CN110252390A - A kind of hydrocracking catalyst and preparation method thereof producing high-quality tail oil - Google Patents
A kind of hydrocracking catalyst and preparation method thereof producing high-quality tail oil Download PDFInfo
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- CN110252390A CN110252390A CN201910612038.7A CN201910612038A CN110252390A CN 110252390 A CN110252390 A CN 110252390A CN 201910612038 A CN201910612038 A CN 201910612038A CN 110252390 A CN110252390 A CN 110252390A
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- molecular sieve
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- tail oil
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- hydrocracking
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002808 molecular sieve Substances 0.000 claims abstract description 44
- 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 44
- 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 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 15
- 229910001593 boehmite Inorganic materials 0.000 claims description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 33
- 239000002199 base oil Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910009112 xH2O Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 monocyclic hydrocarbon Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J35/615—100-500 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
- B01J35/61—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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- 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
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- 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
-
- 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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7892—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
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- 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)
- Catalysts (AREA)
Abstract
The present invention relates to the hydrocracking catalysts and preparation method thereof of production high-quality tail oil, it is not high mainly to solve existing hydrocracking tail oil quality, the problem of cannot be used for production High Quality Lube Base Oils, hydrocracking catalyst of the present invention by using high-quality tail oil, including following components :(a) the metal of VIII group element or its oxide；(b) metal of group vib element or its oxide；(c) Al2O3；(d) USY molecular sieve；(e) technical solution of SSZ-95 molecular sieve preferably solves the technical problem, can be used for producing high-quality hydrocracking tail oil.
Description
Technical field
The invention belongs to hydrocracking catalyst technical fields, and in particular to a kind of to produce being hydrocracked for high-quality tail oil
Catalyst and preparation method thereof.
Background technique
Hydrocracking process is a kind of oil refining work that higher boiling raw material is transformed into low-boiling naphtha and diesel oil distillate
Skill.Its adaptability to raw material is high compared with catalytic cracking, and the yield of diesel oil distillate is high, quality is good.As clean traffic is fired in society
The demand of material oil is continuously increased, and hydrocracking process becomes one of the core process of modern refinery.
Being hydrocracked is one of core process in current petroleum refining industry.The product generated after the hydrogenated cracking of raw material is main
It is gas and the liquid product including solvent naphtha, gasoline component and intermediate oil.Secondly do not turn there are also quite a few
Carburetion, also referred to as hydrocracking tail oil.Hydrocracking tail oil equally obtains good hydro-upgrading in hydrocracking process,
Therefore have aromatic hydrocarbon content low, the features such as impurity contents such as sulphur nitrogen are seldom, cycloalkane and high Determination of Alkane Content.Hydrocracking tail oil
It is not only excellent ethylene cracking material, while can also be used as Lube basic oil material feedstocks.
In the production process of lube base oil, the composition and structure of lubricating oil viscosity index and its hydrocarbon-containifirst have close
The relationship cut.Isoparaffin, the monocyclic hydrocarbon of belt length side chain are highly desirable existing components in high-quality lubricating oil composition.For straight
Alkane ought will affect the low temperature flow of lubricating oil when there are a lot although having very high viscosity index (VI).Therefore, it
High Quality Lube Base Oils are produced using hydrocracking tail oil, the linear paraffin in tail oil should be removed as far as possible.
Hydrocracking catalyst is typical bifunctional catalyst, generally includes difunctional center: one is metal center, one
As be made of group vib metal or group vib with VIII group binary metal system, can also be by aromatic hydrocarbons with hydrogenation/dehydrogenation function
Saturation；Second is the acid centre with cracking function, is provided by amorphous silicon aluminium or molecular sieve, it can crack long-chain
Macromolecular.In addition, molecular sieve can also provide isomerization activity center, isoparaffin is converted by linear paraffin in product,
Reduce product condensation point.Although the usually Y molecular sieve used in hydrocracking catalyst and USY molecular sieve open loop ability is stronger,
But isomerization activity is very low, and linear paraffin content is high in tail oil product.Be conducive to using the molecular sieve with excellent isomery performance
The isomerization performance of hydrocracking catalyst is improved, the content of linear paraffin in tail oil product is reduced, improves low temperature flow, mentions
The quality for rising tail oil, for producing High Quality Lube Base Oils.
Patent US8231778 describes in hydrocracking catalyst that effectively reduce tail oil using Beta molecular sieve solidifying
Point, but the viscosity index (VI) of tail oil can reduce simultaneously.Patent US7300900 is described in hydrocracking catalyst while being used
Two kinds of molecular sieves of ZBM-30 and Y have higher tail oil viscosity index (VI) than Y molecular sieve is used alone.Patent CN
107344110A is described in hydrocracking catalyst while being used Y type molecular sieve and the better ZSM-48 molecule of isomery performance
Sieve, enhances the isomerization reaction of linear paraffin, linear paraffin content in tail oil is made to decline to a great extent.Patent CN106669808A is situated between
Continued a kind of hydrocracking catalyst comprising modified USY molecular sieve, ZSM-48 molecular sieve and Beta zeolite, can produce low
Condensation point hydrocracking tail oil.
Existing result of study show in hydrocracking catalyst using with excellent isomerization performance molecular sieve, can
To reduce the content of linear paraffin in tail oil product, the quality of tail oil is promoted.
Summary of the invention
The first technical problem to be solved by the present invention is that hydrocracking tail oil quality is not high, it is impossible to be used in produces high-quality profit
Lubricant base oil, provides a kind of new hydrocracking catalyst, and the high-quality which has production straight chain hydrocarbon content low adds hydrogen
The characteristics of cracking tail oil.
The second technical problem to be solved by the present invention is to provide the preparation of catalyst described in one of above-mentioned technical problem
Method.
One of to solve above-mentioned technical problem, technical scheme is as follows: production high-quality tail oil is hydrocracked
Catalyst, including following components:
(a) metal of VIII group element or its oxide；
(b) metal of group vib element or its oxide；
(c) Al2O3；
(d) USY molecular sieve；
(e) SSZ-95 molecular sieve.
In above-mentioned technical proposal, based on parts by weight, composition (a) is preferably 0.1 ~ 35 part, and more preferable 15 ~ 25 parts.
In above-mentioned technical proposal, based on parts by weight, composition (b) is preferably 0.1 ~ 15 part, and more preferable 4 ~ 8 parts.
In above-mentioned technical proposal, based on parts by weight, composition (c) is preferably 5 ~ 70 parts, and more preferable 20 ~ 40 parts.
In above-mentioned technical proposal, based on parts by weight, composition (d) is preferably 2 ~ 30 parts, and more preferable 5 ~ 20 parts.
In above-mentioned technical proposal, based on parts by weight, composition (e) is preferably 2 ~ 50 parts, and more preferable 10 ~ 40 parts.
In above-mentioned technical proposal, the group vib element preferably is selected from least one of Mo and W.
In above-mentioned technical proposal, the VIII group element preferably is selected from least one of Co and Ni.
In above-mentioned technical proposal, the USY molecular sieve has the property that specific surface area is 400 ~ 1000 m2/ g, it is excellent
Select 600 ~ 800 m2/g；Total pore volume is 0.45 ~ 1.00 cm3/ g, preferably 0.50 ~ 0.80 ml/g；Its intermediary hole Kong Rongwei
0.10 ~ 0. 50ml/g, preferably 0.20 ~ 0.40ml/g；Si/Al molar ratio is 4 ~ 30, preferably 5 ~ 10.
In above-mentioned technical proposal, the SSZ-95 molecular sieve has the property that specific surface area is 200 ~ 300 m2/ g,
It is preferred that 250 ~ 280 m2/g；Micropore volume is 0.005 ~ 0.03 cm3/ g, preferably 0.10 ~ 0.02 ml/g；Si/Al molar ratio be 8 ~
40, preferably 10 ~ 20.
In above-mentioned technical proposal, the molecular sieve is hydrogen type molecular sieve.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem
The preparation method of hydrocracking catalyst described in case, includes the following steps:
(1) boehmite, USY molecular sieve and SSZ-32 molecular sieve powder are uniformly mixed, acid solution is then added, sufficiently pinches
It is formed after conjunction, re-dry, roasting obtain catalyst carrier；
(2) it disperses the compound of the compound of the element containing group vib, the element containing VIII group in solvent, impregnation steps (1) obtain
Catalyst carrier, it is then dry, roast, obtain hydrocracking catalyst.
In above-mentioned technical proposal, boehmite is after 400-600 DEG C of 4 h of roasting, obtained aluminium oxide, has following property
Matter: specific surface is 150 ~ 400 m2/ g, preferably 200 ~ 330 m2/g；0.3 ~ 0.8 cm of Kong Rongwei3/ g, preferably 0.40 ~ 0.65
cm3/g；In terms of weight fraction, Na constituent content is less than or equal to 0.1%, is preferably smaller than equal to 0.05%.
In above-mentioned technical proposal, acid solution described in step (1) can be the inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, can also
To be the organic acids such as formic acid, acetic acid and citric acid, preferably nitric acid solution；Acid solutions be 0.5wt% ~ 5wt%, preferably 1wt% ~
3wt%。
In above-mentioned technical proposal, step (1) size and shape after molding are preferably similar to traditional be hydrocracked
1.5 ~ 3.5 nm of diameter is more preferably made in commercial catalysts, the section of long 3 ~ 12 nm is round or clover extrudate.
In above-mentioned technical proposal, the dry temperature of step (1) is preferably 80 ~ 200 DEG C, and the time is preferably 2 ~ 24 h.
In above-mentioned technical proposal, the temperature of step (1) roasting is preferably 400 ~ 650 DEG C, and the time is preferably 2 ~ 10 h.
In above-mentioned technical proposal, the compound of the element containing group vib and the compound of the element containing VIII group are without spy
It does not limit, those skilled in the art can reasonably select.
In above-mentioned technical proposal, the solvent that step (2) uses is not particularly limited, as long as being able to achieve the operation of dip loading
, these solvents, which can be, directly to be dissolved, or by adjusting pH dissolution, is also possible to that colloid can be formed or is passed through adjusting
PH forms those of colloid solvent, can be single solvent, or mixed solvent.
In above-mentioned technical proposal, the dry temperature of step (1) is preferably 80 ~ 200 DEG C, and the time is preferably 2 ~ 24 h.
In above-mentioned technical proposal, the temperature of step (1) roasting is preferably 400 ~ 600 DEG C, and the time is preferably 2 ~ 10 h.
Hydrocracking catalyst of the invention carries out presulfurization to catalyst before performance evaluation.In hydrocracked, treated
When VGO feedstock, reaction condition are as follows: in the presence of hydrogen, 12 ~ 18MPa of reaction pressure, 340 ~ 420 DEG C of reaction temperature, hydrogen oil volume
Than 500 ~ 1500,1.0 ~ 8.0 h of volume space velocity when liquid-1。
The method of the present invention compared with the prior art, have the advantages that this catalyst preparation process and meanwhile use compared with
The USY molecular sieve of strong cracking and open loop ability and compared with strong hydrogenation isomerism ability SSZ-95 molecular sieve, two kinds of molecular sieves have mutual
Facilitation is cooperateed with, while promoting the hydroisomerizing ability of hydrocracking catalyst, strengthens open loop ability to supplement straight chain
The loss of viscosity index (VI) caused by after hydrocarbon.When hydrocracked, treated VGO feedstock, available straight chain hydrocarbon content is low, viscosity index (VI)
Still higher high-quality tail oil.Therefore, high-quality hydrocracking tail oil can be produced using this catalyst, for further raw
Produce High Quality Lube Base Oils.
Specific embodiment
The present invention will be further described below by way of examples, but these embodiments are not to the scope of the present invention
It is limited.
Embodiment 1
(1) USY molecular sieve powder, SSZ-95 molecular sieve powder and boehmite powder are uniformly mixed, nitric acid is then added
Solution, extruded moulding after sufficiently mediating, is extruded into the cylindrical particle of 3 to 10 mm long, 2 mm diameters.Again under the conditions of 120 DEG C
It is 12 hours dry, it is finally roasted 8 hours under the conditions of 550 DEG C, obtains catalyst carrier；
The specific surface of aluminium oxide is 1245 m after boehmite roasting2/ g,；0.47 cm of Kong Rongwei3/g
(2) by nickel nitrate (Ni (NO3)2·6H2) and ammonium metatungstate ((NH O4)10W12O41·xH2O it) is scattered in deionized water,
Then the catalyst carrier that impregnation steps (1) obtain, then drying 10 hours under the conditions of 100 DEG C, finally roast under the conditions of 520 DEG C
It burns 5 hours, obtains catalyst；It is obtained nickel oxide (NiO) after the nickel nitrate roasting, obtains three oxygen after the ammonium metatungstate roasting
Change tungsten (WO3)；Based on parts by weight, NiO:WO in the catalyst3:Al2O3: the ratio of USY:SSZ-95 is 5:15:36:12:
32。
Embodiment 2
(1) USY molecular sieve powder, SSZ-95 molecular sieve powder and boehmite powder are uniformly mixed, nitric acid is then added
Solution, extruded moulding after sufficiently mediating, is extruded into the cylindrical particle of 3 to 10 mm long, 2 mm diameters.Again under the conditions of 120 DEG C
It is 12 hours dry, it is finally roasted 8 hours under the conditions of 550 DEG C, obtains catalyst carrier；
The specific surface of aluminium oxide is 245 m after boehmite roasting20.47 cm of/g, Kong Rongwei3/g
(2) by nickel nitrate (Ni (NO3)2·6H2) and ammonium molybdate ((NH O4)2MoO4·4H2O it) is scattered in deionized water, then
The catalyst carrier that impregnation steps (1) obtain, then drying 10 hours under the conditions of 100 DEG C, finally roast 5 under the conditions of 520 DEG C
Hour, obtain catalyst；It is obtained nickel oxide (NiO) after the nickel nitrate roasting, obtains molybdenum trioxide after the ammonium molybdate roasting
(MoO3)；Based on parts by weight, NiO:MoO in the catalyst3:Al2O3: the ratio of USY:SSZ-95 is 5:15:36:12:32.
Embodiment 3
(1) USY molecular sieve powder, SSZ-95 molecular sieve powder and boehmite powder are uniformly mixed, nitric acid is then added
Solution, extruded moulding after sufficiently mediating, is extruded into the cylindrical particle of 3 to 10 mm long, 2 mm diameters.Again under the conditions of 120 DEG C
It is 12 hours dry, it is finally roasted 8 hours under the conditions of 550 DEG C, obtains catalyst carrier；
The specific surface of aluminium oxide is 245 m after boehmite roasting20.47 cm of/g, Kong Rongwei3/g
(2) by nickel nitrate (Ni (NO3)2·6H2) and ammonium metatungstate ((NH O4)10W12O41·xH2O it) is scattered in deionized water,
Then the catalyst carrier that impregnation steps (1) obtain, then drying 10 hours under the conditions of 100 DEG C, finally roast under the conditions of 520 DEG C
It burns 5 hours, obtains catalyst；It is obtained nickel oxide (NiO) after the nickel nitrate roasting, obtains three oxygen after the ammonium metatungstate roasting
Change tungsten (WO3)；Based on parts by weight, NiO:WO in the catalyst3:Al2O3: the ratio of USY:SSZ-95 is 5:15:36:32:
12。
Comparative example 1
(1) USY molecular sieve powder and boehmite powder are uniformly mixed, nitric acid solution is then added, squeezed after sufficiently mediating
Item molding, is extruded into the cylindrical particle of 3 to 10 mm long, 2 mm diameters.It is 12 hours dry under the conditions of 120 DEG C again, finally exist
It is roasted 8 hours under the conditions of 550 DEG C, obtains catalyst carrier；
The specific surface of aluminium oxide is 245 m after boehmite roasting20.47 cm of/g, Kong Rongwei3/g
(2) by nickel nitrate (Ni (NO3)2·6H2) and ammonium metatungstate ((NH O4)10W12O41·xH2O it) is scattered in deionized water,
Then the catalyst carrier that impregnation steps (1) obtain, then drying 10 hours under the conditions of 100 DEG C, finally roast under the conditions of 520 DEG C
It burns 5 hours, obtains catalyst；It is obtained nickel oxide (NiO) after the nickel nitrate roasting, obtains three oxygen after the ammonium metatungstate roasting
Change tungsten (WO3)；Based on parts by weight, NiO:WO in the catalyst3:Al2O3: the ratio of USY is 5:15:36:44.
Comparative example 2
(1) SSZ-95 molecular sieve powder and boehmite powder are uniformly mixed, nitric acid solution is then added, after sufficiently mediating
Extruded moulding is extruded into the cylindrical particle of 3 to 10 mm long, 2 mm diameters.It is 12 hours dry under the conditions of 120 DEG C again, finally
It is roasted 8 hours under the conditions of 550 DEG C, obtains catalyst carrier；
The specific surface of aluminium oxide is 245 m after boehmite roasting20.47 cm of/g, Kong Rongwei3/g
(2) by nickel nitrate (Ni (NO3)2·6H2) and ammonium metatungstate ((NH O4)10W12O41·xH2O it) is scattered in deionized water,
Then the catalyst carrier that impregnation steps (1) obtain, then drying 10 hours under the conditions of 100 DEG C, finally roast under the conditions of 520 DEG C
It burns 5 hours, obtains catalyst；It is obtained nickel oxide (NiO) after the nickel nitrate roasting, obtains three oxygen after the ammonium metatungstate roasting
Change tungsten (WO3)；Based on parts by weight, NiO:WO in the catalyst3:Al2O3: the ratio of SSZ-95 is 5:15:36:44.
Embodiment 4
Catalyst performance evaluation
Hydrogen evaluating apparatus is added to carry out catalyst performance evaluation using two sections of concatenated 100 m1 are small-sized.Use is by volume point before evaluating
The H of number 5%2The H of S and 95%2The gaseous mixture gas of composition carries out presulfurization to catalyst.When evaluating catalyst, feedstock oil and hydrogen
The first reactor equipped with Hydrobon catalyst is first passed through, the second reaction equipped with hydrocracking catalyst is then directly entered
Device, second reactor effluent are to obtain various products afterwards after separation.When evaluating catalyst, the hydrofinishing of first reactor
Catalyst and reaction process condition are completely the same, and the organic nitrogen content in control first reactor outlet effluent is lower than 20ppm；
The reaction temperature of second reactor is adjusted, control conversion ratio is 80%.Conversion ratio calculation formula is as follows:
The raw materials used oil nature of evaluation catalyst performance and reaction process condition are shown in Tables 1 and 2, catalyst reaction performance comparison knot
Fruit is shown in Table 3.The comparing result of embodiment and comparative example is shown, uses USY molecular sieve and compared with strong hydrogenation isomerism ability SSZ-95
The standby catalyst of system with molecular sieve for preparing, when hydrocracked, treated VGO feedstock, available straight chain hydrocarbon content is low, viscosity index (VI) is high height
Quality tail oil.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (10)
1. a kind of hydrocracking catalyst for producing high-quality tail oil, it is characterised in that: including following components:
(a) metal of VIII group element or its oxide；
(b) metal of group vib element or its oxide；
(c) Al2O3；
(d) USY molecular sieve；
(e) SSZ-95 molecular sieve.
2. catalyst according to claim 1, it is characterised in that: based on parts by weight, composition (a) is 0.1 ~ 35 part, group
It is 0.1 ~ 15 part at (b), composition (c) is 5 ~ 70 parts, and composition (d) is 2 ~ 30 parts, and composition (e) is 2 ~ 50 parts.
3. catalyst according to claim 1, it is characterised in that: the group vib element is one of Mo and W or two
Kind.
4. catalyst according to claim 1, it is characterised in that: the VIII group element is one of Co and Ni or two
Kind.
5. catalyst according to claim 1, it is characterised in that: the specific surface area of the USY molecular sieve is 400 ~ 1000
m2/ g, total pore volume are 0.45 ~ 1.00 cm3/ g, it is 0.10 ~ 0.50 cm that intermediary hole hole, which holds,3/ g, Si/Al molar ratio be 4 ~
30。
6. catalyst according to claim 1, which is characterized in that the specific surface area of the SSZ-95 molecular sieve be 200 ~
300 m2/ g, Micropore volume are 0.005 ~ 0.03 cm3/ g, Si/Al molar ratio are 8 ~ 40.
7. catalyst according to claim 1, it is characterised in that: the USY molecular sieve and SSZ-95 molecular sieve are hydrogen
Type molecular sieve.
8. a kind of preparation method of catalyst as described in the appended claim 1, characterized by the following steps:
(1) boehmite, USY molecular sieve and SSZ-32 molecular sieve powder are uniformly mixed, acid solution is then added, sufficiently pinches
It is formed after conjunction, re-dry, roasting obtain catalyst carrier；
(2) it disperses the compound of the compound of the element containing group vib, the element containing VIII group in solvent, impregnation steps (1) obtain
Catalyst carrier, it is then dry, roast, obtain hydrocracking catalyst.
9. preparation method according to claim 8, it is characterised in that: the temperature of step (1) described drying is 80 ~ 200
DEG C, the time is 2 ~ 24 h；The temperature of roasting is 400 ~ 650 DEG C, and the time is 2 ~ 10 h.
10. preparation method according to claim 8, it is characterised in that: the temperature of step (2) described drying is 80 ~ 200
DEG C, the time is 2 ~ 24 h；The temperature of roasting is 400 ~ 600 DEG C, and the time is 2 ~ 10 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111632620A (en) * | 2020-06-16 | 2020-09-08 | 中化泉州石化有限公司 | A medium oil type hydrocracking catalyst |
| CN112221535A (en) * | 2020-10-27 | 2021-01-15 | 中化泉州石化有限公司 | Medium oil type hydrocracking catalyst and preparation method thereof |
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| CN108714434A (en) * | 2018-06-04 | 2018-10-30 | 中国中化股份有限公司 | A kind of light oil type hydrogen cracking catalyst and preparation method thereof |
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| CN101035881A (en) * | 2004-09-08 | 2007-09-12 | 国际壳牌研究有限公司 | Hydrocracking catalyst composition |
| CN102959054A (en) * | 2010-06-29 | 2013-03-06 | 埃克森美孚研究工程公司 | Integrated hydrocracking and dewaxing of hydrocarbons |
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