CN107303496B - A kind of hydrocracking catalyst and its preparation method and application - Google Patents
A kind of hydrocracking catalyst and its preparation method and application Download PDFInfo
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- CN107303496B CN107303496B CN201610252803.5A CN201610252803A CN107303496B CN 107303496 B CN107303496 B CN 107303496B CN 201610252803 A CN201610252803 A CN 201610252803A CN 107303496 B CN107303496 B CN 107303496B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 114
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 113
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000002344 surface layer Substances 0.000 claims abstract description 18
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 16
- 238000007598 dipping method Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- -1 zeolite Ammonium Salt Chemical class 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 238000002803 maceration Methods 0.000 abstract description 8
- 230000009257 reactivity Effects 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 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
- 239000011734 sodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 101100058144 Caenorhabditis elegans bcat-1 gene Proteins 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 101100224937 Paramecium tetraurelia DHC-8 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000519996 Teucrium chamaedrys Species 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000426 electronic spectroscopy Methods 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of hydrocracking catalysts and preparation method thereof, with overall catalyst weight meter, including following component: the silica-alumina supports 30% ~ 80% containing modified Y molecular sieve, active metal 20% ~ 70%, wherein active metal is in terms of metal oxide；Wherein mass percent of the modified Y molecular sieve in silica-alumina supports is 1% ~ 13%, preferably 2% ~ 10%, and surplus is amorphous silica-alumina and/or aluminium oxide；Modified Y molecular sieve lattice constant is 2.425 ~ 2.440；Body phase silica alumina ratio is 20 ~ 50, wherein surface layer silica alumina ratio 50 ~ 120, preferably 60 ~ 100, and surface layer silica alumina ratio is higher than body phase silica alumina ratio 10 ~ 80, preferably 15 ~ 50.Preparation method: including the carrier of modified Y molecular sieve, amorphous silica-alumina and/or aluminium oxide with the maceration extract immersion liquid containing active metal, and then dry, roasting obtains hydrocracking catalyst.Hydrocracking catalyst of the present invention is applied to have good reactivity and anti-nitrogen ability in single-stage hydrocracking technique.
Description
Technical field
The present invention relates to a kind of hydrocracking catalysts and its preparation method and application.
Background technique
Hydrocracking technology is strong with adaptability to raw material, products scheme is flexible, purpose product selectivity is high, good product quality
And added value is high, can directly produce the features such as a variety of high-quality oil products and industrial chemicals.Therefore, which has become reasonable benefit
With limited crude resources, cleaning oil product and the optimum oil Refining Technologies of high-quality industrial chemicals are produced to greatest extent.Add hydrogen
Cracking technology can be mainly divided into three kinds by processing flow: one-stage serial hydrocracking process flow, single-stage hydrocracking technique
Process and two-stage reforming process flow.Wherein one-stage serial process flow setting purification and two reactors of cracking, purification
Organonitrogen removal in raw material to 10 ~ 20ppm or less is added with meeting cracker using Hydrobon catalyst in reactor
After the requirement of hydrogen Cracking catalyst, finishing reactor effluent is directly entered cracker.Two-stage process process equally uses
Two reactors, use hydrogenation catalyst in first reactor, and second reactor uses hydrocracking catalyst, but the
The effluent of one reactor carries out the operation such as gas-liquid separation, and liquid phase enters second two reactor.Compared to one-stage serial
With two-stage reforming technology, single-stage hydrocracking technology is not provided with finishing reactor, using resistance to raw material impurity (sulphur, nitrogen etc.) energy
The stronger hydrocracking catalyst of power, raw material directly carry out hydrocracking process without hydrofinishing, simple with process,
Operation be easy, small investment the features such as, be suitable for maximum production intermediate oil.
In terms of Catalyst For Single-stage Hydrocracking, external more representational technology supplier mainly has Chevron public
Department and Uop Inc..The single hop senior middle school oil hydrocracking catalyst of Chevron company mainly has ICR-106, ICR-120, ICR-
126, ICR-142, ICR-150, ICR-155, ICR-162 etc..It is matched excellent between hydrogenation component and carrier component by carrying out
Change, and the further modification to molecular sieve, the activity of the ICR-142 catalyst of Chevron company exploitation is apparently higher than
ICR-106 amorphous catalyst, and intermediate oil selectivity is suitable with it.The single hop senior middle school oil of Uop Inc.'s exploitation adds hydrogen
Cracking catalyst mainly has HC-102, HC-22, DHC-8, DHC-32, DHC-100, HC-110, HC-115, HC-215 etc..
Single-stage hydrocracking technology requires hydrocracking catalyst to have the stronger energy of resistance to nitrogen due to its own process characteristic
Power, therefore, the hydrocracking catalyst that industrial application process uses generally use amorphous silica-alumina or containing a small amount of high silica alumina ratios
Modified Y or beta-molecular sieve are as its acidic components.Although catalyst has stronger resistance to nitrogen ability, catalyst activity in this way
Poor, reaction temperature is usually more than 400 DEG C.Since reaction temperature is excessively high, limited by aromatic hydrogenation saturation thermodynamical equilibrium, it is excessively high
Reaction temperature it is unfavorable to aromatic hydrogenation saturated reaction, product property is poor.And higher reaction temperature also accelerates catalyst product
Carbon, inactivation affect the cycle of operation of hydrocracking unit.
CN200710158784.0 discloses a kind of hydrocracking catalyst and preparation method thereof containing Y molecular sieve, the hair
Bright middle Y type molecular sieve is obtained with after the mixed aqueous solution of aluminium salt and acid processing hydro-thermal process, and catalyst activity obtained is higher,
But resistance to nitrogen ability is poor.
CN98114489.6 discloses a kind of hydrocracking catalyst of nitrogen-resistant type multiferous middle oil, is used for heavy distillate one
Section serial hydrocracking produces a large amount of intermediate oils, and cracking zone feeds nitrogen content up to 100 μ g/g, but the catalyst activity
It is poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of hydrocracking catalyst and preparation method thereof, and the present invention adds
Hydrogen Cracking catalyst has good reactivity and anti-nitrogen ability.
Hydrocracking catalyst of the invention, with overall catalyst weight meter, including following component: containing modified Y molecular sieve
Silica-alumina supports 30% ~ 80%, active metal 20% ~ 70%, wherein active metal is in terms of metal oxide；Wherein the modification Y points
Mass percent of the son sieve in silica-alumina supports is 1% ~ 13%, preferably 2% ~ 10%, and surplus is amorphous silica-alumina and/or aluminium oxide；
Wherein the modified Y molecular sieve has the property that lattice constant is 2.425 ~ 2.440；Body phase silica alumina ratio is 20 ~ 50,
Middle surface layer silica alumina ratio 50 ~ 120, preferably 60 ~ 100, surface layer silica alumina ratio is higher than body phase silica alumina ratio 10 ~ 80, preferably 15 ~ 50.Wherein institute
The surface layer stated refers to the thickness range of molecular sieve outer surface to 10 ~ 200nm of inside, preferably 50 ~ 190nm；Sodium oxide molybdena quality percentage contains
Amount is less than 1.0%, and preferably smaller than 0.5%；600 ~ 800m of modified Y molecular sieve specific surface area2/g；Hole holds 0.40 ~ 0.70ml/g；It is infrared
0.1 ~ 0.8mmol/g of acid content, preferably 0.2 ~ 0.6mmol/g；Relative crystallinity 60% ~ 90%.
Hydrocracking catalyst of the invention, group VIII of the active metal in the periodic table of elements and/or
Vib metals element, group VIII active metal can be Ni and/or Co, group VIB active metal can be W and/or
Mo, group VIII active metallic content are 3% ~ 15%, and group VIB active metallic content is 10% ~ 40%, in terms of metal oxide.
The specific surface area of hydrocracking catalyst of the invention is 100 ~ 300m20.2 ~ 0.5ml/g of/g, Kong Rongwei.
In hydrocracking catalyst of the present invention, the preparation method of the modified Y molecular sieve, including following content:
(1) Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution by original powder of NaY zeolite；
(2) hydro-thermal process is carried out to the Y molecular sieve after ammonium obtained in step (1) exchange；
(3) to the Y molecular sieve acid dealumination treatment after step (2) hydro-thermal process；
(4) the resulting Y molecular sieve rapid draing of step (3) is handled；
(5) Y molecular sieve that step (4) obtains comes into full contact with liquid or gaseous unsaturated olefin, then oxygenous
Carbon deposit reaction is carried out in atmosphere；
(6) molecular sieve for obtaining step (5) carries out desiliconization processing；
(7) treated after Y molecular sieve filtered, dried through desiliconization for step (6), carries out processing of making charcoal, obtains modified Y points
Son sieve.
Ammonium Salt Ionic exchange process described in step (1) is as follows: it is raw material in ammonium salt aqueous solution using NaY zeolite, 60 ~
It at 120 DEG C, at preferably 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, exchange times are 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O contains
Amount is less than 3.0%；The wherein SiO of NaY zeolite raw material2/Al2O3Molar ratio is 3 ~ 6, sodium oxide molybdena mass percentage 6% ~ 7%；Ammonium salt
It is one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, 0.3 ~ 6.0mol/ of ammonium salt aqueous solution concentration
L, preferably 1.0 ~ 3.0 mol/L.
Step (2) described hydrothermal treatment process is the hydro-thermal process item in itself vapor or under conditions of be passed through vapor
Part are as follows: temperature be 550 ~ 700 DEG C, pressure be 0.01 ~ 0.5MPa, processing the time be 1.0 ~ 6.0 hours, hydro-thermal process number be 1 ~
3 times.
Sour dealumination treatment process described in step (3) is conventional method, i.e. the mixing with inorganic acid and/or organic acid is molten
The Y molecular sieve that liquid processing step (2) obtains.Step (2) inorganic acid that uses of acid treatment process or organic acid be sulfuric acid, hydrochloric acid,
One of nitric acid, citric acid, oxalic acid or acetic acid are a variety of, and the concentration of inorganic acid and/or organic acid is with H+It is calculated as 0.7 ~ 3mol/
L, preferably 1.0 ~ 2.0mol/L；The liquid/solid mass ratio of sour dealumination treatment process is 3:1 ~ 30:1；60 ~ 120 DEG C for the treatment of temperature；Place
Managing the time is 0.5 ~ 3 hour.
Rapid draing treatment conditions described in step (4) are as follows: drying temperature is 100 ~ 200 DEG C, preferably 120 ~ 160 DEG C, is done
The dry time is 1 ~ 60 minute, preferably 3 ~ 30 minutes.General treatment process are as follows: be directly added into step (3) resulting Y molecular sieve
It is warming up in the Muffle furnace or other heating equipments of drying temperature and is roasted in advance.It is handled by rapid draing, removes molecule
Sieve surface moisture.
Unsaturated olefin described in step (5) is the positive structure or isomeric olefine, alkadienes that charcoal atomicity is 2 ~ 10；Wherein institute
The alkene and molecular sieve stated, which come into full contact with, refers to that unsaturated olefin diffuses into inside molecular sieve；When use gaseous state unsaturated olefin
When, gaseous state unsaturated olefin and molecular sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.1 ~ 2 hour；When use liquid
When state unsaturated hydrocarbons, liquid unsaturated olefin and molecular sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.5 ~ 4 are small
When, molecular sieve answers thorough impregnation in liquefied olefines.The alkene comes into full contact with molecular sieve and generally carries out at normal temperature, institute
The unsaturated hydrocarbons state phase stated is phase under room temperature.
Oxygen-containing atmosphere described in step (5) is the mixing of air, the mixture of oxygen and nitrogen or oxygen and inert gas
One of object, the volume fraction of oxygen in the gas phase are 10% ~ 100%, preferably air；Carbon deposit reaction condition are as follows: reaction temperature
50 ~ 500 DEG C of degree, preferably 100 ~ 400 DEG C, the reaction time is 1 ~ 50 hour, preferably 2 ~ 40 hours.
The processing of desiliconization described in step (6) is method well known to those skilled in the art, can be using conventional alkali desiliconization
Method, the lye that alkali desiliconization treatment process uses are the aqueous solution of sodium hydroxide or potassium hydroxide, and wherein the concentration of lye is
0.1wt%~2wt%.50 ~ 100 DEG C of base extraction temperature, the processing time is 0.5 ~ 4 hour, and lye/molecular sieve liquid consolidates mass ratio and is
5:1~10:1。
Step (7) drying condition is 90 DEG C ~ 120 DEG C of temperature, and drying time is 2 ~ 4 hours；Treatment conditions of making charcoal are
It is roasted 2 ~ 4 hours at 400 ~ 600 DEG C, removes remaining carbon deposit on molecular sieve.
The surface layer is formed by internal desiliconization in situ.I.e. the modified Y molecular sieve carries out Y molecular sieve crystal grain before modified
Internal desiliconization, so that the lower internal layer of silica alumina ratio is obtained, thus to obtain the modification Y with surface layer and internal layer of integral structure
Molecular sieve.
The preparation method of hydrocracking catalyst of the invention, including following content:
One, modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide are uniformly mixed according to a certain ratio, dust technology is added
Rear extruded moulding is slurried, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；Wherein the concentration of dust technology be 3wt% ~
30wt%；The drying condition are as follows: 1 ~ 5 hour dry at 80 ~ 120 DEG C；Roasting condition are as follows: at 400 ~ 700 DEG C roast 1 ~
5 hours；
Two, it is impregnated using carrier of the maceration extract containing active metal to step 1, the carrier after dipping is through drying, roasting
It burns, obtains hydrocracking catalyst；The liquid-solid ratio wherein impregnated is 1.5:1 ~ 3:1, using saturation dipping well known in the art
Mode carries out, and the content of group vib metallic compound is calculated as 20 ~ 60g/100ml, group VIII gold by corresponding oxide in maceration extract
The content for belonging to compound is calculated as 3 ~ 20g/100ml by corresponding oxide, and the concentration of metallic compound can be according to production in maceration extract
Product needs adjust accordingly；The wherein drying condition are as follows: 2 ~ 8 hours dry at 90 ~ 150 DEG C；Roasting condition are as follows: In
It is roasted 1 ~ 5 hour at 400 ~ 700 DEG C.
Hydrocracking catalyst of the present invention can be applied to single-stage hydrocracking technological reaction process, general operational requirement(GOR) are as follows:
6.0 ~ 20.0MPa of reaction pressure, 350 ~ 420 DEG C of reaction temperature, 0.3 ~ 3.0h of feed volume air speed-1, hydrogen to oil volume ratio 500:1
~ 2000:1.
In the present invention, silica alumina ratio is the molar ratio of silica and aluminium oxide.
In the present invention, body phase silica alumina ratio refers to the silica alumina ratio of modified molecular screen entirety.
In the present invention, body phase silica alumina ratio is measured using chemical analysis.Surface layer silica alumina ratio uses transmission electron microscope X
Ray electronic spectroscopy measures.
In the method for the present invention, specially treated is carried out to the Y molecular sieve that hydrocracking catalyst uses, i.e., first in air gas
Make to be adsorbed in the unsaturated hydrocarbons such as alkene, the alkadienes on Y molecular sieve surface layer in atmosphere, under heating condition in molecular sieve surface layer carbon deposit, because
This, subsequent alkaline desiliconization treatment process is mainly upper inside molecular sieve to be carried out, and after desiliconization is processed, then molecular sieve is removed in high-temperature roasting
The carbon deposit on surface layer.The method of the present invention carries out desiliconization to Y molecular sieve inner surface by selectivity, it is selective reduce it is internal
Silica alumina ratio reduces the silica alumina ratio of body phase molecule sieve, the silica alumina ratio on Y molecular sieve surface layer is made to be higher than body phase silica alumina ratio.The present invention
Hydrocracking catalyst for showing higher anti-nitrogen ability in single-stage hydrocracking technical process, have preferably activity,
Stability.
Specific embodiment
Below by embodiment, the present invention is further described, but is not so limited the present invention.Involved in embodiment
Percentage is mass percent (except relative crystallinity), and the liquid-solid ratio is that liquid consolidates mass ratio.
Embodiment 1
Molecular sieve modified treatment process:
(1) the NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 0.5mol/L with concentration is according to liquid-solid ratio
3:1 mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.5%；
(2) 620 DEG C of Y molecular sieve obtained to step (1), hydro-thermal process 2 hours under 0.1MPa repeat this process 2 times.
(3) (concentration is with H according to the hydrochloric acid solution of liquid-solid ratio 10:1 and concentration 1.5mol/L for step (2) resulting molecular sieve+
Meter) it mixes, constant temperature is handled 2 hours at 80 DEG C；
(4) 150 DEG C of molecular sieve dry 15min obtained by step (3)；
(5) it takes step (4) resulting molecular sieve to be placed in the closed container full of butadiene atmosphere, controls pressure
0.3MPa is contacted 20 minutes, then, is heated 15 hours in air atmosphere at 200 DEG C；
(6) step (5) resulting Y molecular sieve is mixed according to liquid-solid ratio 5:1 with 0.7% sodium hydroxide solution, 90 DEG C of processing
2 hours；
(7) Y molecular sieve after step (6) alkali process, 120 DEG C drying 2 hours, 550 DEG C roasting 2 hours after, changed
Property Y molecular sieve, number Y-1.
Y-1 molecular sieve transmission electron microscope EDAX results measure its outer surface to 120nm thickness, and surface layer silica alumina ratio is 73,
Molecular sieve phase silica alumina ratio is 31.XRD analysis the result shows that its lattice constant be 2.434, relative crystallinity 78%.Kong Rong
0.55ml/g, specific surface area 690m2/ g, infrared acid analysis result measurement Y-1 meleic acid amount is 0.60mmol/g.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 430g and nickel nitrate 440g to be dissolved in water
Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 36g/100ml and 11g/100ml, molten
Liquid number RY-1；
(2) it takes Y-1 4g to mix with 50g amorphous silicon aluminium and 46g macroporous aluminium oxide, 4g/100ml dust technology is added mixed
Mixing is rolled to extrudable shape in clutch, and extruded moulding obtains carrier T-1 on banded extruder；
(3) T-1 60g is taken 120ml RY-1 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings
It burns 3 hours, obtains hydrocracking catalyst, number Cat-1.
Embodiment 2
Molecular sieve modified treatment process:
(1) the NaY molecular sieve original powder for taking laboratory to prepare, the ammonium nitrate for being 0.8mol/L with concentration is according to liquid-solid ratio 3:1
Mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.0%.
(2) 660 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 2 hours under 0.15MPa；
(3) step (2) resulting molecular sieve is according to liquid-solid ratio 7:1 and H+The hydrochloric acid mixed solution that concentration is 1.8mol/L is mixed
It closes, 95 DEG C are handled 2 hours；
(4) 130 DEG C of molecular sieve dry 20min obtained by step (3)；
(5) the resulting molecular sieve 30min of heptene soaking step (4) is taken, then, 250 DEG C of heating 20 are small in air atmosphere
When；
(6) step (5) resulting molecular sieve is mixed according to liquid-solid ratio 6:1 with 1.3% sodium hydroxide solution, 80 DEG C of processing
3 hours；
(7) Y molecular sieve after step (6) alkali process, 120 DEG C drying 2 hours, 550 DEG C roasting 2 hours after, changed
Property Y molecular sieve, number Y-2.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 480g and nickel nitrate 480g to be dissolved in water
Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 40g/100ml and 12g/100ml, molten
Liquid number RY-2；
(2) it takes Y-2 4g to mix with 50g amorphous silicon aluminium and 46g macroporous aluminium oxide, 4g/100ml dust technology is added mixed
Mixing is rolled to extrudable shape in clutch, and extruded moulding obtains carrier T-2 on banded extruder；
(3) T-2 60g is taken 120ml RY-2 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings
It burns 3 hours, obtains hydrocracking catalyst, number Cat-2.
Y-2 molecular sieve transmission electron microscope EDAX results measure its outer surface to 150nm thickness, and surface layer silica alumina ratio is 69,
Molecular sieve phase silica alumina ratio is 28.XRD analysis the result shows that its lattice constant be 2.435, relative crystallinity 80%.Hole holds 0.52
Ml/g, specific surface area 700m2/ g, it is 0.63mmol/g that infrared analysis result, which measures Y-2 meleic acid amount,.
Embodiment 3
Molecular sieve modified treatment process:
(1) the NaY molecular sieve original powder for taking laboratory to prepare, the ammonium nitrate for being 0.8mol/L with concentration is according to liquid-solid ratio 3:1
Mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.0%.
(2) 600 DEG C of Y molecular sieve obtained to step (1) hydro-thermal process 1.5 hours under 0.3 MPa, repeat this process 2
It is secondary；
(3) step (2) resulting molecular sieve is according to liquid-solid ratio 7:1 and H+The hydrochloric acid mixed solution that concentration is 1.2mol/L is mixed
It closes, 80 DEG C are handled 2.5 hours；
(4) 120 DEG C of molecular sieve dry 35min obtained by step (3)；
(5) the resulting molecular sieve 50min of heptene soaking step (4) is taken, then, 300 DEG C of heating 12 are small in air atmosphere
When；
(6) step (5) resulting molecular sieve is mixed according to liquid-solid ratio 6:1 with 1.2% sodium hydroxide solution, 75 DEG C of processing
2 hours；
(7) Y molecular sieve after step (6) alkali process, 120 DEG C drying 2 hours, 550 DEG C roasting 2 hours after, changed
Property Y molecular sieve, number Y-3.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 480g and nickel nitrate 480g to be dissolved in water
Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 40g/100ml and 12g/100ml, molten
Liquid number RY-3；
(2) it takes Y-3 8g to mix with 40g amorphous silicon aluminium and 52g macroporous aluminium oxide, 4g/100ml dust technology is added mixed
Mixing is rolled to extrudable shape in clutch, and extruded moulding obtains carrier T-3 on banded extruder；
(3) T-3 60g is taken 120ml RY-3 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings
It burns 3 hours, obtains hydrocracking catalyst, number Cat-3.
Y-3 molecular sieve transmission electron microscope EDAX results measure its outer surface to 190nm thickness, and surface layer silica alumina ratio is 70,
Molecular sieve phase silica alumina ratio is 45.XRD analysis the result shows that its lattice constant be 2.431, relative crystallinity 78%.Hole holds 0.52
Ml/g, specific surface area 710m2/ g, it is 0.53mmol/g that infrared analysis result, which measures Y-3 meleic acid amount,.
Embodiment 4
Molecular sieve modified treatment process:
(1) the NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 0.6mol/L with concentration is according to liquid-solid ratio
3:1 mixing, 80 DEG C exchange 3 hours, repeat this process 3 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.0%；
(2) 580 DEG C of Y molecular sieve obtained to step (1), hydro-thermal process 1 hour under 0.1MPa repeat this process 3 times；
(3) (concentration is with H according to the hydrochloric acid solution of liquid-solid ratio 15:1 and concentration 2.0mol/L for step (2) resulting molecular sieve+
Meter) it mixes, constant temperature is handled 2 hours at 90 DEG C；
(4) 160 DEG C of molecular sieve dry 18min obtained by step (3)；
(5) the resulting molecular sieve 40min of hexadiene soaking step (4) is taken, then, 150 DEG C of heating 25 in air atmosphere
Hour；
(6) step (5) resulting molecular sieve is mixed according to liquid-solid ratio 5:1 with 0.8% sodium hydroxide solution, 90 DEG C of processing
1.5 hour；
(7) Y molecular sieve after step (6) alkali process, 120 DEG C drying 2 hours, 550 DEG C roasting 2 hours after, changed
Property Y molecular sieve, number Y-4.
Y-4 molecular sieve transmission electron microscope EDAX results measure its outer surface to 180nm thickness, and surface layer silica alumina ratio is 59,
Molecular sieve phase silica alumina ratio is 34.XRD analysis the result shows that its lattice constant be 2.432, relative crystallinity 85%.Kong Rong
0.48ml/g, specific surface area 730m2/ g, it is 0.60mmol/g that infrared analysis result, which measures Y-4 meleic acid amount,.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 430g and nickel nitrate 440g to be dissolved in water
Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 36g/100ml and 11g/100ml, molten
Liquid number RY-4；
(2) Y-4 6g is taken to mix with 94g macroporous aluminium oxide, be added 4g/100ml dust technology mix in a mixer roll to
Extrudable shape, extruded moulding obtains carrier T-4 on banded extruder；
(3) T-4 60g is taken 120ml RY-1 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings
It burns 3 hours, obtains hydrocracking catalyst, number Cat-4.
Comparative example 1
Using a kind of widely applied hydrocracking catalyst of industry, it is counted as BCat-1, modified Y is removed in catalyst formulation
Outside molecular sieve, remaining composition and method for preparing catalyst are same as Example 1, the Y molecular sieve that catalyst BCat-1 is used
Matter is as follows: molecular sieve SiO2/Al2O3 Molar ratio is 50.XRD analysis the result shows that its lattice constant be 2.429, relative crystallinity
92%, Kong Rong 0.33ml/g, specific surface area 700m2/ g, meleic acid amount are 0.32 mmol/g.
Comparative example 2
Using a kind of widely applied hydrocracking catalyst of industry, it is counted as BCat-2, modified Y is removed in catalyst formulation
Outside molecular sieve, remaining composition and method for preparing catalyst are same as Example 4, the Y molecular sieve that catalyst BCat-2 is used
Matter is as follows: molecular sieve SiO2/Al2O3 Molar ratio is 30.XRD analysis the result shows that its lattice constant be 2.437, relative crystallinity
98%, Kong Rong 0.35ml/g, specific surface area 690m2/ g, meleic acid amount are 0.50 mmol/g.
Embodiment 5
In order to investigate the reactivity worth that Examples and Comparative Examples prepare catalyst, catalyst is carried out on midget plant
Evaluation test, evaluating apparatus use single-stage hydrocracking process flow, are loaded respectively according to embodiment 1 ~ 4 and compared in reactor
Hydrocracking catalyst prepared by example 1 ~ 2, feedstock property, evaluation condition and evaluation result are listed in 1 ~ table of table 5.
1 raw material oil nature of table.
2 evaluation condition of table.
3 evaluation result of table.
4 embodiment 1 of table and 2 catalyst stability comparative test of comparative example.
5 embodiment 3 of table and 1 catalyst stability comparative test of comparative example.
Embodiment 1,3 shows with comparative test of 1 ~ 2 catalyst of comparative example on evaluating apparatus using the method for the present invention system
Standby catalyst is compared with comparative example catalyst, and operation process reactivity and stable product quality are more preferably.
Claims (14)
1. a kind of hydrocracking catalyst, it is characterised in that: with overall catalyst weight meter, including following component: containing modified Y molecule
The silica-alumina supports 30% ~ 80% of sieve, active metal 20% ~ 70%, wherein active metal is in terms of metal oxide；The wherein modification
Mass percent of the Y molecular sieve in silica-alumina supports is 1% ~ 13%, and surplus is amorphous silica-alumina and/or aluminium oxide；It is wherein described
Modified Y molecular sieve have the property that lattice constant be 2.425 ~ 2.440；Body phase silica alumina ratio is 20 ~ 50, wherein surface silicon
For aluminium than 50 ~ 120, surface layer silica alumina ratio is higher than body phase silica alumina ratio 10 ~ 80, wherein the surface layer refers to molecular sieve outer surface to inside 10
The thickness range of ~ 200nm, sodium oxide molybdena mass percentage is less than 1.0%, 600 ~ 800m of specific surface area2/ g, Kong Rong 0.40 ~
0.70ml/g, infrared 0.1 ~ 0.8mmol/g of acid content, relative crystallinity 60% ~ 90%.
2. hydrocracking catalyst described in accordance with the claim 1, it is characterised in that: the active metal is selected from period of element
Group VIII and/or vib metals element in table, group VIII active metal are Ni and/or Co, group VIB activity gold
Category is W and/or Mo, and group VIII active metallic content is 3% ~ 15%, and group VIB active metallic content is 10% ~ 40%, with metal
Oxide meter.
3. hydrocracking catalyst described in accordance with the claim 1, it is characterised in that: the specific surface area of the catalyst be 100 ~
300m20.2 ~ 0.5mL/g of/g, Kong Rongwei.
4. hydrocracking catalyst described in accordance with the claim 1, it is characterised in that: the preparation side of the modified Y molecular sieve
Method, including following content: (1) by original powder of NaY zeolite Ammonium Salt Ionic exchange in ammonium salt aqueous solution is carried out；(2) to step (1)
Obtained in ammonium exchange after Y molecular sieve carry out hydro-thermal process；(3) to the Y molecular sieve acid dealuminzation after step (2) hydro-thermal process
Reason；(4) the resulting Y molecular sieve rapid draing of step (3) is handled；(5) Y molecular sieve that step (4) obtains and liquid or gaseous state
Unsaturated olefin come into full contact with, then in oxygen-containing atmosphere carry out carbon deposit reaction；(6) molecular sieve for obtaining step (5) into
Row desiliconization processing；(7) treated after Y molecular sieve filtered, dried through desiliconization for step (6), carries out processing of making charcoal, is modified
Y molecular sieve.
5. hydrocracking catalyst according to claim 4, it is characterised in that: the exchange of Ammonium Salt Ionic described in step (1)
Process is as follows: being raw material in ammonium salt aqueous solution using NaY zeolite, at 60 ~ 120 DEG C, exchanges 1 ~ 3 hour, exchange times are 1 ~ 4
It is secondary, the NaY zeolite after being exchanged, Na2O content is less than 3.0%；The wherein SiO of NaY zeolite raw material2/Al2O3Molar ratio be 3 ~
6, sodium oxide molybdena mass percentage 6% ~ 7%；Ammonium salt be one of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate or
It is several, 0.3 ~ 6.0mol/L of ammonium salt aqueous solution concentration.
6. hydrocracking catalyst according to claim 4, it is characterised in that: step (2) described hydrothermal treatment process is
In itself vapor or under conditions of be passed through vapor, hydrothermal conditions are as follows: temperature is 550 ~ 700 DEG C, pressure is 0.01 ~
0.5MPa, processing time are 1.0 ~ 6.0 hours, and hydro-thermal process number is 1 ~ 3 time.
7. hydrocracking catalyst according to claim 4, it is characterised in that: sour dealumination treatment described in step (3)
The inorganic acid or organic acid that process uses are one of sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid or a variety of, inorganic
The concentration of acid and/or organic acid is with H+It is calculated as 0.7 ~ 3mol/L, the liquid/solid mass ratio of sour dealumination treatment process is 3:1 ~ 30:1,
60 ~ 120 DEG C for the treatment of temperature, the processing time is 0.5 ~ 3 hour.
8. hydrocracking catalyst according to claim 4, it is characterised in that: the processing of rapid draing described in step (4)
Condition are as follows: drying temperature is 100 ~ 200 DEG C, and drying time is 1 ~ 60 minute.
9. hydrocracking catalyst according to claim 4, it is characterised in that: unsaturated olefin described in step (5) is
The positive structure or isomeric olefine, alkadienes that carbon atom number is 2 ~ 10；Wherein the alkene and molecular sieve, which come into full contact with, refers to insatiable hunger
It is diffused into inside molecular sieve with alkene；When using gaseous state unsaturated olefin, gaseous state unsaturated olefin and molecular sieve bow strip
Part are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.1 ~ 2 hour；When using liquid unsaturated hydrocarbons, liquid unsaturated olefin with point
Son sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.5 ~ 4 hour, molecular sieve answered thorough impregnation in liquefied olefines.
10. hydrocracking catalyst according to claim 4, it is characterised in that: step (5) the carbon deposit reaction condition
Are as follows: 50 ~ 500 DEG C of reaction temperature, the reaction time is 1 ~ 50 hour.
11. hydrocracking catalyst according to claim 4, it is characterised in that: the processing of desiliconization described in step (6) is adopted
With alkali desilication method；The lye that alkali desiliconization treatment process uses is the aqueous solution of sodium hydroxide or potassium hydroxide, wherein lye
Concentration is 0.1wt% ~ 2wt%, and 50 ~ 100 DEG C of base extraction temperature, the processing time is 0.5 ~ 4 hour, lye/molecular sieve liquid stereoplasm
Amount is than being 5:1 ~ 10:1.
12. hydrocracking catalyst according to claim 4, it is characterised in that: step (7) drying condition is temperature
90 DEG C ~ 120 DEG C, drying time is 2 ~ 4 hours；Treatment conditions of making charcoal are to roast 2 ~ 4 hours at 400 ~ 600 DEG C, remove molecular sieve
Upper remaining carbon deposit.
13. a kind of preparation method of hydrocracking catalyst described in claim 1 ~ 12 any claim, it is characterised in that
Including following content: one, being uniformly mixed modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide according to the proportion, dilute nitre is added
Rear extruded moulding is slurried in acid, and dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；Two, using the dipping containing active metal
Liquid impregnates the carrier of step 1, and the carrier after dipping obtains hydrocracking catalyst through drying, roasting.
14. hydrocracking catalyst described in a kind of claim 1 ~ 12 any claim is in single-stage hydrocracking technological reaction
Application in the process, operating condition are as follows: 6.0 ~ 20.0MPa of reaction pressure, 350 ~ 420 DEG C of reaction temperature, feed volume air speed 0.3
~ 3.0h-1, hydrogen to oil volume ratio are 500:1 ~ 2000:1.
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| CN1609175A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Hydroprocessing catalyst and its prepn process |
| CN1608992A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Modified molecular sieve and its prepn process |
| CN101239314A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing amorphous aluminum silicide and preparation thereof |
| CN101618348A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN101722022A (en) * | 2008-10-10 | 2010-06-09 | 中国石油天然气集团公司 | Alkali treatment modifying method of Y-shaped molecular sieve |
| CN102794193A (en) * | 2011-05-24 | 2012-11-28 | 中国石油天然气集团公司 | External surface modification method of microporous molecular sieve |
| CN103011192A (en) * | 2012-12-17 | 2013-04-03 | 中国海洋石油总公司 | Silicon-aluminium carrier comprising molecular sieve and preparation method thereof |
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| CN1609175A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Hydroprocessing catalyst and its prepn process |
| CN1608992A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Modified molecular sieve and its prepn process |
| CN101239314A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing amorphous aluminum silicide and preparation thereof |
| CN101618348A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN101722022A (en) * | 2008-10-10 | 2010-06-09 | 中国石油天然气集团公司 | Alkali treatment modifying method of Y-shaped molecular sieve |
| CN102794193A (en) * | 2011-05-24 | 2012-11-28 | 中国石油天然气集团公司 | External surface modification method of microporous molecular sieve |
| CN103011192A (en) * | 2012-12-17 | 2013-04-03 | 中国海洋石油总公司 | Silicon-aluminium carrier comprising molecular sieve and preparation method thereof |
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