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CN105749963A - Preparation method of hydroisomerization/cracking catalyst and catalyst - Google Patents

Preparation method of hydroisomerization/cracking catalyst and catalyst Download PDF

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CN105749963A
CN105749963A CN201410783599.0A CN201410783599A CN105749963A CN 105749963 A CN105749963 A CN 105749963A CN 201410783599 A CN201410783599 A CN 201410783599A CN 105749963 A CN105749963 A CN 105749963A
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molecular sieve
solution
zsm
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roasting
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CN105749963B (en
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王从新
田志坚
曲炜
马怀军
徐仁顺
王炳春
王冬娥
潘振栋
李鹏
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a preparation method of a hydroisomerization/cracking catalyst. The method specifically comprises the following steps: treating a sodium-type ZSM-22 molecular sieve containing a template agent with an alkaline solution having a certain concentration; washing the obtained product with deionized water, and performing drying and calcination to remove the template agent; performing replacement with an ammonium nitrate solution, performing filtration, washing the obtained product with deionized water, and performing drying and calcination to prepare a hydrogen-type ZSM-22 molecular sieve; mixing the hydrogen-type ZSM-22 molecular sieve with an amorphous oxide and an acid solution, and performing molding and calcination to prepare a carrier; and soaking the carrier in an aqueous solution of soluble salt, and performing drying and calcination to obtain the catalyst. Compared with a catalyst prepared in the prior art, the prepared catalyst can be used in a conversion process of wax in Fischer-Tropsch synthesis, and has favorable catalytic activity and selectivity of target products.

Description

The preparation method of a kind of hysomer/Cracking catalyst and catalyst
Technical field
The invention belongs to molecular sieve catalyst field, the preparation method being specifically related to a kind of hysomer/Cracking catalyst based on ZSM-22 molecular sieve.
Background technology
F-T synthesis (Fischer-Tropschsynthesis) reacts referred to as FT, is with synthesis gas (CO and H2) synthesize the technical process of liquid fuel based on paraffin hydrocarbon when catalyst (such as ferrum system, cobalt system etc.) and appropriate reaction for raw material.Traditional F-T synthesis is characterized as being fraction distribution width, and heavy hydrocarbon content is high, and is straight-chain hydrocarbons.Such heavy paraffin hydrocarbon freezing point is high, is not as suitable as diesel oil or lubricating oil directly uses, therefore, it is necessary to its pour point depression.The main means of n-alkane pour point depression are hysomer and cracking, the bifunctional catalyst with special duct make long-chain normal paraffin be converted into the low isoparaffin of freezing point or little molecule alkane.This bifunctional catalyst is made up of acidic site and metal position two parts, and wherein acidic site is produced by the molecular sieve with special pore passage structure, such as SAPO-11, ZSM-22, ZSM-23, ZSM-5, Beta etc..
For the hydrocarbon class composition that fraction distribution is wider, if only passing through isomerization reaction, it is impossible to making all components be converted to desirable target product, such as condensation point and viscosity index (VI) can not meet demand.Therefore, occurring isomerized while, some high-melting-point normal paraffin components being not susceptible to isomerization reaction need to be carried out suitable cracking, so as to be converted into light diesel or low solidifying lubricating oil.Thus then wish that catalyst has the dual-use function of isomerization and cracking simultaneously.But excessive cracking can also make lighter products increase severely, target product (diesel oil or lubricating oil) yield step-down, both reduce the performance of product, decreased productivity, affect economic benefit.
ZSM-22 molecular sieve is the high-silica zeolite of a kind of synthetic, belongs to TON topological structure, has one-dimensional ten-ring pore passage structure, and port size isIt can adopt different template to synthesize.As US4556477 discloses a kind of method synthesizing ZSM-22 molecular sieve for template with diethylamine hydrochloride.US4902406, US5707600, US5783168 etc. disclose the method synthesizing ZSM-22 molecular sieve for template with 1,6-hexamethylene diamine.
The ZSM-22 molecular sieve silica alumina ratio of conventional method synthesis is high, and acidity is relatively strong, and acid amount is less, and micropore is the duct that molecular sieve is main.Meet the requirement with the active and suitable cracking activity of high isomerization, ZSM-22 molecular sieve must have suitable silica alumina ratio (acidity) and suitable pore-size distribution, thus carrying out while promoting isomerization and cracking and the timely desorption of reactant and product.The mode adopting post processing is molecular sieve modified to ZSM-22, it is possible to makes the silica alumina ratio of molecular sieve be adjusted, and manufactures some molecular sieve intracrystalline mesopores, thus reaching above-mentioned reaction requirement.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind 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 treatment containing template, with deionized water wash solid to eluent in neutrality, dry, roasting removed template method;The solid product obtained is again with ammonium nitrate (NH4NO3) solution exchange, filter, and with deionized water wash, dry, Hydrogen ZSM-22 molecular sieve is made in roasting;
(2) by gained Hydrogen ZSM-22 molecular sieve and amorphous oxide and acid solution kneading, molding, carrier is made in dry after naturally drying, roasting;
(3) by described carrier impregnation in the aqueous solution of group VIII metal soluble-salt, naturally dry be then passed through drying, roasting prepares described hysomer/Cracking catalyst.
In sodium form ZSM-22 molecular sieve in described step (1), template is one or more in diethylamine, 1,6-hexamethylene diamine, 1-butylamine or ethanolamine, and content is the 0.5-30wt.% of sodium form ZSM-22 molecular sieve.
Aqueous slkali in described step (1) is sodium hydroxide (NaOH) aqueous solution or potassium hydroxide (KOH) aqueous solution, and concentration is 0.1-1.0mol/L;Described molecular sieve base extraction is and is completely immersed in by molecular sieve in the alkali liquor that temperature is 20-120 DEG C, and the process time is 10-600min, filters after process, with deionized water wash solid to eluent in neutrality.
Being with ammonium nitrate solution exchange in described step (1) is completely immersed in ammonium nitrate solution by molecular sieve, stirring, the sodium ion on molecular sieve is made to be substituted by ammonium ion,, the sodium form ZSM-22 or the potassium type ZSM-22 molecular sieve that obtain after making base extraction are exchanged into Hydrogen ZSM-22 molecular sieve;Concentration of ammonium nitrate solution used is 0.1-1.0mol/L, and solution usage is all as the criterion with molecular sieve below liquid level;Being 20-100 DEG C by the temperature of ammonium nitrate solution exchange, exchange times is 2-4 time, each 1-8h;After each exchange is complete, filter, and with deionized water wash to eluent in neutrality.
Amorphous oxide in described step (2) is one or two or more kinds in amorphous alumina or amorphous silica-alumina, and its mass ratio with Hydrogen ZSM-22 molecular sieve is 1:10 to 10:1.
Acid solution in described step (2) is aqueous solution of nitric acid or acetic acid aqueous solution, and concentration is 0.1-1.0mol/L;Acid solution addition is molecular sieve and the 10%-100% of unformed oxide gross mass.
The concrete operation method of above-mentioned steps (2) is: mixed homogeneously with amorphous oxide by the Hydrogen ZSM-22 molecular sieve of gained in step (1), and makes support precursor by acid solution modulation, kneading;Banded extruder, tablet machine etc. is used to make support precursor molding;Dry after support precursor after molding naturally being dried, carrier is made in roasting.Wherein kneading temperature is room temperature, and the kneading time is 0.5-12h;Forming temperature is room temperature.
The aqueous solution of the group VIII metal soluble-salt in described step (3) is one or two or more kinds in the nitrate of a kind of in platinum, palladium and iridium or two kinds or three kinds, chloride salt, ammonium complex compound salt or carbonyl complex salt;Catalyst soakage adopts equi-volume impregnating, impregnates 2-12h under room temperature.
Above-mentioned in steps in baking operation before be both needed to gained solid product is dried process, baking temperature is 80-150 DEG C, and the time is 2-8h;Described sintering temperature is 300-700 DEG C, and the time is 4-40h.
Utilizing group VIII metal content in hysomer/Cracking catalyst that method provided by the invention finally prepares is 0.1-5.0wt.%.
The present invention processes means by alkali and adjusts the silica alumina ratio of molecular sieve, makes molecular sieve acid amount increase, and acid strength distribution is adjusted;Alkali processes the intracrystalline mesopore adding molecular sieve simultaneously, and when using the catalyst that this molecular sieve prepares, in course of reaction, material mass transfer is improved, and heavy linear paraffin is effectively converted, and the probability of the little further cracking of molecule isohydrocarbon reduces.
Therefore, compared with prior art, the invention have the advantages that
(1) catalyst prepared by the present invention has the isomerization performance of excellence, has good cracking performance simultaneously for heavy linear paraffin.
(2) catalyst provided by the invention can significantly improve the freezing point of diesel oil and lube base oil.
(3) catalyst prepared by the present invention is particularly well-suited to the conversion of Fischer Tropsch waxes, can be effectively improved the Determination of Diesel Oil in Fischer Tropsch waxes conversion process and lube base oil content.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, it is to be noted that present invention is not limited thereto.
Comparative example 1
Take 100g sodium form ZSM-22 molecular sieve after 550 DEG C of roasting 24h remove template, be placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered A1.Catalytic reaction evaluation result is in Table 2.
Embodiment 1
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 0.2mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B1.Catalytic reaction evaluation result is in Table 2.
Embodiment 2
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 0.4mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B2.Catalytic reaction evaluation result is in Table 2.
Embodiment 3
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 0.6mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B3.Catalytic reaction evaluation result is in Table 2.
Embodiment 4
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 0.8mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B4.Catalytic reaction evaluation result is in Table 2.
Embodiment 5
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 1mol/L, at 80 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B5.Catalytic reaction evaluation result is in Table 2.
Embodiment 6
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 1mol/L, at 80 DEG C, process 240min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B6.Catalytic reaction evaluation result is in Table 2.
Embodiment 7
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 1mol/L, at 60 DEG C, process 240min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B7.Catalytic reaction evaluation result is in Table 2.
Embodiment 8
Taking 100g and contain the sodium form ZSM-22 molecular sieve of 1,6-hexamethylene diamine template, be placed in the NaOH solution that 3L concentration is 1mol/L, at 60 DEG C, process 180min, filter, wash to eluent in neutrality, template is removed in dry and roasting;Products therefrom is placed in the NH that 2L concentration is 0.5mol/L4NO3In solution, at 60 DEG C, exchange 180min, filter, be neutrality with deionized water wash to eluent, exchange continuously (repeats above operation) twice, dries 6h at 120 DEG C, and at 550 DEG C, roasting 24h obtains Hydrogen ZSM-22 molecular sieve (H-ZSM-22).Take 30g aluminium oxide (γ-Al2O3) be mixed with uniformly, adding 80g5wt.%HNO3Solution, kneading 2h under room temperature, adopt extrusion under automatic banded extruder room temperature, naturally dry, dry 4h at 120 DEG C, at 550 DEG C, roasting 8h prepares molecular sieve carrier (H-ZSM-22 carrier).Chloroplatinic acid (H with 10mL platiniferous (Pt) 0.05g/mL solution2PtCl6) the above-mentioned carrier of solution impregnation 100g, prepare 0.5wt.%Pt/H-ZSM-22 catalyst, be numbered B8.Catalytic reaction evaluation result is in Table 2.
Embodiment 9
Catalytic reaction is evaluated:
Raw material: F-T synthesis heavy diesel, character is 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.
Table 1. raw oil character
Product characteristics that table 2. different catalysts is corresponding and evaluation result
Compared with comparative example, adopt catalyst prepared by the present invention can obtain higher isomerisation selectivity and target product (such as diesel oil) yield, and then make oil property be further improved (as freezing point reduces), make catalytic process economy increase simultaneously.

Claims (10)

1.一种临氢异构化/裂化催化剂的制备方法,其特征在于:包括如下步骤:1. A preparation method of hydroisomerization/cracking catalyst, characterized in that: comprise the steps: (1)将含有模板剂的钠型ZSM-22分子筛用碱溶液处理,焙烧后得到的固体产物用硝酸铵溶液交换,焙烧后制得氢型ZSM-22分子筛;(1) Treat the sodium-type ZSM-22 molecular sieve containing the template with an alkali solution, exchange the solid product obtained after roasting with an ammonium nitrate solution, and obtain a hydrogen-type ZSM-22 molecular sieve after roasting; (2)将所得氢型ZSM-22分子筛与无定型氧化物和酸溶液进行混捏、成型,再经焙烧制得载体;(2) kneading and molding the obtained hydrogen ZSM-22 molecular sieve with the amorphous oxide and acid solution, and then roasting to obtain the carrier; (3)将所得载体浸渍于VIII族金属可溶性盐的水溶液中,然后经焙烧制得临氢异构化/裂化催化剂。(3) impregnating the obtained support in an aqueous solution of a soluble salt of Group VIII metal, and then roasting to obtain a hydroisomerization/cracking catalyst. 2.如权利要求1所述的方法,其特征在于:所述步骤(1)中的钠型ZSM-22分子筛中模板剂为二乙胺、1,6-己二胺、1-丁胺或乙醇胺中的一种或几种,含量为钠型ZSM-22分子筛的0.5-30wt.%。2. the method for claim 1 is characterized in that: template agent is diethylamine, 1,6-hexamethylenediamine, 1-butylamine or One or several ethanolamines, the content of which is 0.5-30wt.% of the sodium ZSM-22 molecular sieve. 3.如权利要求1所述的方法,其特征在于:所述步骤(1)中的碱溶液为氢氧化钠水溶液或氢氧化钾水溶液,浓度为0.1-1.0mol/L;所述分子筛用碱液处理即为将分子筛完全浸入温度为20-120℃的碱液中,处理时间为10-600min,处理后用去离子水洗涤固体至洗脱液呈中性。3. The method according to claim 1, characterized in that: the alkali solution in the step (1) is an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and the concentration is 0.1-1.0mol/L; the molecular sieve uses alkali The liquid treatment is to completely immerse the molecular sieve in the alkali solution with a temperature of 20-120°C for 10-600 minutes, and wash the solid with deionized water after treatment until the eluent is neutral. 4.如权利要求1所述的方法,其特征在于:所述步骤(1)中用硝酸铵溶液交换即为将分子筛完全浸入温度为20-100℃的硝酸铵溶液中,搅拌,使分子筛上的钠离子被铵离子替代;硝酸铵溶液浓度为0.1-1.0mol/L,交换次数为2-4次,每次1-8h;每次交换完毕之后,过滤,并用去离子水洗涤至洗脱液呈中性。4. The method according to claim 1, characterized in that: in the step (1), the exchange with ammonium nitrate solution is to completely immerse the molecular sieve in the ammonium nitrate solution at a temperature of 20-100° C., and stir to make the molecular sieve The sodium ions are replaced by ammonium ions; the concentration of ammonium nitrate solution is 0.1-1.0mol/L, and the number of exchanges is 2-4 times, each time 1-8h; after each exchange, filter and wash with deionized water until elution The liquid is neutral. 5.如权利要求1所述的方法,其特征在于:所述步骤(2)中的无定形氧化物为无定形氧化铝或无定形硅铝中的一种或二种以上,其与氢型ZSM-22分子筛的质量比为1:10至10:1。5. The method according to claim 1, characterized in that: the amorphous oxide in the step (2) is one or more of amorphous alumina or amorphous silicon-alumina, which is mixed with hydrogen The mass ratio of ZSM-22 molecular sieve is 1:10 to 10:1. 6.如权利要求1所述的方法,其特征在于:所述步骤(2)中的酸溶液为硝酸水溶液或乙酸水溶液,浓度为0.1-1.0mol/L;酸溶液加入量为分子筛和无定型氧化物总质量的10%-100%。6. the method for claim 1 is characterized in that: the acid solution in the described step (2) is nitric acid aqueous solution or acetic acid aqueous solution, and concentration is 0.1-1.0mol/L; The acid solution add-on is molecular sieve and amorphous 10%-100% of the total mass of oxides. 7.如权利要求1所述的方法,其特征在于:所述步骤(3)中的VIII族金属可溶性盐的水溶液为铂、钯和铱中的一种或二种或三种的硝酸盐、氯化物盐、铵络合物盐或羰基络合物盐中的一种或二种以上;7. the method for claim 1 is characterized in that: the aqueous solution of the VIII group metal soluble salt in the described step (3) is platinum, palladium and iridium one or two or three nitrates, One or more of chloride salts, ammonium complex salts or carbonyl complex salts; 催化剂浸渍采用等体积浸渍法,室温下浸渍2-12h。Catalyst impregnation adopts equal volume impregnation method, impregnation at room temperature for 2-12h. 8.如权利要求1所述的方法,其特征在于:步骤2中混捏温度为室温,混捏时间为0.5-12h;成型温度为室温。8. The method according to claim 1, characterized in that: in step 2, the kneading temperature is room temperature, and the kneading time is 0.5-12h; the molding temperature is room temperature. 9.如权利要求1所述的方法,其特征在于:所述焙烧操作前均需对所得固体产物进行干燥处理,干燥温度均为80-150℃,时间均为2-8h;所述焙烧温度均为300-700℃,时间均为4-40h。9. The method according to claim 1, characterized in that: the obtained solid product needs to be dried before the calcination operation, the drying temperature is 80-150°C, and the time is 2-8h; the calcination temperature Both are at 300-700°C, and the time is 4-40h. 10.一种使用权利要求1-9任一方法制备的临氢异构化/裂化催化剂,其特征在于:催化剂中VIII族金属含量为0.1-5.0wt.%。10. A hydroisomerization/cracking catalyst prepared by the method of any one of claims 1-9, characterized in that the content of Group VIII metals in the catalyst is 0.1-5.0 wt.%.
CN201410783599.0A 2014-12-16 2014-12-16 A kind of preparation method and catalyst of hysomer/Cracking catalyst Active CN105749963B (en)

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