CN105749963B - A kind of preparation method and catalyst of hysomer/Cracking catalyst - Google Patents
A kind of preparation method and catalyst of hysomer/Cracking catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of hysomer/Cracking catalyst.It is as follows：By the certain density alkaline solution treatment of 22 molecular sieves of sodium form ZSM containing template；Obtained product is washed with deionized, dry, roasting removed template method；It is exchanged, is filtered, and be washed with deionized with ammonium nitrate solution again, 22 molecular sieves of Hydrogen ZSM are made in dry, roasting；Carrier is made in 22 molecular sieves of Hydrogen ZSM and amorphous oxide and acid solution kneading, molding, roasting；By the carrier impregnation in the aqueous solution of soluble-salt, the catalyst then is made by dry and roasting.Compared with the catalyst that the prior art uses, catalyst provided by the invention is in the conversion process of Fischer Tropsch waxes, having better catalytic activity and target product selectivity.
Description
Technical field
The invention belongs to molecular sieve catalyst fields, and in particular to and a kind of hysomer based on ZSM-22 molecular sieves/
The preparation method of Cracking catalyst.
Background technology
F- T synthesis (Fischer-Tropsch synthesis) is referred to as FT reactions, is with synthesis gas (CO and H2) be
Raw material synthesizes the technique mistake of the liquid fuel based on paraffin hydrocarbon under the conditions of catalyst (such as iron system, cobalt system) and appropriate reaction
Journey.Traditional F- T synthesis feature is that fraction distribution is wide, and heavy hydrocarbon content is high, and is straight-chain hydrocarbons.Such heavy paraffin hydrocarbon solidifies
Point is high, and being not as suitable as diesel oil or lubricating oil directly uses, therefore, it is necessary to its pour point depression.N-alkane pour point depression it is most main
It is hysomer and cracking to want means, so that long-chain normal paraffin is converted into solidification by the bifunctional catalyst with special duct
Point low isoparaffin or small molecule alkane.The bifunctional catalyst is made of acidic site and metal position two parts, wherein acid
Position is generated by the molecular sieve with special pore passage structure, such as SAPO-11, ZSM-22, ZSM-23, ZSM-5, Beta.
For the wider hydrocarbon class composition of fraction distribution, if only all components can not be made all to turn by isomerization reaction
Ideal target product is turned to, for example condensation point and viscosity index (VI) are unable to meet demand.Therefore, it while isomerization occurs, needs
The high-melting-point normal paraffin component that some are not susceptible to isomerization reaction carries out appropriate cracking, be allowed to be converted into light diesel or
The low solidifying lubricating oil of person.Thus then wish catalyst while there is the dual function of isomerization and cracking.But excessive cracking can also
Lighter products are made to increase severely, target product (diesel oil or lubricating oil) yield is lower, and has both reduced the performance of product, has decreased production
Rate influences economic benefit.
ZSM-22 molecular sieves are a kind of artificial synthesized high-silica zeolites, belong to TON topological structures, have one-dimensional ten-ring
Pore passage structure, port size areDifferent template synthesis can be used in it.As US4556477 discloses one kind
The method for synthesizing ZSM-22 molecular sieves as template using diethylamine hydrochloride.US4902406, US5707600, US5783168 etc.
Disclose the method that ZSM-22 molecular sieves are synthesized as template using 1,6- hexamethylene diamines.
The ZSM-22 molecular sieves silica alumina ratio of conventional method synthesis is high, and acid stronger, acid amount is less, and micropore is molecular sieve master
The duct wanted.Meet with high isomerization activity and suitable for the requirement of cracking activity, it is suitable that ZSM-22 molecular sieves must have
Silica alumina ratio (acidity) and suitable pore-size distribution, carry out and reactants and products while to promote isomerization and cracking
Desorption in time.It is molecular sieve modified to ZSM-22 by the way of post-processing, the silica alumina ratio of molecular sieve can be made to be adjusted, and make
The transgranular mesoporous of some molecular sieves is made, to reach above-mentioned reaction requirement.
Invention content
The object of the present invention is to provide a kind of preparation methods of hysomer-Cracking catalyst.
The present invention is achieved by the following technical solutions：
(1) by the sodium form ZSM-22 molecular sieve alkaline solution treatments containing template, solid is washed with deionized to washing
De- liquid is in neutrality, dry, roasting removed template method；Obtained solid product uses ammonium nitrate (NH again4NO3) solution exchange, filtering,
And be washed with deionized, Hydrogen ZSM-22 molecular sieves are made in dry, roasting；
(2) it by gained Hydrogen ZSM-22 molecular sieves and amorphous oxide and acid solution kneading, molding, does after natural drying
Carrier is made in dry, roasting；
(3) by the carrier impregnation in the aqueous solution of group VIII metal soluble-salt, naturally dry then by it is dry,
Hysomer/the Cracking catalyst is made in roasting.
Template is diethylamine, 1,6- hexamethylene diamines, 1- butylamine or second in sodium form ZSM-22 molecular sieves in the step (1)
One or more of hydramine, content are the 0.5-30wt.% of sodium form ZSM-22 molecular sieves.
Aqueous slkali in the step (1) is sodium hydroxide (NaOH) aqueous solution or potassium hydroxide (KOH) aqueous solution, concentration
For 0.1-1.0mol/L；The molecular sieve is that molecular sieve is completely immersed in the lye that temperature is 20-120 DEG C with base extraction
In, processing time 10-600min is filtered after processing, and solid to eluent is washed with deionized and is in neutrality.
It exchanges to be with ammonium nitrate solution in the step (1) and molecular sieve is completely immersed in ammonium nitrate solution, stir
It mixes, the sodium ion on molecular sieve is made to be substituted by ammonium ion, make ZSM-22 points of the sodium form ZSM-22 obtained after base extraction or potassium type
Son sieve is exchanged into Hydrogen ZSM-22 molecular sieves；Concentration of ammonium nitrate solution used is 0.1-1.0mol/L, and solution usage is with molecular sieve
All below liquid level subject to；The temperature exchanged with ammonium nitrate solution is 20-100 DEG C, and exchange times are 2-4 times, each 1-8h；
It exchanges every time after finishing, filtering, and is washed with deionized to eluent and is in neutrality.
Amorphous oxide in the step (2) be amorphous alumina or one kind in amorphous silica-alumina or two kinds with
On, the mass ratio with Hydrogen ZSM-22 molecular sieves is 1:10 to 10:1.
Acid solution in the step (2) is aqueous solution of nitric acid or acetic acid aqueous solution, a concentration of 0.1-1.0mol/L；Acid is molten
Liquid addition is the 10%-100% of molecular sieve and unformed oxide gross mass.
The concrete operation method of above-mentioned steps (2) is：By the Hydrogen ZSM-22 molecular sieves of gained in step (1) with it is amorphous
Oxide is uniformly mixed, and is used in combination acid solution modulation, kneading that support precursor is made；Before making carrier using banded extruder, tablet press machine etc.
It drives body formed；Carrier is made in support precursor after molding is dry after natural drying, roasting.Wherein kneading temperature is room temperature,
The kneading time is 0.5-12h；Forming temperature is room temperature.
The aqueous solution of group VIII metal soluble-salt in the step (3) be platinum, palladium and iridium in one kind or two kinds or
One or two or more kinds in three kinds of nitrate, chloride salt, ammonium complex compound salt or carbonyl complex salt；Catalyst dipping is adopted
With equi-volume impregnating, 2-12h is impregnated at room temperature.
It is both needed to that processing is dried to obtained solid product before baking operation in above-mentioned all steps, drying temperature is
80-150 DEG C, the time is 2-8h；The calcination temperature is 300-700 DEG C, and the time is 4-40h.
Group VIII metal contains in the hysomer/Cracking catalyst being finally prepared using method provided by the invention
Amount is 0.1-5.0wt.%.
The present invention adjusts the silica alumina ratio of molecular sieve by alkali process means, so that molecular sieve acid amount is increased, acid strength is distributed
To adjustment；Alkali process increases the transgranular mesoporous of molecular sieve simultaneously, using made from the molecular sieve when catalyst, in reaction process
Material mass transfer is improved, and heavy linear paraffin is effectively converted, and the probability of the further cracking of small molecule isohydrocarbon reduces.
Therefore, compared with prior art, the present invention has the following advantages：
(1) catalyst prepared by the present invention has excellent isomerization performance, has simultaneously for heavy linear paraffin good
Good cracking performance.
(2) catalyst provided by the invention can significantly improve the solidification point of diesel oil and lube base oil.
(3) conversion of catalyst prepared by the present invention especially suitable for Fischer Tropsch waxes, can effectively improve Fischer Tropsch waxes
Determination of Diesel Oil in conversion process and lube base oil content.
Specific implementation mode
With reference to specific embodiment, the present invention is further illustrated, it is to be noted that the content of present invention is simultaneously
It is not limited to this.
Comparative example 1
It takes 100g to roast the sodium form ZSM-22 molecular sieves after removing template agent removing for 24 hours at 550 DEG C, it is a concentration of to be placed in 2L
The NH of 0.5mol/L4NO3In solution, at 60 DEG C, 180min is exchanged, filtered, be washed with deionized to eluent and be in neutrality,
It is continuous to exchange (repeating above operation) twice, 6h is dried at 120 DEG C, and acquisition Hydrogen ZSM-22 molecular sieves for 24 hours are roasted at 550 DEG C
(H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, 80g 5wt.%HNO are added3Solution, at room temperature kneading
2h, using automatic banded extruder extrusion at room temperature, naturally dry, the dry 4h at 120 DEG C, molecule is made in roasting 8h at 550 DEG C
Sieve carrier (H-ZSM-22 carriers).With the chloroplatinic acid (H of 10mL platiniferous (Pt) 0.05g/mL2PtCl6) the solution dipping above-mentioned loads of 100g
0.5wt.%Pt/H-ZSM-22 catalyst, number A1 is made in body.Catalysis reaction evaluating the results are shown in Table 2.
Embodiment 1
The sodium form ZSM-22 molecular sieves for taking 100g to contain 1,6- hexamethylene diamine templates, are placed in a concentration of 0.2mol/L's of 3L
In NaOH solution, at 80 DEG C, 180min, filtering are handled, washing to eluent is in neutrality, and drying simultaneously roasts template agent removing；
Products therefrom is placed in the NH of a concentration of 0.5mol/L of 2L4NO3In solution, at 60 DEG C, 180min is exchanged, filters, use deionized water
Washing to eluent is in neutrality, continuous to exchange (repeating above operation) twice, and 6h is dried at 120 DEG C, is roasted for 24 hours at 550 DEG C
Obtain Hydrogen ZSM-22 molecular sieves (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, 80g5wt.% is added
HNO3Solution, kneading 2h at room temperature, using automatic banded extruder extrusion at room temperature, naturally dry, the dry 4h at 120 DEG C, 550
8h is roasted at DEG C, and molecular sieve carrier (H-ZSM-22 carriers) is made.With the chloroplatinic acid of 10mL platiniferous (Pt) 0.05g/mL solution
(H2PtCl6) the solution dipping above-mentioned carriers of 100g, 0.5wt.%Pt/H-ZSM-22 catalyst, number B1 is made.Catalysis reaction
Evaluation result is shown in Table 2.
Embodiment 2
The sodium form ZSM-22 molecular sieves for taking 100g to contain 1,6- hexamethylene diamine templates, are placed in a concentration of 0.4mol/L's of 3L
In NaOH solution, at 80 DEG C, 180min, filtering are handled, washing to eluent is in neutrality, and drying simultaneously roasts template agent removing；
Products therefrom is placed in the NH of a concentration of 0.5mol/L of 2L4NO3In solution, at 60 DEG C, 180min is exchanged, filters, use deionized water
Washing to eluent is in neutrality, continuous to exchange (repeating above operation) twice, and 6h is dried at 120 DEG C, is roasted for 24 hours at 550 DEG C
Obtain Hydrogen ZSM-22 molecular sieves (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, 80g5wt.% is added
HNO3Solution, kneading 2h at room temperature, using automatic banded extruder extrusion at room temperature, naturally dry, the dry 4h at 120 DEG C, 550
8h is roasted at DEG C, and molecular sieve carrier (H-ZSM-22 carriers) is made.With the chloroplatinic acid of 10mL platiniferous (Pt) 0.05g/mL solution
(H2PtCl6) the solution dipping above-mentioned carriers of 100g, 0.5wt.%Pt/H-ZSM-22 catalyst, number B2 is made.Catalysis reaction
Evaluation result is shown in Table 2.
Embodiment 3
The sodium form ZSM-22 molecular sieves for taking 100g to contain 1,6- hexamethylene diamine templates, are placed in a concentration of 0.6mol/L's of 3L
In NaOH solution, at 80 DEG C, 180min, filtering are handled, washing to eluent is in neutrality, and drying simultaneously roasts template agent removing；
Products therefrom is placed in the NH of a concentration of 0.5mol/L of 2L4NO3In solution, at 60 DEG C, 180min is exchanged, filters, use deionized water
Washing to eluent is in neutrality, continuous to exchange (repeating above operation) twice, and 6h is dried at 120 DEG C, is roasted for 24 hours at 550 DEG C
Obtain Hydrogen ZSM-22 molecular sieves (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, 80g5wt.% is added
HNO3Solution, kneading 2h at room temperature, using automatic banded extruder extrusion at room temperature, naturally dry, the dry 4h at 120 DEG C, 550
8h is roasted at DEG C, and molecular sieve carrier (H-ZSM-22 carriers) is made.With the chloroplatinic acid of 10mL platiniferous (Pt) 0.05g/mL solution
(H2PtCl6) the solution dipping above-mentioned carriers of 100g, 0.5wt.%Pt/H-ZSM-22 catalyst, number B3 is made.Catalysis reaction
Evaluation result is shown in Table 2.
Embodiment 4
The sodium form ZSM-22 molecular sieves for taking 100g to contain 1,6- hexamethylene diamine templates, are placed in a concentration of 0.8mol/L's of 3L
In NaOH solution, at 80 DEG C, 180min, filtering are handled, washing to eluent is in neutrality, and drying simultaneously roasts template agent removing；
Products therefrom is placed in the NH of a concentration of 0.5mol/L of 2L4NO3In solution, at 60 DEG C, 180min is exchanged, filters, use deionized water
Washing to eluent is in neutrality, continuous to exchange (repeating above operation) twice, and 6h is dried at 120 DEG C, is roasted for 24 hours at 550 DEG C
Obtain Hydrogen ZSM-22 molecular sieves (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, 80g5wt.% is added
HNO3Solution, kneading 2h at room temperature, using automatic banded extruder extrusion at room temperature, naturally dry, the dry 4h at 120 DEG C, 550
8h is roasted at DEG C, and molecular sieve carrier (H-ZSM-22 carriers) is made.With the chloroplatinic acid of 10mL platiniferous (Pt) 0.05g/mL solution
(H2PtCl6) the solution dipping above-mentioned carriers of 100g, 0.5wt.%Pt/H-ZSM-22 catalyst, number B4 is made.Catalysis reaction
Evaluation result is shown in Table 2.
Embodiment 5
The sodium form ZSM-22 molecular sieves for taking 100g to contain 1,6- hexamethylene diamine templates, are placed in the NaOH of a concentration of 1mol/L of 3L
In solution, at 80 DEG C, 180min, filtering are handled, washing to eluent is in neutrality, and drying simultaneously roasts template agent removing；Gained
Product is placed in the NH of a concentration of 0.5mol/L of 2L4NO3In solution, at 60 DEG C, 180min is exchanged, filters, be washed with deionized
It is in neutrality to eluent, it is continuous to exchange (repeating above operation) twice, 6h is dried at 120 DEG C, is roasted at 550 DEG C and is obtained for 24 hours
Hydrogen ZSM-22 molecular sieves (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, 80g5wt.%HNO is added3
Solution, kneading 2h at room temperature, using automatic banded extruder extrusion at room temperature, naturally dry, the dry 4h at 120 DEG C, at 550 DEG C
It roasts 8h and molecular sieve carrier (H-ZSM-22 carriers) is made.With the chloroplatinic acid (H of 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6)
Solution impregnates the above-mentioned carriers of 100g, and 0.5wt.%Pt/H-ZSM-22 catalyst, number B5 is made.It is catalyzed reaction evaluating result
It is shown in Table 2.
Embodiment 6
The sodium form ZSM-22 molecular sieves for taking 100g to contain 1,6- hexamethylene diamine templates, are placed in the NaOH of a concentration of 1mol/L of 3L
In solution, at 80 DEG C, 240min, filtering are handled, washing to eluent is in neutrality, and drying simultaneously roasts template agent removing；Gained
Product is placed in the NH of a concentration of 0.5mol/L of 2L4NO3In solution, at 60 DEG C, 180min is exchanged, filters, be washed with deionized
It is in neutrality to eluent, it is continuous to exchange (repeating above operation) twice, 6h is dried at 120 DEG C, is roasted at 550 DEG C and is obtained for 24 hours
Hydrogen ZSM-22 molecular sieves (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, 80g5wt.%HNO is added3
Solution, kneading 2h at room temperature, using automatic banded extruder extrusion at room temperature, naturally dry, the dry 4h at 120 DEG C, at 550 DEG C
It roasts 8h and molecular sieve carrier (H-ZSM-22 carriers) is made.With the chloroplatinic acid (H of 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6)
Solution impregnates the above-mentioned carriers of 100g, and 0.5wt.%Pt/H-ZSM-22 catalyst, number B6 is made.It is catalyzed reaction evaluating result
It is shown in Table 2.
Embodiment 7
The sodium form ZSM-22 molecular sieves for taking 100g to contain 1,6- hexamethylene diamine templates, are placed in the NaOH of a concentration of 1mol/L of 3L
In solution, at 60 DEG C, 240min, filtering are handled, washing to eluent is in neutrality, and drying simultaneously roasts template agent removing；Gained
Product is placed in the NH of a concentration of 0.5mol/L of 2L4NO3In solution, at 60 DEG C, 180min is exchanged, filters, be washed with deionized
It is in neutrality to eluent, it is continuous to exchange (repeating above operation) twice, 6h is dried at 120 DEG C, is roasted at 550 DEG C and is obtained for 24 hours
Hydrogen ZSM-22 molecular sieves (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, 80g5wt.%HNO is added3
Solution, kneading 2h at room temperature, using automatic banded extruder extrusion at room temperature, naturally dry, the dry 4h at 120 DEG C, at 550 DEG C
It roasts 8h and molecular sieve carrier (H-ZSM-22 carriers) is made.With the chloroplatinic acid (H of 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6)
Solution impregnates the above-mentioned carriers of 100g, and 0.5wt.%Pt/H-ZSM-22 catalyst, number B7 is made.It is catalyzed reaction evaluating result
It is shown in Table 2.
Embodiment 8
The sodium form ZSM-22 molecular sieves for taking 100g to contain 1,6- hexamethylene diamine templates, are placed in the NaOH of a concentration of 1mol/L of 3L
In solution, at 60 DEG C, 180min, filtering are handled, washing to eluent is in neutrality, and drying simultaneously roasts template agent removing；Gained
Product is placed in the NH of a concentration of 0.5mol/L of 2L4NO3In solution, at 60 DEG C, 180min is exchanged, filters, be washed with deionized
It is in neutrality to eluent, it is continuous to exchange (repeating above operation) twice, 6h is dried at 120 DEG C, is roasted at 550 DEG C and is obtained for 24 hours
Hydrogen ZSM-22 molecular sieves (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, 80g5wt.%HNO is added3
Solution, kneading 2h at room temperature, using automatic banded extruder extrusion at room temperature, naturally dry, the dry 4h at 120 DEG C, at 550 DEG C
It roasts 8h and molecular sieve carrier (H-ZSM-22 carriers) is made.With the chloroplatinic acid (H of 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6)
Solution impregnates the above-mentioned carriers of 100g, and 0.5wt.%Pt/H-ZSM-22 catalyst, number B8 is made.It is catalyzed reaction evaluating result
It is shown in Table 2.
Embodiment 9
It is catalyzed reaction evaluating：
Raw material：F- T synthesis heavy diesel, property are shown in Table 1；Reaction condition：10mL fixed bed reactors, reaction temperature 330
DEG C, reaction pressure 8MPa, air speed 1h-1, hydrogen-oil ratio 600nL/nL.Each evaluating catalyst result is listed in table 2.
1. raw material oil nature of table
The corresponding product characteristics of 2. different catalysts of table and evaluation result
Compared with comparative example, the catalyst prepared using the present invention can get higher isomerisation selectivity and target product
(such as diesel oil) yield, and then oil property is made to be further improved (such as solidification point reduction), while making catalytic process economy
Increase.
Claims (9)
1. a kind of preparation method of hysomer/Cracking catalyst, it is characterised in that：Include the following steps：
（1）By the sodium form ZSM-22 molecular sieve alkaline solution treatments containing template, the solid product nitric acid obtained after roasting
Ammonium salt solution exchanges, and Hydrogen ZSM-22 molecular sieves are made after roasting；
（2）Gained Hydrogen ZSM-22 molecular sieves and unformed oxide and acid solution are subjected to kneading, molding, then fired obtained
Carrier；
（3）Resulting vehicle is impregnated in the aqueous solution of group VIII metal soluble-salt, then fired obtained hysomer/
Cracking catalyst；
The step（1）In aqueous slkali be sodium hydrate aqueous solution or potassium hydroxide aqueous solution, a concentration of 0.1-1.0 mol/
L；It is 20-120 that molecular sieve is as completely immersed in temperature by the molecular sieve with base extractionoIn the lye of C, processing time is
180-600 min are washed with deionized solid to eluent and are in neutrality after processing.
2. the method as described in claim 1, it is characterised in that：The step（1）In sodium form ZSM-22 molecular sieves in template
Agent is one or more of diethylamine, 1,6- hexamethylene diamines, 1- butylamine or ethanol amine, and content is sodium form ZSM-22 molecular sieves
0.5-30 wt.%。
3. the method as described in claim 1, it is characterised in that：The step（1）Middle exchanged with ammonium nitrate solution is that will divide
It is 20-100 that son sieve, which is completely immersed in temperature, oIn the ammonium nitrate solution of C, stirring makes the sodium ion on molecular sieve be substituted by ammonium ion；
Concentration of ammonium nitrate solution is 0.1-1.0 mol/L, and exchange times are 2-4 times, each 1-8h；It exchanges every time after finishing, filtering,
And it is washed with deionized to eluent and is in neutrality.
4. the method as described in claim 1, it is characterised in that：The step（2）In amorphous oxide be amorphous
Change the one or two or more kinds in aluminium or amorphous silica-alumina, the mass ratio with Hydrogen ZSM-22 molecular sieves is 1:10 to 10:1.
5. the method as described in claim 1, it is characterised in that：The step（2）In acid solution be aqueous solution of nitric acid or second
Aqueous acid, a concentration of 0.1-1.0 mol/L；Acid solution addition is the 10%- of molecular sieve and unformed oxide gross mass
100%。
6. the method as described in claim 1, it is characterised in that：The step（3）In group VIII metal soluble-salt water
Solution is one kind or two kinds or three kinds of nitrate, chloride salt, ammonium complex compound salt or carbonyl complex salt in platinum, palladium and iridium
In one or two or more kinds；
Catalyst dipping uses equi-volume impregnating, impregnates 2-12h at room temperature.
7. the method as described in claim 1, it is characterised in that：Kneading temperature is room temperature in step 2, and the kneading time is 0.5-
12h；Forming temperature is room temperature.
8. the method as described in claim 1, it is characterised in that：It is both needed to do obtained solid product before the baking operation
Dry processing, drying temperature are 80-150oC, time are 2-8h；The calcination temperature is 300-700 oC, time is
4-40 h。
9. a kind of hysomer/Cracking catalyst prepared using claim 1-8 either method, it is characterised in that：Catalysis
Group VIII metal content is 0.1-5.0 wt.% in agent.
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| CN109465026B (en) * | 2017-09-07 | 2021-10-29 | 中国石油天然气股份有限公司 | Preparation method of isomerization catalyst taking TON type structure molecular sieve as carrier |
| CN108816279B (en) * | 2018-05-23 | 2021-03-16 | 中国中化股份有限公司 | Preparation method of normal paraffin hydroisomerization catalyst |
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