by-product carbon nine cuts, comprises the full cut of carbon nine, the flash distillation cut after synthetic carbon nine resins, and isolate residual C 9 fraction after other component etc.
During reaction, the metal catalyst that one-stage hydrogenation uses is load type metal catalyst, and wherein metal comprises Ni, Cu, Pd, Ru, Pt, and metal content is 0.1-30wt%; Carrier is oxide carrier or the Carbon Materials with two mesopore composite structures, and oxide carrier is SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3Or Al
2O
3-TiO
2The Main Function of metal catalyst is to carry out hydrogenation reaction to remove diolefine and styrene derivatives etc.The sulfide catalyst that secondary hydrogenation uses is oxide carrier or the Carbon Materials with two mesopore composite structures as loading type NiMo, NiW, CoMo, CoW, NiMoW or CoMoW sulfide catalyst, carrier, and oxide carrier is SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3Or Al
2O
3-TiO
2The Main Function of sulfide catalyst is that hydrofining removes monoene, sulfur-bearing and the compound such as nitrogenous, produces carbon nine products that obtain water-white, tasteless, good security.
The present invention be by cracking ethylene by-product carbon nine cuts metal catalyst select hydrogenation and removing diolefine and styrene derivatives etc. and on sulfide catalyst hydrofining remove monoene, sulfur-bearing and the compound such as nitrogenous, the technology of producing stop bracket gasoline composition or higher aromatics solvent oil.Cracking ethylene by-product carbon nine cuts enter reaction system by feedstock pump, mix with hydrogen by the interchanger heating to enter the one-stage hydrogenation reactor, control feeding temperature at 30-120 ℃, are preferably in 50-100 ℃, hydrogen partial pressure 1-6MPa, volume space velocity 0.5-4.0h
-1With hydrogen to oil volume ratio be 100-1000: 1.Reheat after one-stage hydrogenation and enter second stage reactor, control feeding temperature at 200-350 ℃, hydrogen partial pressure 1-6MPa, volume space velocity 0.5-4.0h
-1With hydrogen to oil volume ratio be 100-1000: 1.Product after secondary hydrogenation is refining enters gas-liquid separator through interchanger, obtains the product after liquid is upgrading, can be used as stop bracket gasoline composition or higher aromatics solvent oil; Hydrogen recycles after separation and purification, and other inflammable gass that produce in reaction are used for the reactive system heating.
Technological method of the present invention also is applicable to cracking ethylene carbon five catalysis upgradings.
The present invention has following beneficial effect:
The first paragraph catalysis selective hydrogenation removes diolefine and styrene derivatives under mild conditions, suppressed its polymerization and coking in following process, has increased the life-span of Hydrobon catalyst; Second segment hydrofining removes monoene, sulfur-bearing and the compound such as nitrogenous, makes product water-white, tasteless, good security, solves the problem of present C 9 fraction in utilizing.The yield that obtains product after upgrading by technology production of the present invention is more than 99.5%, and octane value is greater than 97, and sulphur, nitrogen content are all less than 1ppm, bromine number is less than 3gBr/100g, aromaticity content approximately 85%, the color water-white can stop bracket gasoline composition or higher aromatics solvent oil.Product yield is high, wide scope of material, and reaction conditions is gentle, and technique is simple.
Description of drawings
Accompanying drawing is process flow diagram of the present invention.
In figure: 1. feedstock pump; 2. one-stage hydrogenation reactor; 3. process furnace; 4. second-stage hydrogenation reactor;
5. interchanger; 6. gas-liquid separator; 7. compressor.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
The one-stage hydrogenation catalyzer adopts loading type nickel-based catalyst.Carrier adopts SiO
2-Al
2O
3, specific surface area is at 200-400m
2/ g, pore volume is at 0.5-2.0cm
3/ g, the most probable pore size distribution is at 2-4nm and 10-15nm.The metallic nickel precursor adopts nickelous nitrate, nickel acetate or acetylacetonate nickel.Adopt equi-volume impregnating to prepare loading type nickel-based catalyst through dipping-drying-roasting-steps such as reduction, nickel content is between 5-30%, and is best between 10-20%.
The secondary hydrogenation catalyzer adopts supported cobalt molybdenum sulphide catalyzer.Carrier adopts SiO
2-Al
2O
3, specific surface area is at 200-400m
2/ g, pore volume is at 0.5-2.0cm
3/ g, the most probable pore size distribution is at 2-4nm and 10-15nm.Cobalt molybdenum sulphide precursor adopts Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or Cobaltous diacetate or acetylacetone cobalt and ammonium thiomolybdate.Adopt equi-volume impregnating to prepare supported cobalt molybdenum sulphide catalyzer through dipping-drying-steps such as roasting.
Embodiment 2
The one-stage hydrogenation catalyzer adopts load type palladium catalyst based.Carrier adopts SiO
2-Al
2O
3, specific surface area is at 200-400m
2/ g, pore volume is at 0.5-2.0cm
3/ g, the most probable pore size distribution is at 2-4nm and 10-15nm.The palladium metal precursor adopts Palladous nitrate, Palladous chloride, palladium or palladium acetylacetonate.Adopt equi-volume impregnating through that dipping-drying-roasting-steps such as reduction prepare load type palladium is catalyst based, nickel content is between 0.1-5%, and the best is between 0.5-3%.
The secondary hydrogenation catalyzer adopts load-type nickel molybdenum sulphide catalyzer.Carrier adopts SiO
2-Al
2O
3, specific surface area is at 200-400m
2/ g, pore volume is at 0.5-2.0cm
3/ g, the most probable pore size distribution is at 2-4nm and 10-15nm.Nickel molybdenum sulphide precursor adopts nickelous nitrate or nickel acetate or acetylacetonate nickel and ammonium thiomolybdate.Adopt equi-volume impregnating to prepare load-type nickel molybdenum sulphide catalyzer through dipping-drying-steps such as roasting.
Embodiment 3
A kind of character of cracking ethylene by-product carbon nine cuts is as shown in table 1.The density of cracking ethylene by-product carbon nine feedstock is higher, high than the gasoline boiling range as seen from table, and the sulphur nitrogen content is high, contains a large amount of colloids and diene component.Therefore cracking ethylene by-product carbon nine cuts production stop bracket gasoline compositions or higher aromatics solvent oil need to remove sulphur, nitrogen, colloid and diolefin etc., reduce simultaneously density and boiling range.
The character of table 1 cracking ethylene by-product carbon nine cuts
Embodiment 4
Take cracking ethylene by-product carbon nine cuts as raw material, adopting embodiment 1 preparation nickel catalyst carried is the one-stage hydrogenation catalyzer, supported cobalt molybdenum sulphide catalyzer is the secondary hydrogenation catalyst for refining, utilizes two-stage hydrogenation technical scheme production of the present invention to obtain product composed as follows.Following table 2 sees that reaction process condition and product form:
As shown in Table 2, after 90 ℃ of hydrogenation reactions, diolefin content is reduced to 0.80g. (100g) by 5.0 on nickel catalyst carried
-1, and the content of aromatic hydrocarbons, sulphur and nitrogen does not have to change substantially, oily yield 99.9% shows the nickel catalyst carried good ability that removes diolefin compound that has under mild conditions.Remove C 9 fraction after diolefine on supported cobalt molybdenum sulphide catalyzer in 260 ℃ of hydrofinings, diolefine do not detected in the product that obtains, the content of sulphur and nitrogen is less than 1ppm, aromatic hydrocarbons remains on 86.5%, bromine valency 0.22gBr. (100ml)
-1, show that supported cobalt molybdenum sulphide catalyzer has good desulfurization removing nitric deolefination efficient, low aromatic saturation performance.The product water-white that obtains, free from extraneous odour has good stability.
Embodiment 5
Take cracking ethylene by-product carbon nine cuts as raw material, adopting embodiment 2 preparation load type palladium catalysts is the one-stage hydrogenation catalyzer, load-type nickel molybdenum sulphide catalyzer is the secondary hydrogenation catalyst for refining, utilizes two-stage hydrogenation technical scheme of the present invention to produce to such an extent that product is composed as follows.Following table 3 sees that reaction process condition and product form:
As shown in Table 3, on load type palladium catalyst after 70 ℃ and 3.0MPa hydrogenation reaction, diolefin content is reduced to 0.70g. (100g) by 5.0
-1, and the content of aromatic hydrocarbons, sulphur and nitrogen slightly descends, oily yield 99.9% shows that load type palladium catalyst has the good ability that removes diolefin compound under mild conditions.Remove C 9 fraction after diolefine on load-type nickel molybdenum sulphide catalyzer in 250 ℃ of hydrofinings, diolefine do not detected in the product that obtains, the content of sulphur and nitrogen is less than 1ppm, aromatic hydrocarbons remains on 85.5%, bromine valency 0.20gBr. (100ml)
-1, show that load-type nickel molybdenum sulphide catalyzer has good desulfurization removing nitric deolefination efficient, low aromatic saturation performance.The product water-white that obtains, free from extraneous odour has good stability.
Embodiment 6
Take cracking ethylene by-product carbon nine cuts as raw material, carry out stability experiment 4.0MPa and 75 ℃ on the basis of embodiment 5, table 4 provides the reaction process condition of operation in 700 hours and the product property that obtains at last.
Table 4 reaction process condition and product form
The experimental result of 700 hours as shown in Table 4, on load type palladium catalyst after 75 ℃ and 4.0MPa hydrogenation reaction, diolefin content is reduced to 0.60g. (100g) by 5.0
-1, and the content of aromatic hydrocarbons, sulphur and nitrogen slightly descends, oily yield 99.9% shows that load type palladium catalyst has the good ability that removes diolefin compound under mild conditions.Remove C 9 fraction after diolefine on load-type nickel molybdenum sulphide catalyzer in 250 ℃ of hydrofinings, diolefine do not detected in the product that obtains, the content of sulphur and nitrogen is less than 1ppm, aromatic hydrocarbons remains on 85.0%, bromine valency 0.20gBr. (100ml)
-1, show that load-type nickel molybdenum sulphide catalyzer has good desulfurization removing nitric deolefination efficient, low aromatic saturation performance.The product water-white that obtains, free from extraneous odour has good stability.The above results shows that technology of the present invention has satisfactory stability.
Claims (4)
1. cracking ethylene by-product carbon nine catalysis upgrading methods is characterized in that:
Cracking ethylene by-product carbon nine cuts enter to mix with hydrogen by the interchanger heating by feedstock pump and enter the one-stage hydrogenation reactor, control feeding temperature at 30-120 ℃; Hydrogen partial pressure 1-6MPa, volume space velocity 0.5-4.0 h
-1With hydrogen to oil volume ratio be 100-1000:1; The metal catalyst that one-stage hydrogenation uses is load type metal catalyst, and wherein metal is Cu, Pd, Ru or Pt, and metal content is 0.1-30 wt%; Carrier is oxide carrier or the Carbon Materials with two mesopore composite structures, and oxide carrier is SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3Or Al
2O
3-TiO
2
Reheat after one-stage hydrogenation and enter second stage reactor, control feeding temperature at 200-350
oC, hydrogen partial pressure 1-6MPa, volume space velocity 0.5-4.0 h
-1With hydrogen to oil volume ratio be 100-1000:1; Product after secondary hydrogenation is refining enters gas-liquid separator through interchanger, obtains the product after liquid is upgrading; Hydrogen recycles after separation and purification, and other inflammable gass that produce in reaction are used for the reactive system heating; The sulfide catalyst that secondary hydrogenation uses is oxide carrier or the Carbon Materials with two mesopore composite structures as loading type NiMo, NiW, CoMo, CoW, NiMoW or CoMoW sulfide catalyst, carrier, and oxide carrier is SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3Or Al
2O
3-TiO
2
2. a kind of cracking ethylene by-product carbon nine catalysis upgrading methods according to claim 1, be further characterized in that: the raw material of processing is cracking ethylene by-product carbon nine cuts, comprise the full cut of carbon nine, the flash distillation cut after synthetic carbon nine resins and isolate other component after residual C 9 fraction.
3. a kind of cracking ethylene by-product carbon nine catalysis upgrading methods according to claim 1, be further characterized in that: feeding temperature is at 50-100 ℃.
4. according to claim 1,2 or 3 described a kind of cracking ethylene by-product carbon nine catalysis upgrading methods, be further characterized in that: be applicable to cracking ethylene carbon five.
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| CN103059914B (en) * | 2011-10-21 | 2015-03-18 | 中国石油化工股份有限公司 | Method for removing dienes and nitriles from light petroleum product |
| CN102618326B (en) * | 2012-04-20 | 2013-12-11 | 江苏联东化工股份有限公司 | Method for hydrofining C9 petroleum resin |
| CN102660326A (en) * | 2012-05-31 | 2012-09-12 | 中国石油化工股份有限公司 | Hydroprocessing method of cracking C9 |
| CN104449835B (en) * | 2013-09-24 | 2016-05-18 | 中国石油化工股份有限公司 | The method of cracking carbon nine and above hydrocarbon hydrogenation thereof |
| CN103897731B (en) * | 2014-02-24 | 2016-01-20 | 中国海洋石油总公司 | A kind of catalytic cracking diesel oil and C 10+the method of distillate mixture manufacturing light aromatics |
| CN106554814B (en) * | 2015-09-24 | 2019-05-07 | 中国石油天然气股份有限公司 | Thick C inferior9Fraction multi-stek hydrogenation refining methd |
| CN105859965B (en) * | 2016-04-12 | 2019-06-14 | 抚顺新瑞催化剂有限公司 | The method of catalytic hydrogenation preparation high-quality resin |
| CN106832127B (en) * | 2017-02-10 | 2019-07-30 | 恒河材料科技股份有限公司 | A method of orientation plus hydrogen preparation hydrogenation C 9 petroleum resin |
| CN111234867B (en) * | 2018-11-28 | 2022-03-29 | 中国石油化工股份有限公司 | C for pyrolysis gasoline9+Method for hydrogenating distillate |
| CN111234869B (en) * | 2018-11-28 | 2022-03-29 | 中国石油化工股份有限公司 | C for pyrolysis gasoline9+ fraction hydrogenation process |
| CN112295606B (en) * | 2019-07-25 | 2022-11-18 | 中国科学院宁波材料技术与工程研究所 | Production method of aromatic hydrocarbon solvent oil and solvent oil selective hydrogenation catalyst |
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