CN104148104B - Pyrolysis gasoline hydrogenation processes catalyst and method - Google Patents
Pyrolysis gasoline hydrogenation processes catalyst and method Download PDFInfo
- Publication number
- CN104148104B CN104148104B CN201310179950.0A CN201310179950A CN104148104B CN 104148104 B CN104148104 B CN 104148104B CN 201310179950 A CN201310179950 A CN 201310179950A CN 104148104 B CN104148104 B CN 104148104B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- pyrolysis gasoline
- zeolite
- drippolene
- zsm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010457 zeolite Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 15
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 229910052745 lead Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000000969 carrier Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- -1 BTX aromatic hydrocarbons Chemical class 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 3
- 229910017709 Ni Co Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 238000005336 cracking Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229960000892 attapulgite Drugs 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052625 palygorskite Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 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
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000012263 liquid product Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of pyrolysis gasoline hydrogenation and process catalyst and method, mainly solve Ni Co Mo (W)/Al in existing pyrolysis gasoline hydrogenation purification techniques2O3Hydrobon catalyst can not crack conversion non-aromatics and the technical problem of heavy arene.The present invention includes following component by using in terms of parts by weight: a) 0.01 ~ 1.0 part of at least one in Pt or Pd；B) 97 ~ 99.99 parts of fine grain ZSM-5 5 Zeolite supports, ZSM 5 zeolite grain is smaller in size than 800nm；C) 0 ~ 2 part of auxiliary agent, the auxiliary agent technical scheme of at least one in La, Sn, Pb or Zn preferably solves this problem, can be used in the production that drippolene produces BTX aromatic hydrocarbons.
Description
Technical field
The present invention relates to a kind of pyrolysis gasoline hydrogenation and process catalyst and method.
Background technology
Drippolene is the general name of the by-product C5 ~ 204 DEG C cut during preparing ethylene by steam cracking, essentially from the condensate liquid between water quick cooling tower reactor, debutanization tower reactor and the compressor section of ethylene cracker.Owing to cracking stock, cracking mode, the cracking type of furnace and cracking severity exist notable difference, by-product composition change is very big, and drippolene yield is about the 60 ~ 80% of ethylene yield, and its yield, composition are relevant to the raw material of naphtha and cracking severity.The whole world particularly Asia ethylene industry rapid growth in recent years, by-product drippolene yield synchronizes to be significantly increased.
The composition of drippolene is considerably complicated, and containing having more than 200 kinds of components, including alkane, cycloalkane, diolefin, alkene, cycloolefin, alkynes, aromatic hydrocarbons, alkenyl arene and condensed ring heavy aromatics etc., wherein arene content is up to 60 ~ 75%, is the important sources of aromatic hydrocarbons.Drippolene extremely unstable, during depositing, easily polymerization generates oligomer (green oil) and colloid, it is impossible to directly use, additionally, possibly together with the impurity such as sulphur, nitrogen in drippolene, then the method for the most industrial general employing two-stage hydrogenation carries out solvent extraction.First paragraph hydrogenation uses precious metals pd/Al2O3
Catalyst or Ni catalyst, be mainly hydrogenated with the diolefin of poor heat stability；Second segment uses non-noble metal Ni-Co-Mo/Al2O3
Catalyst carries out hydrogenation of olefins, and removes the plurality of impurities including sulfide.It is one of most important process for purification of oil product it can also be used to the refining modification of drippolene that hydrofinishing processes.Be usually the most in the presence of hydrogen and a catalyst, make the objectionable impurities such as the sulphur in raw material, oxygen, nitrogen be changed into corresponding hydrogen sulfide, water, ammonia and remove, and make alkene and diene hydrogenation saturated.Active metal component in Hydrobon catalyst is often two kinds (referred to as binary metal components) in molybdenum, tungsten, cobalt, nickel, and carrier is mainly aluminum oxide.
Although drippolene processes through traditional secondary hydrogenation, and alkene can be hydrogenated with and remove the impurity such as sulphur, nitrogen, but non-aromatics can not carry out cracking to be converted, therefore the composition of the drippolene of two-stage hydrogenation is broadly divided into alkane, cycloalkane, BTX aromatic hydrocarbons and part heavy arene, it is still necessary to carry out solvent extraction BTX aromatic hydrocarbons.Aromatics Extractive Project is the difference according to aromatic hydrocarbons, non-aromatics solubility in a solvent, reach to separate the purpose of target aromatic hydrocarbons, although solvent extraction BTX can obtain the BTX aromatic hydrocarbons of higher degree, however it is necessary that the solvent extraction apparatus of a set of complexity, and extraction solvent needs constantly to supplement during extraction procedure, therefore solvent extraction occupies drippolene and produces the larger proportion of BTX aromatic hydrocarbons cost.
The cracking of non-aromatics and heavy aromatics take off alkyl and can realize on acid centre.United States Patent (USP) US3,729,409 non-aromaticss proposing to mix with aromatic hydrocarbons are reacted by hydrocracking in the presence of a catalyst and are changed into low-carbon alkanes, can isolate aromatic hydrocarbons by vapour-liquid separator from non-aromatics.Additionally, United States Patent (USP) US3,849,290 and 3,950,241 also proposed the linear hydrocarbon component mixed with aromatic hydrocarbons hydrogenated cracking reaction in the presence of ZSM-5 type zeolite changes into gaseous component to increase the arene content in liquid composition with the method preparing high-quality volatile oil constituents.Korea S's SK patent CN1217892C passes through similar approach, the upgrading such as reformate and drippolene can be prepared as liquefied petroleum gas and light aromatics, but the raw material used is secondary hydrogenation drippolene.
Containing higher sulphur, nitrogen impurity in drippolene, noble metal hydrogenating component is easily made to be poisoned, typically be there is by catalyst modification or load the metal component realization hydrogenation of highly hydrogenated activity, it is also possible to by changing content of metal, the decentralization of carried metal is adjusted.Additionally the too strong meeting of hydrogenation activity causes another side reaction aromatic ring saturated.United States Patent (USP) US5,865,986 proposes to use sulphur compound to control metal active.Additionally, in United States Patent (USP) US6, in 001,241, control degree of hydrogenation with lead or bismuth.The raw material that may contain suppression metal hydrogenation performance component complex for raw material, the drippolene raw material of such as sulfur compound, can consider two kinds of metal composite of Pt, Pd together, this all can have good sulfur resistance thus keep good Hydrogenation than being used alone any one metal of Pt, Pd.Two kinds of metal composite of Pt, Pd can produce mutually electro ultrafiltration or chemical action rather than separately exist in catalyst, thus provide excellent hydrogenation and sulfur resistance.
Summary of the invention
One of the technical problem to be solved is Ni-Co-Mo (W)/Al in existing pyrolysis gasoline hydrogenation purification techniques2O3Hydrobon catalyst can not crack conversion non-aromatics and the technical problem of heavy arene, it is provided that the effective catalyst of a kind of new Zeolite support carried noble metal.This catalyst is in pyrolysis gasoline hydrogenation processes, not only achieve hydrodesulfurization and alkene is saturated, also achieving non-aromatics hydrocracking is light paraffins, and heavy arene part lighting generates the BTX light aromatics of high added value, and product can separate and recover BTX aromatic hydrocarbons by simple distillation.The two of the technical problem to be solved are to provide a kind of method processed with one of solution relevant art problem corresponding catalyst for pyrolysis gasoline hydrogenation.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of pyrolysis gasoline hydrogenation processes catalyst, includes following component: a) in terms of parts by weight
0.01 ~ 1.0 part of at least one in Pt or Pd；B) 97 ~ 99.99 parts of small crystal grain ZSM-5 zeolite carriers, ZSM-5 zeolite crystallite dimension is less than 800nm；C) 0 ~ 2 part of auxiliary agent, at least one in La, Sn, Pb or Zn of auxiliary agent.
In technique scheme, pyrolysis gasoline hydrogenation processes catalyst and it is characterized in that in terms of parts by weight, and the consumption of at least one in Pt or Pd is preferably 0.01 ~ 0.5 part；The consumption of at least one in La, Sn, Pb or Zn is preferably 0.01 ~ 0.5 part；ZSM-5 zeolite crystallite dimension is preferably 30～800 nm；The silica/alumina mole ratio of ZSM-5 zeolite is preferably 30 ~ 150；Binding agent in ZSM-5 zeolite carrier content by weight percentage is preferably not greater than the 70% of vehicle weight；The binding agent used during the shaping of ZSM-5 zeolite carrier is preferably selected from least one in aluminum oxide, silica or concave convex rod.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: with one-stage hydrogenation drippolene and hydrogen as raw material, reaction temperature be 260 ~ 400 ° of C, reaction pressure be 1.0 ~ 5.0Mpa, the weight (hourly) space velocity (WHSV) of drippolene is 1.0 ~ 6.0 hours-1Under conditions of hydrogen/drippolene volume ratio is 400 ~ 1000, raw material and catalyst haptoreaction, the organosulfur compound in raw material is made to be converted into hydrogen sulfide, carry out olefin(e) compound being hydrogenated with, non-aromatics and heavy arene carry out hydrocracking simultaneously, and catalyst used includes following component in terms of parts by weight:
A) 0.01 ~ 1.0 part of at least one in Pt or Pd；
B) 97 ~ 99.99 parts of small crystal grain ZSM-5 zeolite carriers, ZSM-5 zeolite crystallite dimension is less than 800nm；
C) 0 ~ 2 part of auxiliary agent, at least one in La, Sn, Pb or Zn of auxiliary agent.
In technique scheme, reaction temperature is preferably 300 ~ 400 ° of C, and reaction pressure is preferably 2.0 ~ 4.0 Mpa, and the weight (hourly) space velocity (WHSV) of drippolene is preferably 2.0 ~ 5.0 hours-1, hydrogen/drippolene volume ratio is preferably 400 ~ 800.
The preparation method of catalyst of the present invention is as follows: zeolite is with sodium form preparation synthesis, then ion exchange is carried out with the acid solution such as ammonium salt solution or hydrochloric acid, carry out roasting after exchange and be converted into h-type zeolite, then exchanged by ion or at least one metal of dipping method introducing Pt or Pd, use palladium bichloride, palladium nitrate, ammonium chloropalladate, ammonium chloropalladite, platinum nitrate, chloroplatinic acid, ammonium chloroplatinate, ammonium chloroplatinite, dichloro four ammonium closes at least one the aqueous solution of platinum as precursor, hydrogenation activity for regulation noble metal adds La, Sn, at least one in Pb or Zn is as assistant metal.After h-type zeolite introduces Pt or Pd, it is dried under less than 200 ° of C, then at 300 ~ 600 ° of C, dried catalyst is calcined.The catalyst of the present invention is applicable to one section of pyrolysis gasoline hydrogenation and processes, and then produces BTX aromatic hydrocarbons without extracting.
The catalyst of the present invention uses small crystal grain ZSM-5 zeolite as acidic components, there is sour density big, the feature that aperture is unobstructed, metal hydrogenation component has the advantages that Hydrogenation is moderate, has good activity and stability in process the reaction preparing BTX aromatic hydrocarbons for one-stage hydrogenation pyrolysis gasoline hydrogenation.It it is 2.0 ~ 5.0 hours in 300 ~ 400 ° of C of inlet temperature, reaction pressure 2.0 ~ 4.0Mpa, the weight (hourly) space velocity (WHSV) of liquid charging stock-1, hydrogen/drippolene volume basis is 400 ~ 800, one section of drippolene carries out hydrotreating, desulfurized effect and non-aromatics cracking degree high, improves the concentration of BTX in liquid product, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated, but these embodiments are not to limit the scope of the present invention.
Detailed description of the invention
[embodiment 1 ~ 3]
With TPAOH (TPAOH) solution with tetraethyl orthosilicate (TEOS) as raw material, according to mol ratio (TPA)2O:5.5 TEOS:90H2It is stirred overnight under O room temperature and mixes, then under 80 ° of C aging 72 hours, prepare seeding director.With Ludox and aluminum sulfate as raw material, the mol ratio being made into crystallization mother liquor is 28 Na2O:3.3Al2O3: 100 SiO2: 4000
H2O, the seeding director and the 1 of 4% of its weight 5 % is added in crystallization mother liquor, 6-hexamethylene diamine, reaction system is reacted 72 hours in 100 milliliters of crystallizing kettles under 150 ° of C, after filtration washing, drying, roasting, the bright product of XRD stave of sample is the ZSM-5 zeolite of high-crystallinity, SEM characterization result shows zeolite granular a size of 30 ~ 40 ran, and it is 360 meters squared per gram that physical absorption measures its BET specific surface area.Product and ammonium nitrate solution carry out ion exchange, carry out roasting and be converted into h-type zeolite after exchange.With aluminum oxide, Ludox and attapulgite clay, h-type zeolite is shaped respectively, prepare salic by weight percentage 35% Zeolite support, containing silica with the Zeolite support of mass ratio range 29% and containing concave convex rod with the Zeolite support of mass ratio range 67%, respectively at above-mentioned three kinds of supported on carriers Pt and Pd, at 450 DEG C, calcining obtains catalyst a, b and c in 4 hours.
[embodiment 4 ~ 7]
With TPAOH (TPAOH) solution with tetraethyl orthosilicate (TEOS) as raw material, according to mol ratio (TPA)2O:5.5 TEOS:90H2It is stirred overnight under O room temperature and mixes, then under 80 ° of C aging 72 hours, prepare seeding director.With Ludox and aluminum sulfate as raw material, the mol ratio being made into crystallization mother liquor is 28 Na2O:0.67Al2O3: 100 SiO2: 4000
H2O, the seeding director of its weight 10 % is added in crystallization mother liquor, reaction system is reacted 24 hours in 100 milliliters of crystallizing kettles under 180 ° of C, after filtration washing, drying, roasting, the bright product of XRD stave of sample is the ZSM-5 zeolite of high-crystallinity, SEM characterization result shows zeolite granular a size of 100 ~ 200 ran, and physical absorption measures its BET specific surface area 355 meters squared per gram.Product and ammonium nitrate solution carry out ion exchange, carry out roasting and be converted into h-type zeolite after exchange.Using attapulgite clay to be shaped h-type zeolite, prepare the Zeolite support containing concave convex rod with mass ratio range 30%, respectively at above-mentioned supported on carriers Pt and Pb, Pt and Zn, the Sn of Pd and La, Pt sum, at 450 DEG C, calcining obtains catalyst d, e, f and g in 4 hours.
[embodiment 8]
With TPAOH (TPAOH) solution with tetraethyl orthosilicate (TEOS) as raw material, according to mol ratio (TPA)2O:5.5 TEOS:90H2It is stirred overnight under O room temperature and mixes, then under 80 ° of C aging 72 hours, prepare seeding director.Weigh 250 grams of White Carbon blacks, add 10 grams of sesbania powder, aluminum sulfate solution [83.4 grams of Al2(SO4)3·18H2O is dissolved in 50 grams of water] and 40 grams of seeding directors, the Ludox (mass percent 40 wt%) adding 470 grams carries out kneading shaping as binding agent.Reactor is previously added the 40wt% ethylenediamine solution of 40 grams, the cylindric product of 100 grams of above-mentioned preparations is placed in reactor and after porous stainless steel net upper seal, under 180 ° of C, carries out gas-solid phase processor 3 days.Product washs with distilled water after taking out, and obtains adhesiveless ZSM-5 zeolite in 550 ° of C roastings after drying in air atmosphere.The bright product of XRD stave is ZSM-5 zeolite, the zeolite grain 600 ~ 800nm of formed body, and physical absorption measures its BET specific surface area 341 meters squared per gram.Product and ammonium nitrate solution carry out ion exchange, carry out roasting and be converted into h-type zeolite after exchange, supporting Pt and Zn on Hydrogen adhesiveless ZSM-5 zeolite, and at 450 DEG C, calcining obtains catalyst h in 4 hours.
Table 1
[comparative example 1]
The commodity ZSM-4 zeolite (SiO that will buy2/Al2O3Mol ratio is 60, and crystallite dimension is 2000 ~ 3000 nm) swap washing with ammonium nitrate solution, drying, roasting obtain Hydrogen ZSM-5 zeolite, and physical absorption measures its BET specific surface area 317 meters squared per gram.Using attapulgite clay to be shaped h-type zeolite, prepare the Zeolite support containing concave convex rod with mass ratio range 30%, load weight is than the Zn of the Pt and 0.08% of meter 0.05%, and at 450 DEG C, calcining obtains comparative example catalyst in 4 hours.
[embodiment 9]
This example demonstrates that the application that embodiment 1～8 gained catalyst processes at pyrolysis gasoline hydrogenation.
Take the embodiment of the present invention 1～8 gained catalyst each 40ml loading fixed bed reactors and carry out reaction examination.Catalyst in fixed bed reactors in 320 ~ 400 ° of C of inlet temperature, reaction pressure 2.8 Mpa, the weight (hourly) space velocity (WHSV) 3.5 hours of liquid charging stock-1, hydrogen/hydrocarbon raw material volume basis is to check and rate in the case of 600, and the one-stage hydrogenation drippolene raw material composition of employing is by weight percentage: < C6NA
It is 7.15%；C6~C8NA is 7.15%;Benzene is 48.64%；Toluene is 22.30%；Ethylbenzene is 7.06%；Styrene is 0.25%；Dimethylbenzene is 6.90%；C9Component is 0.39%；C10 +Component is 0.93%, and bromine valency is 16.51 gBr2/ 100g oil, S content is 169 ppm.Product calculates liquid yield after stripping tower, is analyzed fluid product composition, and reaction result is listed in table 2.
[comparative example 2]
Take comparative example 1 gained catalyst 40 ml and load fixed bed reactors, use raw material similarly to Example 9 and condition to carry out reaction examination.Reaction result is listed in table 2.
Table 2
[embodiment 10]
This example demonstrates that embodiment 8 gained catalyst changes the result of the test of process conditions in pyrolysis gasoline hydrogenation processes.
Catalyst h is loaded fixed bed reactors, and loadings is 40ml, is passed through one section of drippolene and hydrogen, changes process conditions and tests.The one-stage hydrogenation drippolene raw material composition used is by weight percentage: < C6NA
It is 7.15%；C6~C8NA is 7.15%;Benzene is 48.64%；Toluene is 22.30%；Ethylbenzene is 7.06%；Styrene is 0.25%；Dimethylbenzene is 6.90%；C9Component is 0.39%；C10 +Component is 0.93%, and bromine valency is 16.51 gBr2/ 100g oil, S content is 169 ppm.Product calculates liquid yield after stripping tower, is analyzed fluid product composition, and the result of the test after reaction 48h is shown in Table 3.
Table 3
Claims (10)
1. pyrolysis gasoline hydrogenation processes a catalyst, includes following component in terms of parts by weight:
A) 0.01～1.0 part of at least one in Pt or Pd；
B) 97～99.99 parts of small crystal grain ZSM-5 zeolite carriers, ZSM-5 zeolite crystallite dimension is less than or equal to 800nm；
C) 0～2 part of auxiliary agent, at least one in La, Sn, Pb or Zn of auxiliary agent；
Wherein, described drippolene is one-stage hydrogenation drippolene.
Pyrolysis gasoline hydrogenation the most according to claim 1 processes catalyst, it is characterised in that in terms of parts by weight, the consumption of at least one in Pt or Pd is 0.01～0.5 part.
Pyrolysis gasoline hydrogenation the most according to claim 1 processes catalyst, it is characterised in that in terms of parts by weight, the consumption of at least one in La, Sn, Pb or Zn is 0.01～0.5 part.
Pyrolysis gasoline hydrogenation the most according to claim 1 processes catalyst, it is characterised in that ZSM-5 zeolite crystallite dimension is 30～800nm.
Pyrolysis gasoline hydrogenation the most according to claim 1 processes catalyst, it is characterised in that the silica/alumina mole ratio of described ZSM-5 zeolite is 30～150.
Pyrolysis gasoline hydrogenation the most according to claim 1 processes catalyst, it is characterised in that the binding agent content by weight percentage in described ZSM-5 zeolite carrier is not more than the 70% of vehicle weight.
Pyrolysis gasoline hydrogenation the most according to claim 1 processes catalyst, it is characterised in that at least one in aluminum oxide, silica or concave convex rod of the binding agent used during the shaping of described ZSM-5 zeolite carrier.
8. the method that catalyst described in claim 1 is used for pyrolysis gasoline hydrogenation process, it is characterized in that with one-stage hydrogenation drippolene and hydrogen as raw material, reaction temperature be 260～400 DEG C, reaction pressure be 1.0～5.0MPa, the weight (hourly) space velocity (WHSV) of drippolene is 1.0～6.0 hours-1Under conditions of hydrogen/drippolene volume ratio is 400～1000, raw material and catalyst haptoreaction, the organosulfur compound in raw material is made to be converted into hydrogen sulfide, carry out olefin(e) compound being hydrogenated with, non-aromatics and heavy arene carry out hydrocracking simultaneously, and catalyst used includes following component in terms of parts by weight:
A) 0.01～1.0 part of at least one in Pt or Pd；
B) 97～99.99 parts of small crystal grain ZSM-5 zeolite carriers, ZSM-5 zeolite crystallite dimension is less than or equal to 800nm；
C) 0～2 part of auxiliary agent, at least one in La, Sn, Pb or Zn of auxiliary agent.
The method that pyrolysis gasoline hydrogenation the most according to claim 8 processes, it is characterised in that reaction temperature is 300～400 DEG C, reaction pressure is 2.0～4.0MPa.
The method that pyrolysis gasoline hydrogenation the most according to claim 8 processes, it is characterised in that the weight (hourly) space velocity (WHSV) of drippolene is 2.0～5.0 hours-1, hydrogen/drippolene volume ratio is 400～800.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310179950.0A CN104148104B (en) | 2013-05-16 | 2013-05-16 | Pyrolysis gasoline hydrogenation processes catalyst and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310179950.0A CN104148104B (en) | 2013-05-16 | 2013-05-16 | Pyrolysis gasoline hydrogenation processes catalyst and method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104148104A CN104148104A (en) | 2014-11-19 |
| CN104148104B true CN104148104B (en) | 2016-09-07 |
Family
ID=51873844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310179950.0A Active CN104148104B (en) | 2013-05-16 | 2013-05-16 | Pyrolysis gasoline hydrogenation processes catalyst and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104148104B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582791B (en) * | 2015-10-14 | 2019-04-12 | 中国石油化工股份有限公司 | Catalyst for benzene and ethane ethylbenzene |
| CN107282090B (en) * | 2016-04-12 | 2019-04-12 | 中国石油化工股份有限公司 | The catalyst that ethane is reacted with benzene |
| CN107282100B (en) * | 2016-04-12 | 2019-07-09 | 中国石油化工股份有限公司 | The catalyst of ethane alkylated reaction |
| CN107282098B (en) * | 2016-04-12 | 2019-01-25 | 中国石油化工股份有限公司 | The catalyst reacted for ethane with benzene |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045208B (en) * | 2006-03-27 | 2010-05-12 | 中国石油化工股份有限公司 | Dealkylation and alkyl-transfering catalyst for C9 or more heavy aromatic hydrocarbons |
| CN101734986A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Method for hydrogenation pyrolysis of prolific benzene and xylene by using pyrolysis gasoline |
| CN102744098B (en) * | 2011-04-20 | 2016-04-13 | 中国石油化工股份有限公司 | The catalyst of heavy aromatics hydrocracking volume increase BTX aromatic hydrocarbons and trimethylbenzene |
-
2013
- 2013-05-16 CN CN201310179950.0A patent/CN104148104B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104148104A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101348733B (en) | Method for producing light arene and light alkane from hydrocarbon raw material | |
| TWI478768B (en) | Catalysts and methods for the production of light aromatics and light alkanes from hydrocarbon feedstocks | |
| CN101570698B (en) | Method for catalyzing and transforming naphtha | |
| CN101376823B (en) | Benzin naphtha catalytic reforming method | |
| CN101348405B (en) | Method for preparing light arene and light alkane from hydrocarbon raw material | |
| CN101307254B (en) | Process for producing cleaning gasoline from poor-quality gasoline | |
| EP2690160A1 (en) | Method for producing single-ring aromatic hydrocarbons | |
| CN102744098B (en) | The catalyst of heavy aromatics hydrocracking volume increase BTX aromatic hydrocarbons and trimethylbenzene | |
| CN101347742B (en) | Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials | |
| JP2007154151A (en) | Method for producing 6-8c aromatic hydrocarbon | |
| CN104148104B (en) | Pyrolysis gasoline hydrogenation processes catalyst and method | |
| CN105080592A (en) | Aromatic olefin-reducing catalyst and use thereof | |
| CN103509601B (en) | Technological process for co-production of propane by aromatization of carbon tetrad-hydrocarbon | |
| CN106914260A (en) | Oil product hydrofining catalyst, preparation method and application thereof | |
| CN108659883A (en) | The method and system of gasoline desulfurization and aromatisation | |
| CN103146429B (en) | Method for hydrotreating liquefied gas | |
| CN109562354A (en) | The method for being used to prepare hydrocracking catalyst | |
| CN105562019B (en) | The catalyst of mercaptan thioetherification | |
| CN110653003A (en) | A kind of solid acid catalyst, preparation method and a kind of alkylation reaction method thereof | |
| CN100383222C (en) | A kind of catalytic reforming method using light hydrocarbon as raw material | |
| KR20240129045A (en) | Method and system for producing solvent oil from raffinate oil | |
| CN105268473A (en) | Hydrocarbon oil desulphurization catalyst, and preparation method thereof, and hydrocarbon oil desulphurization method | |
| RU2458103C1 (en) | Catalyst carrier for reforming of gasoline fractions and method of its production | |
| CN102746093B (en) | Heavy aromatics hydrocracking is utilized to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene | |
| US12269998B2 (en) | Method and system for processing gasoline fractions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |