CN103878017B - A kind of base metal isomerization catalyst and method for making thereof and application - Google Patents
A kind of base metal isomerization catalyst and method for making thereof and application Download PDFInfo
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Abstract
A kind of base metal isomerization catalyst is made up of the transition metal oxide of ten-ring molecular sieve and load Raney's nickel, wherein the weight ratio of components of the transition metal oxide of ten-ring molecular sieve and load Raney's nickel is 0.2-5:1, and the weight ratio of components of transition metal oxide and Raney's nickel is 0.05-2:1.It is low that the present invention has cost, and it is active good to have for Fischer-Tropsch wax isomery lube base oil, the advantage that stereoselectivity is high.
Description
Technical field
The present invention relates to a kind of catalyst, is a kind of non-precious metal catalyst for hydro-isomerization and its preparation method and application specifically.
Technical background
Along with the fast development of auto industry and the enhancing of environmental protection consciousness, top-grade lubricating oil accounting in the market share is increasing, the production of top-grade lubricating oil, and base oil quality is a very important ring, and high-quality feed of base oil is in long term structural shortage.
In the thick product of F-T synthesis, soft wax refers to that carbon number distribution concentrates on C
25-50fraction section, its proportion in on-gaseous product is about 25-30%, and saturation degree is high, hardly sulfur-bearing, nitrogen, aromatic hydrocarbons, is prepare the rare quality raw materials of top-grade lubricating oil base oil.Fischer-Tropsch synthetic mainly improves its low temperature flowability as lube base oil, is namely obtained the top-grade lubricating oil base oil product of low pour point, high viscosity index by isomerization reaction.At present, the foreign oil companies such as Shell, Exxon-Mobil adopt the selective isomerization technology of oil from Fischer-Tropsch synthesis to prepare high-grade lube base oil, viscosity index (VI) is greater than 140, and obtains huge commercial interest, and correlation technique also monopolized by above-mentioned company.
The key problem in technology that Fischer-Tropsch synthetic prepares lube base oil is straight chain alkane isomerization, from theory, petrochemical industry can be assisted other process for refining to process by isomerization technique completely and be obtained APIIII class lubricating oil base oil, but the complexity of raw material sources makes its processing cost remain high, and cannot mention in the same breath with synthetic lubricant base oil (PAO).F-T synthesis route is prepared lube base oil and is had Fundamental Physical Properties close to PAO, and cost but only has its part, becomes the important selection of top-grade lubricating oil base oil production line, has broad application prospects in future.
Typical isomerization catalyst is a kind of bifunctional catalyst, comprises acid function and hydrogenation/dehydrogenation function.Acid carrier is mainly molecular sieve or oxide, it provides the acidic site of isomerization/cracking, wherein the selective activization of one dimension tubulose ten-ring duct molecular sieve inhibits the generation of the more much higher branched chain isomer of cracking activity well, effectively improve isomerisation selectivity and monomethyl isomers yield, the lubricating oil of low condensation point, high viscosity index (HVI) can be prepared; Metal position is then to provide hydrogenation/dehydrogenation function, external disclosed patent at present, as US6179994, EP0321302A2, US5565086A, EP0635556A1, and domestic disclosed patent, as CN101052465A, CN1305871A, CN1792451A, CN102441416A, CN1448476A etc., the metal used is group VIII noble metals Pt, Pd, catalyst cost is remained high, have impact on the economic interests of relevant enterprise.
Summary of the invention
For solving the problem, the invention provides a kind of cheapness, the isomerization catalyst of hydrogenation/dehydrogenation function and its preparation method and application.
Raney's nickel (RaneyNi) is the metallic Ni catalyst of spongy pore structure, has excellent hydrogenation and hydro-isomerization function, and transition metal oxide, as V
2o
5, Cr
2o
3, Fe
2o
3, MoO
3etc. the dehydrogenation with excellence, the combination of the two successfully instead of the precious metals pt/Pd catalyst with hydrogenation/dehydrogenation function.
Catalyst of the present invention is made up of the transition metal oxide of ten-ring molecular sieve and load Raney's nickel, wherein the weight ratio of components of the transition metal oxide of ten-ring molecular sieve and load Raney's nickel is 0.2-5:1, and the weight ratio of components of transition metal oxide and Raney's nickel is 0.05-2:1.
Described ten-ring molecular sieve is the molecular sieve of the structure types such as AEL, TON, MTT, MEL, FER of one dimension tubulose, be preferably ZSM-22, ZSM-23, SAPO-11 and SAPO-41, be more preferably the SAPO-11 molecular sieve that synthesis relatively simply has AEL topological structure.
Described transition metal oxide is selected from V
2o
5, Cr
2o
3, Fe
2o
3, MoO
3deng one.
Catalyst of the present invention is prepared according to following steps:
(1) by catalyst composition, ten-ring molecular sieve is taken;
(2) form by final catalyst, by Ni-Al alloy and transition metal oxide mechanical mixture abundant, with after soaking 0.5-12h in the NaOH solution of 0.5-50.0 (wt) % at 40-100 DEG C, be washed with distilled water to neutrality, after drying, obtain the transition metal oxide of load Raney's nickel;
(3) transition metal oxide of ten-ring molecular sieve, load Raney's nickel, extrusion aid sesbania powder, water are become plastic paste, extruded moulding with the abundant kneading of peptizing agent, after drying, 250-500 DEG C roasting 2-10h, obtain catalyst.
Ten-ring molecular sieve described in step (1) is the molecular sieve of the structure types such as AEL, TON, MTT, MEL, FER of one dimension tubulose, be preferably ZSM-22, ZSM-23, SAPO-11 and SAPO-41, can prepare according to the method for patent CN103101924A, CN101508445, CN102381716A, CN101613114, CN102815720A, CN103011196A, CN102372289A etc.
Ni-Al alloy described in step (2) is NiAl
3-Al, NiAl
3, Ni
2al
3one,
Peptizing agent described in step (3) is the one of nitric acid, hydrochloric acid, acetic acid, formic acid etc.
Kaolinite Preparation of Catalyst of the present invention reacts on fixed bed reaction apparatus, can be used for the isomery processing procedure of the various direct-connected paraffinic feedstock of initial boiling point more than 160 DEG C, and be specially adapted to the hydro-isomerization processing procedure of Fischer-Tropsch wax, the character of Fischer-Tropsch wax is in table 1.Catalyst needs to carry out reduction treatment, reducing condition before charging: hydrogen atmosphere, SV=500-2000h
-1(v/v), 400-500 DEG C, 0.1-1.0Mpa, recovery time 4-24h.Reaction condition: 350-500 DEG C, Hydrogen Vapor Pressure 2.0-8.0MPa, liquid hourly space velocity (LHSV) is 0.2-2.5h
-1(v/v), hydrogen to oil volume ratio 200-1200, is preferably: 350-400 DEG C, Hydrogen Vapor Pressure 3.0-5.0MPa, liquid hourly space velocity (LHSV) 0.5-1.5h
-1, hydrogen to oil volume ratio 300-600.
Catalyst of the present invention has the low outstanding advantages of cost, and it is active good to have for Fischer-Tropsch wax isomery lube base oil, the advantage that stereoselectivity is high.
Detailed description of the invention
Embodiment 1
SAPO-11 molecular sieve is prepared: 50ml deionized water, 10ml phosphoric acid, 12g boehmite, 3.5ml ethyl orthosilicate, 10ml di-n-propylamine are mixed successively according to the method described in patent CN101503201A, stir evenly, pH is regulated to be 6.5, proceed to band teflon lined reactor 180 DEG C at crystallization 48h, through cooling, washing, filtration, drying, obtained molecular screen primary powder, 600 DEG C of roasting 5h obtain SAPO-11 molecular sieve;
By final catalyst weight composition RaneyNi:V
2o
5=0.05:1, takes a certain amount of NiAl
3-Al, with a certain amount of V
2o
5mechanical mixture is abundant, at 90 DEG C, be washed with distilled water to neutrality after soaking 6h in the NaOH solution of 5.0 (wt) %, drying obtains (RaneyNi/V
2o
5; By final catalyst weight composition RaneyNi/V
2o
5: SAPO-11=5:1, takes a certain amount of above-mentioned SAPO-11 molecular sieve, with RaneyNi/V
2o
5and sesbania powder, water and 2.0 (wt) % nitric acid fully mix, pinch into plastic paste, extruded moulding, dry, obtain catalyst after 350 DEG C of roasting 4h, weight consists of RaneyNi:V
2o
5: SAPO-11=0.24:4.76:1.
Get above-mentioned catalyst 10g, apply in fixed bed reactors, reducing condition is: pure hydrogen, SV=500h
-1(v/v), 400 DEG C, 0.1Mpa, recovery time 24h.Reaction condition: 350 DEG C, Hydrogen Vapor Pressure 2.0MPa, liquid hourly space velocity (LHSV) is 0.2h
-1(v/v), hydrogen to oil volume ratio 200.The present embodiment is raw materials used is fischer-tropsch product wax, and its character is in table 2, and catalyst reaction performance is in table 5.
Embodiment 2
ZSM-22 molecular sieve is prepared: after 10.4g deionized water being mixed with 0.07g aluminum sulfate according to the method described in patent CN103101924A, add 0.22gKOH wherein, 0.43g1 is added after stirring clarification, 6-hexamethylene diamine, under agitation adds 3g tetraethyl orthosilicate, continues to stir until after dissolution homogeneity formation silica-alumina gel, be placed in reactor 185 DEG C of crystallization 24h, product suction filtration, oven dry, obtain ZSM-22 molecular screen primary powder, and 550 DEG C of roasting 6h obtain ZSM-22 molecular sieve;
By final catalyst weight composition RaneyNi/:Cr
2o
3=0.1:1, takes a certain amount of NiAl
3, with a certain amount of Cr
2o
3mechanical mixture is abundant, and at 100 DEG C, be washed with distilled water to neutrality after soaking 0.5h in the NaOH solution of 50 (wt) %, drying obtains RaneyNi/Cr
2o
3; By final catalyst weight composition RaneyNi/Cr
2o
3: SAPO-11=4:1, takes a certain amount of above-mentioned ZSM-22 molecular sieve, with RaneyNi/Cr
2o
3and sesbania powder, water and 1.0 (wt) % hydrochloric acid fully mix, pinch into plastic paste, extruded moulding, dry, obtain catalyst after 330 DEG C of roasting 5h, weight consists of RaneyNi:Cr
2o
3: ZSM-22=0.36:3.64:1.
Get above-mentioned catalyst 10g, apply in fixed bed reactors, reducing condition is: pure hydrogen, SV=750h
-1(v/v), 410 DEG C, 0.2Mpa, recovery time 20h.Reaction condition: 380 DEG C, Hydrogen Vapor Pressure 3.0MPa, liquid hourly space velocity (LHSV) is 0.5h
-1(v/v), hydrogen to oil volume ratio 3000.The present embodiment is raw materials used is fischer-tropsch product wax, and its character is in table 2, and catalyst reaction performance is in table 5.
Embodiment 3
Prepare SAPO-11 molecular sieve according to the method described in patent CN102381716A: take 10.85g boehmite, be dissolved in wiring solution-forming in 18.0g deionized water, heating, stir 0.5h; Measuring 9.7ml di-n-propylamine is added drop-wise in the solution obtained in last step, stirs 2h, then takes 10.3g Ludox again and join in this solution, stirs 2h, obtains aqueous slurry; When aqueous slurry is heated to 80 DEG C, be added drop-wise in aqueous slurry, pH=7.0 by 16.45g phosphoric acid, stir 1h, obtain colloidal mixture, its mole consists of di-n-propylamine: Al
2o
3: P
2o
5: 0.6SiO
2: 50H
2o, by this colloidal mixture in 190 DEG C of magnificent 24h of crystalline substance, by much filtrate cooling washing, 110 DEG C of dry 12h, then in Muffle furnace 600 DEG C of roasting 4h, obtain SAPO-11 molecular sieve, finally consist of Al
2o
3: P
2o
5: SiO
2=1:0.44:0.3.
By final catalyst weight composition RaneyNi:Fe
2o
3=0.2:1, takes a certain amount of Ni
2al
3, with a certain amount of Fe
2o
3mechanical mixture is abundant, and at 50 DEG C, be washed with distilled water to neutrality after soaking 6h in the NaOH solution of 2 (wt) %, drying obtains RaneyNiFe
2o
3; By final catalyst weight composition RaneyNiFe
2o
3: SAPO-11=3:1, takes a certain amount of above-mentioned SAPO-11 molecular sieve, with RaneyNiFe
2o
3and sesbania powder, water and 3.0 (wt) % acetic acid fully mix, pinch into plastic paste, extruded moulding, dry, obtain catalyst after 360 DEG C of roasting 6h, weight consists of RaneyNi:Fe
2o
3: SAPO-11=0.5:2.5:1.
Get above-mentioned catalyst 10g, apply in fixed bed reactors, reducing condition is: pure hydrogen, SV=1000h
-1(v/v), 420 DEG C, 0.3Mpa, recovery time 16h.Reaction condition: 400 DEG C, Hydrogen Vapor Pressure 4.0MPa, liquid hourly space velocity (LHSV) 1.0h
-1(v/v), hydrogen to oil volume ratio 500.The present embodiment is raw materials used is fischer-tropsch product wax, and its character is in table 3, and catalyst reaction performance is in table 5.
Embodiment 4
ZSM-23 molecular screen is prepared: under agitation according to method described in patent CN101613114, diluting 38.2 parts of weight concentrations with 88 parts of water is the concentrated sulfuric acid of 98.7%, obtain dilution heat of sulfuric acid, dripping 96 parts of weight concentrations is wherein the ethamine of 65.8, makes solution A.Then under stirring, solution A is slowly added dropwise to 357 parts of waterglass (SiO
2weight concentration 24.93%, Na
2o weight concentration 7.33%) in obtain mixed liquid B.Again the 20 parts of water being dissolved with 9 parts of KOH are added dropwise in mixed liquid B, finally add 1.2 parts of ZSM-22 molecular sieves as crystal seed, stir and form gel, proceed to in teflon-lined stainless steel cauldron, brilliant China 24 hours at 155 DEG C, after crystallization terminates, through Distillation recovery ethamine, Separation of Solid and Liquid, washing, drying, 500 DEG C of roasting 10h, obtain ZSM-23 molecular screen.
By final catalyst weight composition RaneyNi:MoO
3=0.5:1, takes a certain amount of NiAl
3-Al, with a certain amount of MoO
3mechanical mixture is abundant, and at 60 DEG C, be washed with distilled water to neutrality after soaking 6h in the NaOH solution of 10 (wt) %, drying obtains RaneyNi/MoO
3; By final catalyst weight composition RaneyNi/MoO
3: SAPO-11=2:1, takes a certain amount of above-mentioned ZSM-23 molecular screen, RaneyNi/MoO
3and sesbania powder, water and 5.0 (wt) % formic acid fully mix, pinch into plastic paste, extruded moulding, dry, obtain catalyst after 300 DEG C of roasting 8h, weight consists of RaneyNi:MoO
3: ZSM-23=0.67:1.33:1.
Get above-mentioned catalyst 10g, apply in fixed bed reactors, reducing condition is: pure hydrogen, SV=1250h
-1(v/v), 4350 DEG C, 0.5Mpa, recovery time 12h.Reaction condition: 420 DEG C, Hydrogen Vapor Pressure 5.0MPa, liquid hourly space velocity (LHSV) is 1.2h
-1(v/v), hydrogen to oil volume ratio 700.The present embodiment is raw materials used is fischer-tropsch product wax, and its character is in table 3, and catalyst reaction performance is in table 5.
Embodiment 5
SAPO-11 molecular sieve is prepared: 50ml deionized water, 8ml phosphoric acid, 20g boehmite, 5.5ml Ludox, 10ml di-n-propylamine are mixed successively according to the method described in patent CN101503201A, stir evenly, pH is regulated to be 7.0, proceed to band teflon lined reactor 160 DEG C at crystallization 120h, through cooling, washing, filtration, drying, obtained molecular screen primary powder, 580 DEG C of roasting 4h obtain SAPO-11 molecular sieve.
By final catalyst weight composition RaneyNi:V
2o
5=1:1, takes a certain amount of NiAl
3, with a certain amount of V
2o
5mechanical mixture is abundant, and at 70 DEG C, be washed with distilled water to neutrality after soaking 6h in the NaOH solution of 3.0 (wt) %, drying obtains RaneyNi/V
2o
5; By final catalyst weight composition RaneyNi/V
2o
5: SAPO-11=1:1, takes a certain amount of above-mentioned SAPO-11 molecular sieve, with RaneyNi/V
2o
5and sesbania powder, water and 0.5 (wt) % nitric acid fully mix, pinch into plastic paste, extruded moulding, dry, obtain catalyst after 250 DEG C of roasting 10h, weight consists of RaneyNi:V
2o
5: SAPO-11=0.5:0.5:1.
Get above-mentioned catalyst 10g, apply in fixed bed reactors, reducing condition is: pure hydrogen, SV=1500h
-1(v/v), 430 DEG C, 0.7Mpa, recovery time 10h.Reaction condition: 450 DEG C, Hydrogen Vapor Pressure 6.0MPa, liquid hourly space velocity (LHSV) is 1.5h
-1(v/v), hydrogen to oil volume ratio 800.The present embodiment is raw materials used is fischer-tropsch product wax, and its character is in table 4, and catalyst reaction performance is in table 5.
Embodiment 6
ZSM-5 molecular sieve is prepared: be that the phosphoric acid of 85%, boehmite, di-n-butylamine and Ludox join in deionized water successively by mass fraction, under the rotating speed of 1000r/min, stir 6h, namely obtain Primogel according to method described in patent CN103011196A; Two, the Primogel obtained in step one is placed in teflon-lined stainless steel crystallizing kettle, crystallization 36h at 180 DEG C, then room temperature is cooled to, be cooled to room temperature produce crystallization product through successively through centrifugal, washing and 120 DEG C at dry 124h, finally roasting 60h at 570 DEG C, naturally cools to room temperature and namely obtains SAPO-41 molecular sieve; Mass fraction described in step one is the phosphoric acid of 85% and the mass ratio of boehmite is 1:(0.3-1.2); Mass fraction described in step one is the phosphoric acid of 85% and the mass ratio of di-n-butylamine is 1:(11-2.4); Mass fraction described in step one is the phosphoric acid of 85% and the mass ratio of Ludox is 1:(0.05-1.0); Mass fraction described in step one is the phosphoric acid of 85% and the mass ratio of deionized water is 1:(3.1-5.1).
By final catalyst weight composition RaneyNi:Cr
2o
3=1.5:1 takes a certain amount of Ni
2al
3, with a certain amount of Cr
2o
3mechanical mixture is abundant, and at 80 DEG C, be washed with distilled water to neutrality after soaking 6h in the NaOH solution of 4.0 (wt) %, drying obtains RaneyNi/Cr
2o
3; By final catalyst weight composition RaneyNi/Cr
2o
3: SAPO-11=0.5:1, takes a certain amount of above-mentioned ZSM-41 molecular sieve, with RaneyNi/Cr
2o
3and sesbania powder, water and 0.2 (wt) % acetic acid fully mix, pinch into plastic paste, extruded moulding, dry, obtain catalyst after 400 DEG C of roasting 3h, weight consists of RaneyNi:Cr
2o
3: ZSM-41=0.3:0.2:1.
Get above-mentioned catalyst 10g, apply in fixed bed reactors, reducing condition is: pure hydrogen, SV=1750h
-1(v/v), 4850 DEG C, 0.58Mpa, recovery time 8h.Reaction condition: 480 DEG C, Hydrogen Vapor Pressure 7.0MPa, liquid hourly space velocity (LHSV) is 2.0h
-1(v/v), hydrogen to oil volume ratio 1000.The present embodiment is raw materials used is fischer-tropsch product wax, and its character is in table 4, and catalyst reaction performance is in table 5.
Embodiment 7
SAPO-11 molecular sieve is prepared: 90ml propyl alcohol, 8ml phosphoric acid, 12g boehmite, 3.5ml Ludox, 15ml di-n-propylamine are mixed successively according to the method described in patent CN101503201A, stir evenly, pH is regulated to be 7.0, proceed to band teflon lined reactor 180 DEG C at crystallization 120h, through cooling, washing, filtration, drying, obtained molecular screen primary powder, 550 DEG C of roasting 8h, obtain SAPO-11 molecular sieve.
By final catalyst weight composition RaneyNi:Fe
2o
3=2:1, takes a certain amount of NiAl
3, with a certain amount of Fe
2o
3mechanical mixture is abundant, and at 40 DEG C, be washed with distilled water to neutrality after soaking 6h in the NaOH solution of 0.5 (wt) %, drying obtains RaneyNi/Fe
2o
3; By final catalyst weight composition RaneyNi/Fe
2o
3: SAPO-11=0.2:1, takes a certain amount of above-mentioned SAPO-11 molecular sieve, with RaneyNi/Fe
2o
3and sesbania powder, water and 0.1 (wt) % nitric acid fully mix, pinch into plastic paste, extruded moulding, dry, obtain catalyst after 500 DEG C of roasting 2h, weight consists of RaneyNi:Fe
2o
3: SAPO-11=0.14:0.07:1.
Get above-mentioned catalyst 10g, apply in fixed bed reactors, reducing condition is: pure hydrogen, SV=2000h
-1(v/v), 500 DEG C, 1.0Mpa, recovery time 4h.Reaction condition: 500 DEG C, Hydrogen Vapor Pressure 8.0MPa, liquid hourly space velocity (LHSV) is 2.5h
-1(v/v), hydrogen to oil volume ratio 1200.The present embodiment is raw materials used is fischer-tropsch product wax, and its character is in table 4, and catalyst reaction performance is in table 5.
The character of table 1 fischer-tropsch product wax
| Viscosity (40 DEG C), mm 2/s | Pour point, DEG C | Wax content, wt% | Isomerisation degree, % | Boiling range/ |
| 19～21 | 20～25 | 65～95 | 5～12 | 300℃～500℃ |
Table 2 embodiment 1,2 Fischer-Tropsch wax character used
| Viscosity (40 DEG C), mm 2/s | Pour point, DEG C | Wax content, wt% | Isomerisation degree, % | Boiling range/ |
| 17.87 | 20 | 79.8 | 8.9 | 300℃～360℃ |
Table 3 embodiment 3,4 Fischer-Tropsch wax character used
| Viscosity (40 DEG C), mm 2/s | Pour point, DEG C | Wax content, wt% | Isomerisation degree, % | Boiling range/ |
| 19.96 | 23 | 89.8 | 10.2 | 360℃～450℃ |
Table 4 embodiment 5,6,7 Fischer-Tropsch wax character used
| Viscosity (40 DEG C), mm 2/s | Pour point, DEG C | Wax content, wt% | Isomerisation degree, % | Boiling range/ |
| 20.42 | 25 | 91.5 | 11.7 | 420℃～500℃ |
The isomerization performance of the process feedstock oil of table 5 catalyst
Claims (9)
1. a base metal isomerization catalyst, it is characterized in that catalyst is made up of the transition metal oxide of ten-ring molecular sieve and load Raney's nickel, wherein the weight ratio of components of the transition metal oxide of ten-ring molecular sieve and load Raney's nickel is 0.2-5:1, and the weight ratio of components of transition metal oxide and Raney's nickel is 0.05-2:1;
Described ten-ring molecular sieve is the molecular sieve of AEL, TON, MTT, MEL or FER structure type of one dimension tubulose;
Described transition metal oxide is V
2o
5, Cr
2o
3, Fe
2o
3, MoO
3in one.
2. a kind of base metal isomerization catalyst as claimed in claim 1, is characterized in that described ten-ring molecular sieve is ZSM-22, ZSM-23, SAPO-11 and SAPO-41.
3. a kind of base metal isomerization catalyst as claimed in claim 2, is characterized in that described ten-ring molecular sieve is SAPO-11 molecular sieve.
4. the preparation method of a kind of base metal isomerization catalyst as described in any one of claim 1-3, is characterized in that comprising the following steps:
(1) by catalyst composition, ten-ring molecular sieve is taken;
(2) form by final catalyst, by Ni-Al alloy and transition metal oxide mechanical mixture abundant, with after soaking 0.5-12h in the NaOH solution of 0.5-50.0wt% at 40-100 DEG C, be washed with distilled water to neutrality, after drying, obtain the transition metal oxide of load Raney's nickel;
(3) transition metal oxide of ten-ring molecular sieve, load Raney's nickel, extrusion aid sesbania powder, water are become plastic paste, extruded moulding with the abundant kneading of peptizing agent, after drying, 250-500 DEG C roasting 2-10h, obtain catalyst.
5. the preparation method of a kind of base metal isomerization catalyst as claimed in claim 4, is characterized in that the Ni-Al alloy described in step (2) is NiAl
3-Al, NiAl
3, Ni
2al
3in one.
6. the preparation method of a kind of base metal isomerization catalyst as claimed in claim 4, the peptizing agent that it is characterized in that described in step (3) is the one in nitric acid, hydrochloric acid, acetic acid, formic acid.
7. the application of a kind of base metal isomerization catalyst as described in any one of claim 1-3, it is characterized in that catalyst reacts on fixed bed reaction apparatus, for the isomery processing procedure of the various direct-connected paraffinic feedstock of initial boiling point more than 160 DEG C, catalyst needs to carry out reduction treatment before charging, reducing condition: hydrogen atmosphere, volume space velocity is 500-2000h
-1, 400-500 DEG C, 0.1-1.0Mpa, recovery time 4-24h; Reaction condition: 350-500 DEG C, Hydrogen Vapor Pressure 2.0-8.0MPa, liquid hourly space velocity (LHSV) is 0.2-2.5h
-1, hydrogen to oil volume ratio 200-1200.
8. the application of a kind of base metal isomerization catalyst as claimed in claim 7, is characterized in that reaction condition: 350-400 DEG C, Hydrogen Vapor Pressure 3.0-5.0MPa, liquid hourly space velocity (LHSV) 0.5-1.5h
-1, hydrogen to oil volume ratio 300-600.
9. the application of a kind of base metal isomerization catalyst as claimed in claim 7, it is characterized in that the various direct-connected paraffinic feedstock of initial boiling point more than 160 DEG C is Fischer-Tropsch wax, the character of Fischer-Tropsch wax is as following table
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| CN105582972B (en) * | 2014-10-24 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of isomerization-visbreaking catalyst and its preparation method and application and a kind of Fischer Tropsch waxes isomerization-visbreaking method |
| CN105521817B (en) * | 2014-10-24 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of catalyst with hydroisomerization and its preparation method and application and a kind of method for producing lube base oil |
| CN105521818B (en) * | 2014-10-24 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of hydroisomerisation catalysts and its preparation method and application and a kind of Fischer Tropsch waxes hydroisomerization process |
| US10710058B2 (en) * | 2016-08-02 | 2020-07-14 | Sabic Global Technologies B.V. | Process for preparing hydrocracking catalyst |
| CN108031486B (en) * | 2017-11-30 | 2020-09-18 | 西北化工研究院 | Preparation method and application of catalyst for preparing lubricating oil base oil from Fischer-Tropsch light component wax |
| CN115108565B (en) * | 2022-08-29 | 2022-11-25 | 中国科学院山西煤炭化学研究所 | Hydrogen-type FER molecular sieve and preparation method and application thereof |
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| CN1304793A (en) * | 2000-09-11 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Middle-temp isomerizing catalyst and its preparing process |
| CN101052465A (en) * | 2004-10-26 | 2007-10-10 | 环球油品公司 | Isomerized catalyzer and method thereof |
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| CN101052465A (en) * | 2004-10-26 | 2007-10-10 | 环球油品公司 | Isomerized catalyzer and method thereof |
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