CN108102698A - A kind of method for producing lube base oil - Google Patents
A kind of method for producing lube base oil Download PDFInfo
- Publication number
- CN108102698A CN108102698A CN201611051788.4A CN201611051788A CN108102698A CN 108102698 A CN108102698 A CN 108102698A CN 201611051788 A CN201611051788 A CN 201611051788A CN 108102698 A CN108102698 A CN 108102698A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ton
- rare earth
- molecular sieve
- earth element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002199 base oil Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 60
- 230000000694 effects Effects 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims description 47
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 230000001588 bifunctional effect Effects 0.000 claims description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000004996 alkyl benzenes Chemical class 0.000 abstract description 4
- 239000000314 lubricant Substances 0.000 abstract description 3
- 239000001993 wax Substances 0.000 description 17
- 238000006317 isomerization reaction Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- -1 small molecule hydrocarbon Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/046—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being an aromatisation step
-
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- 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
- B01J35/63—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
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methods for producing lube base oil.Raw material Fischer-Tropsch wax is generated alkylbenzene by the present invention under the effect of the catalyst, and reaching reduces Fischer-Tropsch wax pour point, produces the purpose of base oil of high viscosity index lubricant.The method of the present invention not only increases the selectivity of pour point depression process, and also improves the yield of the lube base oil of Fischer-Tropsch wax production.
Description
Technical field
The present invention relates to a kind of methods for producing lube base oil.Specifically using Fischer-Tropsch wax as raw material, using hydro carbons
The method of conversion production lube base oil.
Background technology
To ensure the low temperature fluidity of lube base oil, it is necessary to reduce the pour point of feed of base oil.Base oil pour point depression
Technique mainly includes solvent dewaxing, catalytic dewaxing（Hydro dewaxing）And isomerization dewaxing.Solvent dewaxing is the method with physical separation
There is component to separate with low condensation point the high condensation point wax component in raw material to achieve the purpose that reduce base oil pour point.Catalytic dewaxing（Face
Hydrogen pour point depression）It is under catalyst containing ZSM-5 molecular sieve and hydrogen effect, lube cut is by shape slective cracking, by its N-alkanes
The hydrocarbon pyrolysis is into small molecule hydrocarbon to reduce condensation point.Isomerization dewaxing technique is containing SAPO-11, ZSM-22, ZSM-23 and ZSM-48 etc.
Under molecular sieve catalyst and hydrogen effect, by selective isomerization, the n-alkane of high-solidification point is converted into isoparaffin, it is real
Now reduce the purpose of pour point.
CN CN200710063010.X, CN201010615901.3 and CN201210143102.X use hydroisomerizing
Changing (isomerization dewaxing) technique reduces Fischer-Tropsch wax condensation point production lube base oil.US 4,943,672 is (different using hydroisomerization
Structure dewaxes) and solvent dewaxing group technology reduction Fischer-Tropsch wax condensation point production lube base oil.US7,198,710 proposes one kind
By the method for Fischer-Tropsch wax production base oil of high viscosity index lubricant.First Fischer-Tropsch wax is fractionated to obtain light component and restructuring
Point, then carrying out hydroisomerizing dewaxing respectively reduces raw material pour point, can obtain the light lubricating oil base oil that pour point is met the requirements.
Hydroisomerizing dewaxes heavy constituent since pour point is unqualified, further reduces the pour point of heavy constituent using the method for solvent dewaxing, most
After obtain the satisfactory heavy lubricant base stock product of pour point.
Above existing Fischer-Tropsch wax isomerization dewaxing or solvent dewaxing etc. reduce the technology of pour point, are limited by process selectivity,
The yield of lube base oil product is relatively low.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of side that lube base oil is produced using Fischer-Tropsch wax as raw material
Method.Fischer-Tropsch wax is converted into alkylbenzene in the method for the present invention, reduces the pour point of Fischer-Tropsch wax, and product yield is higher.
The present invention provides a kind of method for producing lube base oil, and the described method includes following contents：
（1）Into the first reaction zone after Fischer-Tropsch wax and hydrogen mixing, it is anti-that dehydrocyclization occurs under the action of bifunctional catalyst
It should；
（2）By step（1）Obtained reaction effluent carries out gas-liquid separation, after isolated liquid phase effluent and hydrogen mix
Into the second hydroconversion reaction zone, hydrofining reaction occurs under Hydrobon catalyst effect；
（3）By step（2）Obtained hydrofinishing effluent carries out gas-liquid separation, and separating obtained liquid product obtains not through distillation
With the lube base oil of viscosity grade.
In the method for the present invention, the Fischer-Tropsch wax refers to that the Fischer-Tropsch product that synthesis gas is obtained by Fischer-Tropsch synthesis evaporates entirely
Point or Fischer-Tropsch product heavy constituent, the boiling range of the heavy constituent is 350-700 DEG C.
In the method for the present invention, step（2）Isolated gas phase can be cycled partly or entirely as the first reaction zone.
In the method for the present invention, step（1）Described in bifunctional catalyst include TON types molecular sieve, metal component and nothing
Machine refractory oxide；The wherein described TON types molecular sieve is the TON type molecular sieves containing rare earth element；Inorganic refractory oxide is
One or more of aluminium oxide, titanium oxide, boron oxide, silica, zirconium oxide and magnesia, metal component are noble metal, can
Think platinum and/or palladium.For the bifunctional catalyst in terms of the weight of catalyst, composition is as follows：The type molecules of TON containing rare earth element
Sieve 10wt%~95wt%；Metal component is calculated as 0.05wt%~5.0wt%, inorganic refractory oxide 15wt%~40wt% with metal.
The rare earth element is in terms of oxide（RE2O3）Content in the catalyst is 1wt%~15wt%, is preferably 3wt%~10wt%.
The bifunctional catalyst specific surface area is 200~350m2/ g, pore volume are 0.3~0.5mL/g.
In the method for the present invention, the TON types molecular sieve for ZSM-22 molecular sieves, Nu-10 molecular sieves, KZ-2 molecular sieves and
One or more in ISI-1 molecular sieves are preferably ZSM-22 molecular sieves.The silica alumina ratio of the TON types molecular sieve is 50
~200, it is preferably 80~160.
In the method for the present invention, the rare earth element is lanthanum, in cerium, praseodymium, promethium, samarium, europium, dysprosium, gadolinium, erbium, thulium, yttrium, lutetium
One or more are preferably lanthanum and/or cerium.Its precursor is to be dissolvable in water the salt of water, such as chloride, nitrate and acetic acid
Salt is preferably nitrate.
In the method for the present invention, the types of TON containing the rare earth element molecular sieve is by rare-earth compound and TON type molecular sieves
It directly mixes, then in 20~300 DEG C of dry 1h~48h, then roasts 0.5h~10h at 400 DEG C~800 DEG C, obtain containing dilute
The TON type molecular sieves of earth elements.
In the method for the present invention, step（1）Described in the first reaction zone improved by the way of catalyst grading loading
The selectivity of paraffin dehydrogenation cyclization.Load bifunctional catalyst A, double successively according to the flow direction of Fischer-Tropsch wax and hydrogen
Function catalyst B and bifunctional catalyst C.TON types molecular sieve content difference containing rare earth element in the bifunctional catalyst A
For 42wt%~45wt%, in the bifunctional catalyst B TON type molecular sieve contents containing rare earth element be respectively 60wt%~
The TON type molecular sieve contents containing rare earth element are respectively 72wt%~75wt% in 64wt%, the bifunctional catalyst C, and described
The admission space ratio of bifunctional catalyst A, bifunctional catalyst B and bifunctional catalyst C are 40~50 in one reaction zone：40
~30：30~20.
In the method for the present invention, the reaction condition of first reaction zone is：Temperature is 350 DEG C~480 DEG C, is preferably 420
DEG C~480 DEG C, hydrogen partial pressure is 0.05MPa~1.0MPa, is preferably 0.05~0.30MPa, volume space velocity 0.1h-1~3.0h-1, it is preferably 0.5h-1~2.0h-1, hydrogen to oil volume ratio 50:1~1500:1, it is preferably 200:1~800:1.
In the method for the present invention, step（2）The middle Hydrobon catalyst used is conventional reduced form hydrofinishing catalysis
Agent, can be noble metal catalyst or reduced state nickel catalyst, when for noble metal catalyst when, the active metal be Pt, Pd
One or both of, active metal is generally 0.05%~1% in the weight content of catalyst, when for reduced state nickel catalyst
When, active metal is calculated as 30%~80% with oxide weight, and catalyst carrier is generally Al2O3Or Al2O3-SiO2, can contain
P, the auxiliary agents such as Ti, B, Zr.Conventional reduction is carried out using procatalyst, ensures hydrogenation active metals during the reaction in also
Ortho states.The field general goods catalyst can be selected or prepared by this field commonsense method.
In the method for the present invention, step（2）Described in the reaction condition of the second hydroconversion reaction zone be：Temperature for 150 DEG C~
280 DEG C, be preferably 210 DEG C~260 DEG C, and hydrogen partial pressure is 6.0MPa~18.0MPa, preferably 10.0~15.0MPa, volume space velocity
For 0.3h-1~3.0h-1, it is preferably 0.6h-1~1.2h-1, hydrogen to oil volume ratio 400:1~1500:1, it is preferably 600:1~800:
1。
In the method for the present invention, step（3）Described in distillation vacuum distillation may be employed, the condition of the vacuum distillation is：
5~40 millimetres of mercury of tower top pressure is distilled, is preferably 5~15 millimetress of mercury；Destilling tower column bottom temperature is 250 DEG C~350 DEG C, excellent
Elect 280 DEG C~320 DEG C as.
Under the action of the bifunctional catalyst that raw material Fischer-Tropsch wax loads in the first reaction zone in the method for the present invention, take
It asks wax that dehydrocyclization reaction generation alkylbenzene occurs, passes through the relationship analysis of the condensation point to hydro carbons and viscosity index (VI) and molecular structure
After find, the alkylbenzene of same carbon number is more much lower than the condensation point of n-alkane, and can meet lube base oil to low temperature
The demand of mobility.The method of the present invention can reach reduction Fischer-Tropsch wax as existing isomerization dewaxing or CATALYTIC DEWAXING TECHNIQUE and coagulate
The purpose of point.Advantage of the invention is that the long-chain mononuclear aromatics compound of identical condensation point has higher viscosity than isoparaffin
Index, so the viscosity index (VI) of lube base oil produced by the invention is higher than the viscosity index (VI) of isomerization dewaxing base oil.Due to
Molecular sieve is substantially increased using rare-earth element modified TON type molecular sieves using bifunctional catalyst in the method for the present invention
Acid and acid strength, reduces the reaction temperature of the first reaction zone, reduces the formation of process carbon deposit.And first in reaction zone
Dehydrocyclization pour point depression process carry out under low pressure, the investment of device can be substantially reduced.In addition, the first reaction zone uses catalyst
Grading loading mode, using dehydrogenation reaction be temperature drop process the characteristics of, the activity of Proper Match dehydrogenation reaction temperature and catalyst,
The selectivity of dehydrocyclization process is improved, while reduces the content of molecular sieve in catalyst on the whole, reduces catalyst
Production cost.
Specific embodiment
Illustrate the particular content and effect of the method for the present invention below by specific embodiment.Following implementation column will be to this hair
The method of bright offer is further described, but scope not thereby limiting the invention.Fischer-Tropsch wax used in the present invention
Matter is shown in Table 1, step（2）The physicochemical property of the Hydrobon catalyst of middle use is shown in Table 2.
1 feedstock property of table
2 Hydrobon catalyst property of table
| Project | Data |
| Chemical composition, wt% | |
| Pd | 0.20 |
| Pt | 0.30 |
| Carrier γ-Al2O3 | Surplus |
| Physical property | |
| Pore volume, mL.g-1 | ≮0.5 |
| Specific surface area, m2.g-1 | ≮220 |
| Crushing strength, N.cm-1 | ≮100 |
| Bulk density, g.cm-3 | 0.55~0.62 |
| Shape | Cylindrical bars |
| Size, mm | Φ 3 × (3~8) |
| Project | Data |
| Chemical composition, weight % | |
| Platinum (Pt) | 0.2-0.5 |
| Physical property | |
| Appearance and size (φ × L)/mm | (1.4-1.6) × (3~8) |
| Pore volume, mL.g-1 | ≥0.30 |
| Specific surface area ,/m2.g-1 | ≥180 |
| Bulk density, g.cm-3 | 0.65~0.75 |
| Crushing strength, N.cm-1 | ≥100 |
| Shape | Cylindrical bars |
Embodiment 1
The preparation method of bifunctional catalyst used in the present invention：
（1）The ZSM-22 molecular sieves that method according to Chinese patent CN1565969A embodiments 1 is prepared, al mole ratio are
95, specific surface area 220m2/ g, pore volume 0.23mL/g.
（2）It will（NH4）2Ce(NO3)6（Beijing Chemical Plant produces, and analysis is pure）And water is configured to Ce2O3Weight percent is dense
The aqueous solution for 15% is spent, by step（1）1500 grams of obtained molecular sieve is sufficiently mixed with 2000 grams of above-mentioned aqueous solutions containing cerium, in
When freeze-day with constant temperature 8 is small at 120 DEG C, when constant temperature calcining 8 is small at 460 DEG C, Ce is obtained2O3Weight percent content is 15% containing cerium
ZSM-22。
（3）By 1000 grams of steps（2）Obtained molecular sieve containing cerium and 500 grams of SB alumina powders are sufficiently mixed, and are then added in
100 gram weight concentration are 40% dust technology and suitable water, and kneading is into plastic paste, and extrusion is into the cylinder of a diameter of 1.2mm
Item by the molding when 120 DEG C of constant temperature 8 are small, then when constant temperature 6 is small at 550 DEG C, obtains catalyst carrier, consisting of：
75wt% modified ZSM-5s -23 and 25wt% aluminium oxide.
（4）With containing H2PtCl6Aqueous solution, using saturation impregnate method platinum is loaded into step（3）Obtained carrier
On, when constant temperature 6 is small at 150 DEG C, when constant temperature 8 is small at 500 DEG C, bifunctional catalyst 1 is obtained, composition and physico-chemical property are shown in Table
3, reaction condition and reaction result are shown in Table 6.
Embodiment 2
The preparation method of the bifunctional catalyst is with embodiment 1, the difference is that rare-earth compound used is La
(NO3)3·6H2O（Beijing Chemical Plant produces, and analysis is pure）, La in solution containing lanthanum used2O3Content is 2.5 wt%, and hydrogenation component is
Palladium, containing palladium compound used are palladium nitrate, and for wherein palladium in terms of metal, solution concentration 3.2wt% obtains bifunctional catalyst
2, composition and physico-chemical property are shown in Table 3, and reaction condition and reaction result are shown in Table 6.
Embodiment 3
Using the molecular sieves of ZSM-22 containing cerium obtained and method for preparing catalyst in embodiment 1, it is respectively according to molecular sieve content
42%th, 60% and 72% three kinds of bifunctional catalysts 4,5 and 6 are made, composition and physico-chemical property are shown in Table 4, catalyst 4,5 and 6 according to
Volume ratio 40:40:30 carry out grading loading, and reaction condition and reaction result are shown in Table 6.
Embodiment 4
Using the molecular sieves of ZSM-22 containing lanthanum obtained and method for preparing catalyst in embodiment 2, it is respectively according to molecular sieve content
45%th, 64% and 75% three kinds of bifunctional catalysts 7,8 and 9 are made, composition and physico-chemical property are shown in Table 5, catalyst 7,8 and 9 according to
Volume ratio 50:30:20 carry out grading loading, and reaction condition and reaction result are shown in Table 6.
Comparative example 1
The preparation method of the bifunctional catalyst is with embodiment 1, the difference is that molecular sieve used is without containing rare earth member
Plain solution treatment obtains bifunctional catalyst 3, and composition and physico-chemical property are shown in Table 3, and reaction condition and reaction result are shown in Table 6.
Comparative example 2
Step（1）Using traditional isomerization dewaxing catalyst, trade name FIW-12（Sinopec catalyst branch company produces）, into
The condition and reaction result of row isomerization dewaxing reaction are shown in Table 6.
3 bifunctional catalyst of table, 1,2,3 physical property
4 bifunctional catalyst of table, 4,5,6 physical property
5 bifunctional catalyst of table, 7,8,9 physical property
6 reaction condition of table and reaction result
Table 6 the result shows that, the method for the present invention is more preferable than traditional isomerization dewaxing pour point depression process choosing, that is, improves lubrication oil base
The yield of plinth oil product, while the viscosity index (VI) of obtained base oil is also higher.Using rare-earth element modified TON molecular sieves and
Catalyst grade is matched somebody with somebody, and reduces the reaction temperature of the first reaction zone, reduces the formation of process carbon deposit.
Claims (16)
1. a kind of method for producing lube base oil, the described method includes following contents：
（1）Into the first reaction zone after Fischer-Tropsch wax and hydrogen mixing, it is anti-that dehydrocyclization occurs under the action of bifunctional catalyst
It should；
（2）By step（1）Obtained reaction effluent carries out gas-liquid separation, after isolated liquid phase effluent and hydrogen mix
Into the second hydroconversion reaction zone, hydrofining reaction occurs under Hydrobon catalyst effect；
（3）By step（2）Obtained hydrofinishing effluent carries out gas-liquid separation, and separating obtained liquid product obtains not through distillation
With the lube base oil of viscosity grade.
2. according to the method for claim 1, it is characterised in that：The Fischer-Tropsch wax refers to that synthesis gas passes through F- T synthesis mistake
The full fraction of Fischer-Tropsch product or the heavy constituent of Fischer-Tropsch product that journey obtains, the boiling range of the heavy constituent is 350-700 DEG C.
3. according to the method for claim 1, it is characterised in that：Step（1）Described in bifunctional catalyst include TON types
Molecular sieve, metal component and inorganic refractory oxide；The wherein described TON types molecular sieve is the TON type molecules containing rare earth element
Sieve；Inorganic refractory oxide one or more of for aluminium oxide, titanium oxide, boron oxide, silica, zirconium oxide and magnesia,
Metal component is noble metal, is specially platinum and/or palladium.
4. according to the method for claim 1, it is characterised in that：The bifunctional catalyst in terms of the weight of catalyst,
Composition is as follows：The type molecular sieves of TON containing rare earth element 10wt%~95wt%；Metal component is calculated as 0.05wt%~5.0wt% with metal,
Inorganic refractory oxide 15wt%~40wt%.
5. according to the method for claim 4, it is characterised in that：In the types of TON containing the rare earth element molecular sieve, rare earth element
In terms of oxide（RE2O3）Composition in the catalyst is 1wt%~15wt%, is preferably 3wt%~10wt%.
6. according to the method for claim 1, it is characterised in that：The bifunctional catalyst specific surface area for 200~
350m2/ g, pore volume are 0.3~0.5mL/g.
7. according to the method for claim 3, it is characterised in that：The TON types molecular sieve is ZSM-22 molecular sieves, Nu-
One or more in 10 molecular sieves, KZ-2 molecular sieves and ISI-1 molecular sieves are preferably ZSM-22 molecular sieves.
8. according to the method for claim 3, it is characterised in that：The silica alumina ratio of the TON types molecular sieve for 50~
200, it is preferably 80~160.
9. according to the method for claim 3, it is characterised in that：The rare earth element for lanthanum, cerium, praseodymium, promethium, samarium, europium,
One or more in dysprosium, gadolinium, erbium, thulium, yttrium, lutetium are preferably lanthanum and/or cerium.
10. according to the method for claim 3, it is characterised in that：The types of TON containing the rare earth element molecular sieve is by rare earth member
Plain compound is directly mixed with TON types molecular sieve, then in 20~300 DEG C of dry 1h~48h, is then roasted at 400 DEG C~800 DEG C
0.5h~10h is burnt, obtains the TON type molecular sieves containing rare earth element.
11. according to the method for claim 1, it is characterised in that：Step（1）Described in the first reaction zone according to Fischer-Tropsch wax
Bifunctional catalyst A, bifunctional catalyst B and bifunctional catalyst C are loaded successively with the flow direction of hydrogen, it is described difunctional
The TON type molecular sieve contents containing rare earth element are respectively 42wt%~45wt% in catalyst A, are contained in the bifunctional catalyst B
The TON type molecular sieve contents of rare earth element are respectively 60wt%~64wt%, containing rare earth element in the bifunctional catalyst C
TON type molecular sieve contents are respectively 72wt%~75wt%.
12. according to the method for claim 11, it is characterised in that：Bifunctional catalyst A, double work(in first reaction zone
The admission space ratio of energy catalyst B and bifunctional catalyst C is 40~50：40~30：30~20.
13. according to the method for claim 1, it is characterised in that：The reaction condition of first reaction zone is：Temperature is
350 DEG C~480 DEG C, be preferably 420 DEG C~480 DEG C, and hydrogen partial pressure is 0.05MPa~1.0MPa, is preferably 0.05~0.30MPa,
Volume space velocity is 0.1h-1~3.0h-1, it is preferably 0.5h-1~2.0h-1, hydrogen to oil volume ratio 50:1~1500:1, it is preferably 200:1
~800:1.
14. according to the method for claim 1, it is characterised in that：Step（2）Described in the second hydroconversion reaction zone reaction
Condition is：Temperature is 150 DEG C~280 DEG C, is preferably 210 DEG C~260 DEG C, and hydrogen partial pressure is 6.0MPa~18.0MPa, is preferably
10.0~15.0MPa, volume space velocity 0.3h-1~3.0h-1, it is preferably 0.6h-1~1.2h-1, hydrogen to oil volume ratio 400:1~
1500:1, it is preferably 600:1~800:1.
15. according to the method for claim 1, it is characterised in that：Step（3）Described in distillation using vacuum distillation.
16. according to the method for claim 15, it is characterised in that：The condition of the vacuum distillation is：Distill tower top pressure 5
~40 millimetress of mercury are preferably 5~15 millimetress of mercury；Destilling tower column bottom temperature is 250 DEG C~350 DEG C, preferably 280 DEG C~
320℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611051788.4A CN108102698B (en) | 2016-11-25 | 2016-11-25 | Method for producing lubricating oil base oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611051788.4A CN108102698B (en) | 2016-11-25 | 2016-11-25 | Method for producing lubricating oil base oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108102698A true CN108102698A (en) | 2018-06-01 |
| CN108102698B CN108102698B (en) | 2020-07-03 |
Family
ID=62205182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611051788.4A Active CN108102698B (en) | 2016-11-25 | 2016-11-25 | Method for producing lubricating oil base oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108102698B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745940A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Production method of low-cloud-point lubricating oil base oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173193A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Paraffinic hydrocarbon shape selecting isomerization catalyst and method for producing the same |
| CN101942321A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method for producing base oil of lubricating oil by isomerization dewaxing |
| CN102533329A (en) * | 2010-12-31 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax |
| CN105316036A (en) * | 2014-06-16 | 2016-02-10 | 中国石油化工股份有限公司 | Method of producing ultrahigh-viscosity-index lubricant base oil |
-
2016
- 2016-11-25 CN CN201611051788.4A patent/CN108102698B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173193A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Paraffinic hydrocarbon shape selecting isomerization catalyst and method for producing the same |
| CN101942321A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method for producing base oil of lubricating oil by isomerization dewaxing |
| CN102533329A (en) * | 2010-12-31 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax |
| CN105316036A (en) * | 2014-06-16 | 2016-02-10 | 中国石油化工股份有限公司 | Method of producing ultrahigh-viscosity-index lubricant base oil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745940A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Production method of low-cloud-point lubricating oil base oil |
| CN112745940B (en) * | 2019-10-30 | 2023-01-10 | 中国石油化工股份有限公司 | Production method of low-cloud-point lubricating oil base oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108102698B (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3342844A1 (en) | Method for manufacturing lubricant base oil | |
| CN101596462B (en) | Hydroisomerizaion catalyst and preparation method thereof | |
| CN101722031B (en) | Shape -selective isomerization catalyst for long-chain normal paraffin as well as preparation method and application thereof | |
| JP3036685B2 (en) | Hydrogen reduction and isomerization of petroleum products containing benzene | |
| CN104399520B (en) | Catalyst for producing high-octane-number gasoline composition from heavy aromatic hydrocarbons and preparation method of catalyst | |
| CN101173193B (en) | Paraffinic hydrocarbon shape selecting isomerization catalyst and method for producing the same | |
| TW200900145A (en) | Hydroisomerization catalyst, method of dew axing hydrocarbon oil, process for producing base oil, and process for producing lube base oil | |
| CN112322349B (en) | Full conversion method and device for producing light aromatic hydrocarbon from catalytic diesel oil | |
| CN101942320A (en) | Method for producing base oil by isodewaxing | |
| CN101942321A (en) | Method for producing base oil of lubricating oil by isomerization dewaxing | |
| CN102441416B (en) | Paraffin hydrocarbon shape selective isomerization catalyst, preparation method and application thereof | |
| CN103769191B (en) | Catalyst, reaction unit and reaction method for F-T synthesis wax oil mild hydrogenation cracking | |
| CN101942322B (en) | Lubricating oil base oil producing method | |
| CN109622022A (en) | A kind of preparation method and application of high dispersive Pt modified Nano HZSM-5 catalyst | |
| CN108102698A (en) | A kind of method for producing lube base oil | |
| CN102441417B (en) | Paraffin hydrocarbon shape selective isomerization catalyst, preparation method and application thereof | |
| CN111036204B (en) | Glycerol hydrogenolysis method | |
| Walendziewski et al. | Selectivity of platinum–zirconia catalysts in n-paraffins hydroisomerisation process | |
| CN104383961A (en) | Catalyst for hydrocracking heavy aromatics for producing high-purity BTX aromatics and preparing method of catalyst | |
| CN100364668C (en) | Method for preparing surface modified IIB metal oxide hydrogenation catalyst | |
| CN103418412B (en) | Catalytic reforming catalyst and preparation method thereof | |
| CN106582780B (en) | Alloy-type heavy aromatics lightening catalyst and preparation method thereof | |
| CN115282992B (en) | Preparation method of amorphous nickel phosphide catalyst loaded by in-situ synthesized multistage hole ZSM-5 molecular sieve | |
| CN102311805B (en) | Vaseline production method | |
| RU2536585C1 (en) | Catalyst, method of manufacturing thereof and process of diesel fuel hydroisomerisation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |