CN112642473A - Preparation method of SBA-15/ZSM-5 composite molecular sieve, catalyst and application of catalyst in double-branched-chain isomerization - Google Patents
Preparation method of SBA-15/ZSM-5 composite molecular sieve, catalyst and application of catalyst in double-branched-chain isomerization Download PDFInfo
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B01J2229/10—After treatment, characterised by the effect to be obtained
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
本发明涉及石油加工领域，公开了一种SBA‑15/ZSM‑5复合分子筛材料的制备方法及在双支链异构化中的应用。特别涉及一种具有适宜酸性和梯级孔道结构的SBA‑15/ZSM‑5复合分子筛材料的低成本绿色制备方法及其负载非贵金属制得耐硫型双支链异构化催化剂，在催化裂化(FCC)汽油加氢异构反应中得以应用，本发明以天然矿物为原料无模板剂绿色合成ZSM‑5分子筛纳米晶前驱液，然后通过采用低酸度预水解方法原位组装制备出SBA‑15/ZSM‑5复合分子筛载体，极大地降低了生产成本、缓解了设备腐蚀且减少了污染物的排放。因此，本发明方法具有良好的经济和环境效益，对推进工业化进程提供了技术支持。
The invention relates to the field of petroleum processing, and discloses a preparation method of an SBA-15/ZSM-5 composite molecular sieve material and its application in double branched chain isomerization. In particular, it relates to a low-cost green preparation method of SBA-15/ZSM-5 composite molecular sieve material with suitable acidity and stepped pore structure, and a non-precious metal loaded non-precious metal to obtain a sulfur-resistant double-branched isomerization catalyst, which is used in catalytic cracking ( FCC) gasoline hydrogenation isomerization reaction, the present invention uses natural minerals as raw materials to synthesize ZSM-5 molecular sieve nanocrystal precursor liquid without template agent, and then prepares SBA-15/ ZSM‑5 composite molecular sieve carrier greatly reduces production costs, eases equipment corrosion and reduces pollutant emissions. Therefore, the method of the present invention has good economic and environmental benefits, and provides technical support for advancing the industrialization process.
Description
Technical Field
The invention relates to the field of petroleum processing, in particular to a preparation method of an SBA-15/ZSM-5 composite molecular sieve material and application thereof in double-branched chain isomerization.
Background
China gradually executes the strict national VI emission standard from 2019, the requirement on the oil upgrading technology is further improved, catalytic cracking (FCC) gasoline is always the main blending component in the motor gasoline in China, and the main difficulty of the oil quality upgrading in China is to reduce the gasoline olefin and keep the octane number. The isomerized oil has high octane number and low sulfur content, and does not contain olefin, aromatic hydrocarbon and benzene, so the isomerization of the alkane becomes a research hotspot in the field of producing high-octane gasoline.
Molecular sieves are one of the more commonly used supports for FCC gasoline isomerization catalysts. Although microporous molecular sieves have good acidity and shape-selective catalytic performance, molecular diffusion resistance is large due to narrow microporous channels, cracking is serious due to excessively strong acidity, carbon deposit is easily caused in the reaction process, and the defects limit the use of the microporous molecular sieves in macromolecular reaction. Due to the large pore diameter and pore volume of the mesoporous SBA-15 molecular sieve, the problems of mass transfer and diffusion limitation in the reaction process can be effectively solved, but the demand of isomerization reaction cannot be met due to the weak acidity of the surface of the mesoporous SBA-15 molecular sieve. If the two advantages can be combined together, the mesoporous and microporous composite molecular sieve based on SBA-15 and the preparation method thereof can be widely applied, and the method mainly comprises a nano-assembly method, a pore wall crystallization method, a hard template method, a soft template method and the like. The synthesis process of the mesoporous molecular sieve can not be separated from the use of a template agent in a strong acid system, the traditional microporous molecular sieve mostly adopts a synthesis method of a chemical reagent, the template agent or a directing agent, the compounding process usually needs two steps, and if the synthesis cost of one step can be saved, the cost is also reduced for the whole synthesis process, so the invention has the advantages that the template-free green synthesis precursor material is utilized in the synthesis part of the microporous molecular sieve, the low-concentration acid is adopted for compounding in the compounding stage, the cost is saved in the reaction process, and the method is economic and environment-friendly.
Vu et al (Journal of Materials Science,2014,49(16), 5676-.
Qian et al (Chemical Science,2011,2(10),2006-0) synthesize a zeolite/SBA-15 molecular sieve material with a core-shell structure by using an ultra-dilute template solution, in the process, firstly, a Chemical reagent and the template are used for synthesizing a microporous molecular sieve with complete crystallization, then, magnesium sulfate is added into an acid solution in which a few P123 templates are dissolved, and SBA-15 grows on the surface of the microporous molecular sieve under a hydrothermal condition.
CN107858529A discloses a method for preparing ZSM-5/SBA-15, which comprises dissolving P123 in deionized water at 45 ℃, adding hydrochloric acid solution and stirring, then adding ZSM-5 molecular sieve and stirring, then adding tetraethoxysilane and reacting for 24h, transferring into a polyethylene tetrafluoro inner container of a reaction kettle, preserving heat at 100 ℃ for 3-5h, and then compounding with chitosan, wherein the molecular sieve obtained by the method has the problem of non-uniform compounding.
CN105238423A synthesizes Al-SBA-15 by using a recrystallization method, then takes the Al-SBA-15 as a raw material, adds a template agent, a silicon-aluminum source of a chemical reagent and the like, stirs the mixture, puts the mixture into a reaction kettle for recrystallization, then carries out suction filtration and drying, and puts dried solid powder into a tubular furnace for roasting to obtain Ni/ZSM-5/SBA-15. The process utilizes chemical reagent, strong acid and microporous template agent, and is non-green.
CN108441245A discloses a synthesis method of a ZSM-5/MCM41 composite molecular sieve by an epicrystal growth method, which is to dissolve the ZSM-5 molecular sieve by a sodium hydroxide strong alkali solution, then add hexadecyl trimethyl ammonium bromide as a mesoporous template agent, perform two-stage hydrothermal crystallization and finally synthesize the composite molecular sieve. The method is not only complicated in process, but also discharges a large amount of strong alkali solution.
CN102107143B discloses a preparation method of EUO/mesoporous composite molecular sieve, which comprises the steps of using a chemical reagent as a raw material, simultaneously adding a template agent and a surfactant, firstly, hydrothermally synthesizing the EUO molecular sieve from the raw material under the action of the template agent, then adjusting pH, and adding the surfactant to carry out a composite process of a mesoporous molecular sieve. This process has a high cost in both stages.
CN107777700A discloses a method for synthesizing a microporous ZSM-5 molecular sieve by using natural kaolin and water glass as raw materials without a template agent, and a crystallization mother liquor is used for carrying out alkali treatment on the molecular sieve to prepare a step pore molecular sieve.
CN201710270575.9 discloses a Beta molecular sieve with step holes synthesized by taking kaolin or rectorite activated by sub-molten salt as a raw material through one-step hydrothermal crystallization without adding an organic template agent. The method provided by the invention has the advantages that natural minerals activated by sub-molten salt are used as all aluminum sources and part of silicon sources, and no organic template agent is used in the synthesis process, so that the synthesis cost of the Beta molecular sieve is greatly reduced, and the greenness of the molecular sieve material production process is remarkably improved.
CN107879358A discloses a method for synthesizing an X-type molecular sieve by using diatomite as a silicon source and a part of an aluminum source and adopting a hydrothermal method. According to the invention, diatomite and aluminum hydroxide are added into a sodium hydroxide solution for dissolving, then in-situ assembly is carried out, and the X-type molecular sieve is obtained after hydrothermal crystallization.
Although various molecular sieve materials such as ZSM-5, BEA, X and the like are synthesized by taking natural clay minerals as raw materials, at present, no report is found for obtaining the composite SBA-15/ZSM-5 molecular sieve by taking precursors of the molecular sieves synthesized by the minerals as raw materials through assembly, so that a new synthesis technology of the composite molecular sieve is further developed on the basis of optimizing a front-stage synthesis process without using a template agent, a hydrocarbon isomerization catalyst carrier with high activity and high selectivity is developed, and a technical support is provided for upgrading the oil quality in China.
Disclosure of Invention
The invention provides a low-cost green preparation method of an SBA-15/ZSM-5 composite molecular sieve material with a suitable acidic and step pore structure, and aims to solve the problems that a single microporous ZSM-5 molecular sieve has low selectivity and severe cracking of double-branched isoparaffin due to narrow pore channel, small specific surface area and over-strong acidity in catalytic cracking (FCC) gasoline hydroisomerization, and a single mesoporous SBA-15 molecular sieve has low yield of isoparaffin due to weak acidity. The invention is characterized in that: the method comprises the steps of taking natural minerals as raw materials, synthesizing ZSM-5 nanocrystalline precursor liquid in a template-free environment, preparing an SBA-15/ZSM-5 composite molecular sieve carrier by adopting a low-acidity prehydrolysis method through in-situ assembly, enabling a silicon-aluminum source to be better dissolved in a system before assembly, overcoming the defects of large acid amount, serious corrosion to equipment, difficult waste liquid treatment and the like in the traditional strong acid system for synthesizing mesoporous materials by adopting a low-acidity assembly system, greatly reducing the production cost, reducing the equipment corrosion and reducing the emission of pollutants.
The invention achieves the above purposes through the following technical means, and the first aspect of the invention provides a preparation method of a micro-mesoporous SBA-15/ZSM-5 composite molecular sieve, which comprises the following steps:
step (1), activation of natural minerals: performing high-temperature roasting or sub-molten salt activation treatment on natural minerals to serve as a silicon source and an aluminum source for synthesizing ZSM-5 nanocrystals;
step (2), preparing a ZSM-5 nanocrystal precursor liquid: mixing and stirring an alkali source, deionized water, an aluminum source, a silicon source and a seed crystal uniformly, then aging at 20-100 ℃ for 1-15 h, crystallizing at 100-200 ℃ for 12-60 h, cooling after crystallization is finished, and stirring uniformly to obtain a ZSM-5 nanocrystal precursor liquid, wherein the mixture is expressed in terms of mole ratio of oxides and comprises the following components:
SiO2/Al2O3＝10～300，
Na2O/SiO2＝0.01～0.3，
H2O/SiO2＝5～40，
the dosage of the ZSM-5 seed crystal is 0.1-10% of the total mass of the reactants;
step (3), prehydrolysis: adding the prepared ZSM-5 nanocrystalline precursor liquid and a supplementary silicon source into an acid solution, wherein the mass ratio of the nanocrystalline precursor liquid to the supplementary silicon source to the acid solution is as follows: 1-12:1-20: 5-30; adjusting the pH value to 2-7, carrying out pre-hydrolysis treatment at 10-80 ℃ for 1-10 h, and standing for 1-5 h;
step (4), preparing the sodium type composite molecular sieve: slowly dripping the mixed solution obtained by pre-hydrolysis into a mesoporous template P123 (triblock copolymer, EO)20PO70EO20) Aging the solution at 10-80 ℃ for 5-40 h, and then aging the solution at 30-150 DEG CCrystallizing for 10-60 hours, after the crystallization is finished, filtering and washing a crystallized product to be neutral, drying a filter cake at 50-150 ℃, and then roasting in a muffle furnace at 200-800 ℃ for 2-10 hours to remove a template agent, thereby obtaining the sodium SBA-15/ZSM-5 composite molecular sieve;
step (5), preparing the SBA-15/ZSM-5 composite molecular sieve: heating and stirring the sodium SBA-15/ZSM-5 molecular sieve and 0.1-2 mol/L inorganic ammonium salt solution at 50-100 ℃ for 3-8 h according to the mass ratio of 1: 5-1: 20, repeating the operation, performing suction filtration, washing and drying, and finally roasting in a muffle furnace at 300-700 ℃ for 3-10 h to obtain the SBA-15/ZSM-5 composite molecular sieve.
In the preparation method of the mesoporous SBA-15/ZSM-5 composite molecular sieve provided by the present invention, preferably, in the step (1), the mixture is expressed in terms of mole ratio of oxides, and the composition ratio is as follows:
SiO2/Al2O3＝20～100，
Na2O/SiO2＝0.1～0.2，
H2O/SiO2＝10～30，
the dosage of the ZSM-5 seed crystal is 0.05-0.3% of the total mass of the reactants.
In the preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve provided by the invention, preferably, the natural mineral is one or more of bentonite, rectorite, chlorite, diatomite, sepiolite, montmorillonite and bauxite. Wherein the high-temperature roasting temperature is 600-1000 ℃, and the condition of activating the sub-molten salt is that the mineral, the sodium hydroxide and the water are uniformly mixed according to the mass ratio of 1: 1-2: 5-20 and then are placed in an oven at 100-300 ℃ for drying.
In the preparation method of the mesoporous SBA-15/ZSM-5 composite molecular sieve provided by the invention, preferably, the alkali source is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, sodium acetate, sodium hydroxide, potassium hydroxide, calcium hydroxide and concentrated ammonia water.
In the preparation method of the mesoporous SBA-15/ZSM-5 composite molecular sieve, the aging temperature in the step (2) is preferably 50-100 ℃, and the aging time is preferably 5-10 hours; the crystallization temperature is 140-180 ℃, and the crystallization time is 15-30 h.
In the preparation method of the mesoporous SBA-15/ZSM-5 composite molecular sieve provided by the invention, preferably, the silicon supplementing source is one or more of water glass, silica sol, sodium silicate, tetraethyl orthosilicate, silica gel, methyl orthosilicate or white carbon black.
In the preparation method of the mesoporous SBA-15/ZSM-5 composite molecular sieve, preferably, the acidic solution in the steps (3) and (4) is one or more of sulfuric acid, hydrochloric acid and phosphoric acid; the pH adjusting solution is hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide or ammonia water solution.
In the preparation method of the mesoporous SBA-15/ZSM-5 composite molecular sieve provided by the invention, preferably, in the step (3), the mass ratio of the ZSM-5 nanocrystal precursor liquid to the supplemental silicon source is 3-8: 4-10; the pH value of the mixed solution is 2-7, the prehydrolysis temperature is 20-60 ℃, the prehydrolysis time is 2-6 hours, and the standing time is 2-5 hours.
In the preparation method of the mesoporous SBA-15/ZSM-5 composite molecular sieve, preferably, in the step (4), the aging temperature is 30-70 ℃, and the aging time is 15-30 h; the crystallization temperature is 70-120 ℃, and the crystallization time is 15-30 h; the roasting temperature is 400-700 ℃, and the roasting time is 4-8 h.
In the preparation method of the mesoporous SBA-15/ZSM-5 composite molecular sieve provided by the present invention, preferably, in step (5), the inorganic ammonium salt solution is an aqueous solution of ammonium carbonate, ammonium sulfate, ammonium chloride or ammonium nitrate; the concentration of the inorganic ammonium salt solution is 0.5-1 mol/L.
In the preparation method of the mesoporous SBA-15/ZSM-5 composite molecular sieve, preferably, in the step (5), the roasting temperature is 400-650 ℃, and the roasting time is 4-7 h.
In the preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve provided by the invention, preferably, the prepared micro-mesoporous SBA-15/ZSM-5 composite molecular sieve has a mesoporous specific surface area of 600-800 m2A specific surface area of the micropores is 100 to 200m2The mesoporous aperture is 8-12 nm.
The invention also provides the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve prepared by the method.
Secondly, the invention provides a sulfur-resistant double-branched chain isomerization catalyst, which comprises a carrier and an active component, wherein the carrier is a micro-mesoporous SBA-15/ZSM-5 composite molecular sieve prepared by the preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve; the active component is one or more of Ni, Mo, W, Co and Fe, and the content of the active component is 0.1-10% of the total mass of the catalyst in terms of mass fraction of oxides.
The invention provides a preparation method of the sulfur-resistant double-branched chain isomerization catalyst, which comprises the following steps:
(1) preparing active component substances into impregnation liquid, and impregnating the impregnation liquid on the formed composite molecular sieve carrier;
(2) drying at 60-140 ℃ for 10-20 h, and roasting at 300-800 ℃ for 1-7 h to obtain the catalyst.
Fourthly, the invention provides the application of the sulfur-tolerant double-branched chain isomerization catalyst in the hydrogenation process of FCC gasoline.
According to an embodiment of the present invention, the present invention can be further described as follows:
firstly, the invention discloses a preparation method of an SBA-15/ZSM-5 composite molecular sieve material, which comprises the following steps:
(1) activation of natural minerals: and (3) performing high-temperature roasting or sub-molten salt activation treatment on the natural minerals to be used as a silicon source and an aluminum source for synthesizing the ZSM-5 nanocrystalline.
(2) Silicon source, aluminum source and H2Adding O, an alkali source and a seed crystal into a beaker, and adjusting the molar ratio of a synthesis system to SiO2/Al2O3＝10～300，Na2O/SiO2＝0.01～0.3，H2O/SiO2Stirring for 0.1-1 h, adding 0.01-0.5 g of ZSM-5 seed crystal, aging for 1-15 h at 20-100 ℃, then transferring to a stainless steel autoclave with a polytetrafluoroethylene lining, crystallizing for 12-60 h at 100-200 ℃, taking out after crystallization is finished, and uniformly stirring to obtain the ZSM-5 nanocrystal precursor liquid.
(3) Adding 1-12 g of the nanocrystalline precursor liquid and 1-20 g of a supplementary silicon source into 5-30 g of an acidic solution, adjusting the pH of the solution to 2-7, carrying out prehydrolysis at 10-80 ℃ for 1-10 h, and then standing for 1-5 h.
(4) And slowly dropwise adding the mixed solution into an inorganic acid solution in which a mesoporous template agent P123 is dissolved, aging for 5-40 h at 10-80 ℃, finally transferring the solution into a stainless steel autoclave with a polytetrafluoroethylene lining, crystallizing for 10-60 h at 30-150 ℃, filtering and washing a crystallized product to be neutral after crystallization is finished, placing a filter cake in an oven for drying overnight at 50-150 ℃, roasting in a muffle furnace at 200-800 ℃ for 2-10 h, and demolding to obtain the sodium SBA-15/ZSM-5 composite molecular sieve.
(5) Heating and stirring a sodium SBA-15/ZSM-5 molecular sieve and 0.1-2 mol/L inorganic ammonium salt solution at 50-100 ℃ for 3-8 h according to the mass ratio of 1: 5-1: 20, repeatedly performing ion exchange for 2 times, performing suction filtration, washing and drying, and finally roasting in a muffle furnace at 300-700 ℃ for 3-10 h to obtain the hydrogen SBA-15/ZSM-5 composite molecular sieve carrier.
According to the preparation method, the natural mineralized substance adopted in the step (1) preferably comprises one or more of bentonite, rectorite, chlorite, diatomite, sepiolite, montmorillonite and bauxite. Wherein the high-temperature roasting temperature is 600-1000 ℃, and the condition of activating the sub-molten salt is that the mineral, the sodium hydroxide and the water are uniformly mixed according to the mass ratio of 1: 1-2: 5-20 and then are placed in an oven at 100-300 ℃ for drying.
According to the preparation method, SiO is fed in the step (2) in the preferred mode2/Al2O3＝20～100，Na2O/SiO2＝0.1～0.2，H2O/SiO210-30 g of ZSM-5 seed crystal.
According to the preparation method, in the step (2), the aging is preferably carried out for 5-10 hours at the aging temperature of 50-100 ℃; preferably, the crystallization is carried out at the crystallization temperature of 140-180 ℃ for 15-30 h.
According to the preparation method provided by the invention, the silicon source supplement adopted in the step (3) is preferably one or more of water glass, silica sol, tetraethyl orthosilicate, methyl orthosilicate or white carbon black and the like.
According to the production method of the present invention, the inorganic acid solution in steps (3) and (4) of the present invention is preferably an aqueous solution of sulfuric acid, hydrochloric acid or phosphoric acid. The pH adjusting solution is preferably hydrochloric acid, sulfuric acid, phosphoric acid or sodium hydroxide, potassium hydroxide, or ammonia water solution.
According to the preparation method provided by the invention, in the step (3), the preferable amount of the nano-crystal is 3-8 g, the preferable amount of the silicon source is 4-10 g, the preferable pH value of the mixed solution is 2-6, the preferable prehydrolysis temperature is 20-60 ℃, the preferable prehydrolysis time is 2-6 hours, and the preferable standing time is 2-5 hours.
According to the preparation method, the aging temperature in the step (4) is preferably aging for 15-30 h at 30-70 ℃; the crystallization temperature is preferably 70-120 ℃ for 15-30 h.
According to the preparation method, the preferable molecular sieve carrier in the step (4) is roasted for 4-8 hours at 400-700 ℃ in a muffle furnace.
According to the production method of the present invention, the inorganic ammonium salt solution in the step (5) of the present invention is preferably an aqueous solution of ammonium carbonate, ammonium sulfate, ammonium chloride or ammonium nitrate.
According to the preparation method, in the step (5), the concentration of the inorganic ammonium salt solution is preferably 0.5-1 mol/L, and the solution is roasted in a muffle furnace at 400-650 ℃ for 4-7 h.
The invention also provides a sulfur-resistant double-branched chain isomerization catalyst, which comprises a carrier and an active component, wherein the carrier is an SBA-15/ZSM-5 composite molecular sieve material with a micro-mesoporous structure, which is obtained by taking the ZSM-5 with micropores as a precursor nanocrystal under the action of a mesoporous template. The carrier surface load active component is one or more of Ni, Mo, W, Co and Fe, and the content of the active component is 0.1-10% by mass percentage of oxide. The preparation method of the isomerization catalyst comprises the following steps: preparing an active component substance into a dipping solution, dipping the dipping solution on a formed composite molecular sieve carrier, drying the dipping solution at the temperature of 60-140 ℃ for 10-20 h, and roasting the dipping solution at the temperature of 300-800 ℃ for 1-7 h to finally obtain the hydroisomerization catalyst.
In conclusion, the invention provides a preparation process route of the SBA-15/ZSM-5 composite molecular sieve carrier, and the obtained composite molecular sieve carrier has the following advantages:
the ZSM-5 nanocrystalline precursor liquid provided by the invention is prepared by adopting low-cost natural mineral raw materials without using a template agent, breaks through the process route of synthesizing a microporous molecular sieve by using a traditional template agent as a chemical reagent, and greatly reduces the cost and the pollution emission.
In the in-situ assembly stage provided by the invention, the mixed solution is fully dissolved by adopting a prehydrolysis method, the micropore-mesopore assembly process is accelerated, the use amount and the discharge concentration of acid liquor are reduced by adopting a high-pH-value acidic solution, the difficulties of large acid amount, serious corrosion to equipment, difficult waste liquid treatment and the like in the traditional strong acid synthetic mesoporous material system are overcome, and the problem of environmental pollution caused by excessive waste liquid discharge is effectively solved.
The isomerization catalyst carrier prepared by the invention has uniform morphology and a micro-mesoporous composite pore structure, and has proper acid strength, wherein the specific surface area of the mesopore is 600-800 m2A specific surface area of the micropores is 100 to 200m2The mesoporous aperture can reach 8-12 nm. The method organically couples the advantages of the microporous molecular sieve and the mesoporous material.
The sulfur-tolerant double-branched chain isomerization catalyst provided by the invention is applied to the FCC gasoline hydrogenation process, the use of non-noble metal effectively solves the toxic action of sulfur-containing compounds in raw oil on active components, the micro-mesoporous composite step pore channel structure accelerates mass transfer diffusion of long-chain normal alkane in the isomerization process, increases the accessibility of acid sites, improves the dispersibility of active metal, slows down coking and inactivation of the catalyst, particularly improves the selectivity of double-branched chain isoparaffin, avoids cracking reaction, further improves the liquid yield and reduces the loss of the octane number of the product gasoline.
Drawings
FIG. 1 is the X-ray diffraction (XRD) spectrum of the SBA-15/ZSM-5 composite molecular sieve carrier prepared in example 1 of the present invention.
FIG. 2 shows the SBA-15/ZSM-5 composite molecular sieve carrier prepared in example 1 of the present inventionN of (A)2Adsorption desorption and pore size distribution profile.
Detailed Description
The following examples further illustrate the practice of the present invention in detail, but should not be construed as limiting the scope of the invention. The raw material reagents used in the invention are all commercial products.
Preparation of experimental reagents:
preparation of synthetic raw materials such as natural minerals: the rectorite, the diatomite, the bauxite and the solid silica gel are commercially available products, and the main components of the rectorite are as follows: SiO 22Is 43.2 wt% of Al2O3The content of (B) was 37.2 wt%. The diatomite comprises the following main components: SiO 22Is 93.2 wt% of Al2O3The content of (B) is 3.3 wt%; the main composition of bauxite: 52.85 wt% Al2O3Is 20.87 wt%; SiO of solid silica gel2Content of (B) 89.2 wt%, H2The O content was 9.9 wt%. The seed crystals used were a commercial grade ZSM-5 molecular sieve finished product produced by southern kaiko university catalyst plant having a silica to alumina molar ratio of 38.
Example 1
Activation of natural minerals: weighing 40g of diatomite powder, and roasting at 800 ℃ for 6 h; weighing 80g of rectorite, 80g of sodium hydroxide and 300g of water, mechanically stirring for 1h at normal temperature, activating for 10h in a 200 ℃ oven, and crushing for later use.
Preparing a ZSM-5 nanocrystal precursor liquid: 10g of activated diatomite, 1.8g of activated rectorite, 1.5g of NaOH and 0.2g of seed crystal are weighed and dissolved in 60g of deionized water, then the mixture is aged in 80 ℃ water bath for 4h, the mixture is put into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and the temperature is raised to 170 ℃ for standing and crystallization for 24 h. And cooling to room temperature after crystallization is finished, and uniformly stirring for later use.
Pre-hydrolyzing a composite material silicon-aluminum source: adding 5g of the nanocrystalline precursor liquid and 5g of tetraethoxysilane into 18g of hydrochloric acid solution, adjusting the pH value of the solution to be 2, carrying out prehydrolysis at 60 ℃ for 5 hours, and then standing for 4 hours.
Preparing the composite molecular sieve: slowly dropwise adding the prehydrolysis solution into a template agent P123 solution (a solution obtained by adding 1.5g of P123 into 42g of 1M hydrochloric acid solution and fully dissolving the mixture), aging at 30 ℃ for 18h, finally transferring the solution into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining for crystallization at 100 ℃ for 20h, filtering and washing a crystallized product to be neutral after crystallization is finished, placing a filter cake in an oven for drying at 120 ℃ overnight, roasting in a muffle furnace at 500 ℃ for 5h, and demolding to obtain the sodium type SBA-15/ZSM-5 composite molecular sieve; heating and stirring the sodium SBA-15/ZSM-5 molecular sieve and 1mol/L ammonium carbonate solution at 60 ℃ for 5 hours, repeatedly performing ion exchange for 2 times, performing suction filtration, washing and drying, and finally roasting in a 600 ℃ muffle furnace for 3-10 hours to obtain the hydrogen SBA-15/ZSM-5 composite molecular sieve carrier.
Preparation of the catalyst:
adding nickel chloride hexahydrate and cobalt acetate into deionized water to prepare a steeping fluid, dropwise adding the steeping fluid into the SBA-15/ZSM-5 carrier, drying at 100 ℃, and roasting at 550 ℃ for 6 hours to obtain the catalyst 1. Active metal component in the catalyst: the cobalt oxide content was 5.6 wt% and the nickel oxide content was 6.4 wt%.
Example 2
This example provides a SBA-15/ZSM-5 composite molecular sieve support material, which is prepared by the same steps as in example 1, with only some of the parameters being modulated, as follows:
preparing a ZSM-5 nanocrystal precursor liquid: weighing 8.5g of activated diatomite, 2.7g of 600 ℃ activated bauxite, 1.3g of NaOH and 0.14g of seed crystal, dissolving in 60g of deionized water, carrying out water bath aging at 80 ℃ for 4h, putting the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, heating to 170 ℃, standing and crystallizing for 24 h. And cooling to room temperature after crystallization is finished, and uniformly stirring for later use.
Pre-hydrolyzing a composite material silicon-aluminum source: adding 5g of the nanocrystalline precursor liquid and 4.2g of methyl orthosilicate into 18g of hydrochloric acid solution, adjusting the pH value of the solution to be 4, carrying out prehydrolysis at 60 ℃ for 5 hours, and then standing for 4 hours.
Preparing the composite molecular sieve: slowly dropwise adding the prehydrolysis solution into a template agent P123 solution (a solution obtained by adding 1g P123 to 42g of 0.5M hydrochloric acid solution and fully dissolving the mixture), aging at 30 ℃ for 18h, finally transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining for crystallization at 100 ℃ for 20h, filtering and washing a crystallized product to be neutral after crystallization is finished, placing a filter cake in an oven for drying at 120 ℃ overnight, roasting in a muffle furnace at 500 ℃ for 5h, and demolding to obtain the sodium type SBA-15/ZSM-5 composite molecular sieve; heating and stirring the sodium SBA-15/ZSM-5 molecular sieve and 1mol/L ammonium carbonate solution at 60 ℃ for 5 hours, repeatedly performing ion exchange for 2 times, performing suction filtration, washing and drying, and finally roasting in a 600 ℃ muffle furnace for 3-10 hours to obtain the hydrogen SBA-15/ZSM-5 composite molecular sieve carrier.
Preparation of the catalyst:
adding nickel chloride hexahydrate and cobalt acetate into deionized water to prepare a steeping fluid, dropwise adding the steeping fluid into the SBA-15/ZSM-5 carrier, drying at 100 ℃, and roasting at 550 ℃ for 6 hours to obtain the catalyst 2. Active metal component in the catalyst: the cobalt oxide content was 6.1 wt% and the nickel oxide content was 6.3 wt%.
Example 3
This example provides a SBA-15/ZSM-5 composite molecular sieve support material, which is prepared by the same steps as in example 1, with only some of the parameters being modulated, as follows:
preparing a ZSM-5 nanocrystal precursor liquid: 6.9g of activated diatomite, 1g of 600 ℃ activated bauxite, 1.5g of rectorite, 0.8g of NaOH and 0.17g of seed crystal are dissolved in 60g of deionized water, then the mixture is aged in 80 ℃ water bath for 4h, the mixture is put into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and the temperature is raised to 170 ℃ for static crystallization for 24 h. And cooling to room temperature after crystallization is finished, and uniformly stirring for later use.
Pre-hydrolyzing a composite material silicon-aluminum source: adding 5g of the nanocrystalline precursor liquid and 4g of methyl orthosilicate into 20g of hydrochloric acid solution, adjusting the pH value of the solution to be 5, carrying out prehydrolysis at 60 ℃ for 5 hours, and then standing for 4 hours.
Preparing the composite molecular sieve: slowly dropwise adding the prehydrolysis solution into a template agent P123 solution (a solution obtained by adding 1.5g of P123 into 40g of 2M hydrochloric acid solution and fully dissolving the mixture), aging at 30 ℃ for 18h, finally transferring the solution into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining for crystallization at 100 ℃ for 20h, filtering and washing a crystallized product to be neutral after crystallization is finished, placing a filter cake in an oven for drying at 120 ℃ overnight, roasting in a muffle furnace at 500 ℃ for 5h, and demolding to obtain the sodium type SBA-15/ZSM-5 composite molecular sieve; heating and stirring the sodium SBA-15/ZSM-5 molecular sieve and 1mol/L ammonium carbonate solution at 60 ℃ for 5 hours, repeatedly performing ion exchange for 2 times, performing suction filtration, washing and drying, and finally roasting in a 600 ℃ muffle furnace for 3-10 hours to obtain the hydrogen SBA-15/ZSM-5 composite molecular sieve carrier.
Preparation of the catalyst:
adding nickel chloride hexahydrate and cobalt acetate into deionized water to prepare a steeping fluid, dropwise adding the steeping fluid into the SBA-15/ZSM-5 carrier, drying at 100 ℃, and roasting at 550 ℃ for 6 hours to obtain the catalyst 3. Active metal component in the catalyst: the cobalt oxide content was 6.3 wt% and the nickel oxide content was 5.9 wt%.
Example 4
This example provides a SBA-15/ZSM-5 composite molecular sieve support material, which is prepared by the same steps as in example 1, with only some of the parameters being modulated, as follows:
preparing a ZSM-5 nanocrystal precursor liquid: weighing 4g of activated diatomite, 3g of solid silica gel, 3.1g of rectorite, 1g of NaOH and 0.18g of seed crystal in 60g of deionized water, aging in 80 ℃ water bath for 4h, putting the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, heating to 170 ℃, standing and crystallizing for 24 h. And cooling to room temperature after crystallization is finished, and uniformly stirring for later use.
Pre-hydrolyzing a composite material silicon-aluminum source: 4.5g of the nanocrystalline precursor liquid, 3.2g of methyl orthosilicate and 1.4g of water glass are added into 20g of hydrochloric acid solution, the pH value of the solution is adjusted to be 6, prehydrolysis is carried out at 60 ℃ for 5 hours, and then standing is carried out for 4 hours.
Preparing the composite molecular sieve: slowly dropwise adding the prehydrolysis solution into a template agent P123 solution (a solution obtained by adding 1g P123 to 40g of 1.5M hydrochloric acid solution and fully dissolving the mixture), aging at 30 ℃ for 18h, finally transferring the solution to a stainless steel autoclave with a polytetrafluoroethylene lining for crystallization at 100 ℃ for 20h, filtering and washing a crystallized product to be neutral after crystallization is finished, placing a filter cake in an oven for drying at 120 ℃ overnight, roasting in a muffle furnace at 500 ℃ for 5h, and demolding to obtain the sodium type SBA-15/ZSM-5 composite molecular sieve; heating and stirring the sodium SBA-15/ZSM-5 molecular sieve and 1mol/L ammonium carbonate solution at 60 ℃ for 5 hours, repeatedly performing ion exchange for 2 times, performing suction filtration, washing and drying, and finally roasting in a 600 ℃ muffle furnace for 3-10 hours to obtain the hydrogen SBA-15/ZSM-5 composite molecular sieve carrier.
Preparation of the catalyst:
adding nickel chloride hexahydrate and cobalt acetate into deionized water to prepare a steeping liquor, dropwise adding the steeping liquor to the SBA-15/ZSM-5 carrier, drying at 100 ℃, and roasting at 550 ℃ for 6 hours to obtain the catalyst 4. Active metal component in the catalyst: the cobalt oxide content was 6.8 wt% and the nickel oxide content was 6.1 wt%.
Example 5
The molecular sieve preparation of this example is the same as example 3 except that the surface of the SBA-15/ZSM-5 composite molecular sieve is not impregnated with nickel oxide and the catalyst preparation procedure is the same as example 1.
Example 6
The molecular sieve preparation of this example was the same as example 3 except that the surface of the SBA-15/ZSM-5 composite molecular sieve was not impregnated with cobalt oxide and the catalyst preparation procedure was the same as example 1 to obtain catalyst 6.
Comparative example 1
The catalyst was prepared as in example 1 except that the molecular sieve used in this comparative example was a ZSM-5 molecular sieve, the composite portion was not used, and the evaluation conditions of the comparative catalyst were the same as in example 1.
Comparative example 2
The catalyst preparation is the same as example 1 except that the molecular sieve adopted in the comparative example is the ZSM-5 molecular sieve obtained by the comparative experiment and the mesoporous SBA-15 molecular sieve physical mixed carrier is obtained by independent synthesis, and the evaluation conditions of the comparative catalyst are the same as example 1.
The evaluation of the reactivity of the catalyst was carried out in a 10mL mini continuous flow fixed bed reactor, and the product was collected and analyzed by gas chromatography, and the results are shown in Table 2. And (3) vulcanization process: the catalyst is pre-vulcanized by stages at the temperature of 150-320 ℃ by using vulcanized oil, the vulcanized oil is straight-run gasoline, and the vulcanizing agent is CS2Heating up in stages at 320 ℃ under 150 ℃ and 3MPa, changing into FCC gasoline replacement for 12h after vulcanization is finished, and adjusting to reverse reactionThe isomerization reaction of the catalytic cracking gasoline is carried out according to the process conditions. The reaction process conditions are as follows: the temperature of the reactor is 300 ℃, the reaction pressure is 1.8MPa, and the volume space velocity is 2.5h-1Hydrogen to oil volume ratio 320, sample for GC analysis after about 48h of reaction.
TABLE 1 specific surface area and pore size distribution of composite molecular sieve support
TABLE 2 catalyst hydroisomerization reaction results
| Catalyst and process for preparing same | Conversion (%) | Double branched chain selectivity (%) | Cracking selectivity (%) |
| Catalyst 1 | 85.5 | 17.7 | 10.3 |
| Catalyst 3 | 86.2 | 18.1 | 11.7 |
| |
71.6 | 14.1 | 13.6 |
| Catalyst 6 | 74.2 | 14.6 | 12.8 |
| Comparative example 1 | 99.8 | 2.0 | 97.6 |
| Comparative example 2 | 75.5 | 15.3 | 65.4 |
Compared with the hydroisomerization results of comparative examples 1 and 2, the catalysts 1 and 3 have the advantages of higher conversion rate, less cracking, high selectivity of double branched chains, good activity and better hydroisomerization performance. The reaction is run for 800h, the conversion rates of the hydroisomerization catalysts 1 and 3 are hardly reduced and are respectively 85.3 percent and 86.0 percent, and the selectivity of the double branched chain is maintained at about 18.0 percent. In general, the large aperture of the composite molecular sieve catalyst can effectively inhibit the generation of side reactions such as carbon deposition, excessive cracking and the like, and improve the selectivity of macromolecular products. The large specific surface of the carrier of the catalyst can improve the dispersion density of the active metal, effectively improve the activity of the catalyst, maintain good reaction performance of the catalyst, and have good economic benefit and industrial application prospect.
The above description is only an embodiment of the present invention, but the present invention is not limited thereto, and those skilled in the art can make many modifications without departing from the spirit of the present invention, and these modifications are within the protection of the present invention.
Claims (15)
1. A preparation method of a micro-mesoporous SBA-15/ZSM-5 composite molecular sieve is characterized by comprising the following steps:
step (1), performing high-temperature roasting or sub-molten salt activation treatment on natural minerals to obtain a silicon source and an aluminum source for synthesizing ZSM-5 nanocrystals;
and (2) mixing and uniformly stirring an alkali source, deionized water, a silicon source, an aluminum source and ZSM-5 seed crystals prepared in the step (1), then aging at 20-100 ℃ for 1-15 h, crystallizing at 100-200 ℃ for 12-60 h, cooling after crystallization is finished, and uniformly stirring to obtain a ZSM-5 nanocrystal precursor liquid, wherein the mixture is expressed in the form of oxide molar ratio and comprises the following components:
SiO2/Al2O3＝10～300，
Na2O/SiO2＝0.01～0.3，
H2O/SiO2＝5～40，
the dosage of the ZSM-5 seed crystal is 0.1-10% of the total mass of the reactants;
and (3) adding the ZSM-5 nanocrystal precursor liquid prepared in the step (2) and a silicon supplementing source into an acid solution, wherein the mass ratio of the nanocrystal precursor liquid to the silicon supplementing source to the acid solution is as follows: 1-12:1-20: 5-30; adjusting the pH value to 2-7, carrying out prehydrolysis treatment for 1-10 h at 10-80 ℃, and standing for 1-5 h to obtain a prehydrolyzed mixed solution;
slowly dripping the mixed solution obtained in the step (3) into an acid solution of a mesoporous template P123 (triblock copolymer, EO20PO70EO20), aging for 5-40 h at 10-80 ℃, then crystallizing for 10-60 h at 30-150 ℃, filtering and washing a crystallized product to be neutral after crystallization is finished, drying a filter cake at 50-150 ℃, and then roasting for 2-10 h at 200-800 ℃ in a muffle furnace to remove the template, thereby obtaining the sodium SBA-15/ZSM-5 composite molecular sieve;
and (5) heating and stirring the sodium SBA-15/ZSM-5 molecular sieve prepared in the step (4) and 0.1-2 mol/L inorganic ammonium salt solution at 50-100 ℃ for 3-8 h according to the mass ratio of 1: 5-1: 20, repeating the operation once, then carrying out suction filtration, washing and drying, and finally roasting in a muffle furnace at 300-700 ℃ for 3-10 h to obtain the SBA-15/ZSM-5 composite molecular sieve.
2. The method for preparing the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve according to claim 1, wherein in the step (1), the mixture is expressed in terms of mole ratio of oxides, and the composition ratio is as follows:
SiO2/Al2O3＝20～100，
Na2O/SiO2＝0.1～0.2，
H2O/SiO2＝10～30，
the dosage of the ZSM-5 seed crystal is 0.05-0.3% of the total mass of the reactants.
3. The preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 1, wherein the natural mineral is one or more of bentonite, rectorite, chlorite, diatomite, sepiolite, montmorillonite and bauxite; wherein the high-temperature roasting temperature is 600-1000 ℃, and the condition of activating the sub-molten salt is that the mineral, the sodium hydroxide and the water are uniformly mixed according to the mass ratio of 1: 1-2: 5-20 and then are placed in an oven at 100-300 ℃ for drying.
4. The preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 1, wherein the alkali source is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, sodium acetate, sodium hydroxide, potassium hydroxide, calcium hydroxide and concentrated ammonia water.
5. The preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 1, wherein the aging temperature in the step (2) is 50-100 ℃, and the aging time is 5-10 h; the crystallization temperature is 140-180 ℃, and the crystallization time is 15-30 h.
6. The preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 1, wherein the supplementary silicon source is one or more of water glass, silica sol, sodium silicate, tetraethyl orthosilicate, silica gel, methyl orthosilicate or white carbon black.
7. The preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 1, wherein the acidic solution in steps (3) and (4) is one or more of sulfuric acid, hydrochloric acid and phosphoric acid; the pH adjusting solution is hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide or ammonia water solution.
8. The preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve according to claim 1, wherein in the step (3), the mass ratio of the ZSM-5 nanocrystal precursor liquid to the supplemental silicon source is 3-8: 4-10; the pH value of the mixed solution is 2-7, the prehydrolysis temperature is 20-60 ℃, the prehydrolysis time is 2-6 hours, and the standing time is 2-5 hours.
9. The preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 1, wherein in the step (4), the aging temperature is 30-70 ℃, and the aging time is 15-30 h; the crystallization temperature is 70-120 ℃, and the crystallization time is 15-30 h; the roasting temperature is 400-700 ℃, and the roasting time is 4-8 h.
10. The method for preparing the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 1, wherein in the step (5), the inorganic ammonium salt solution is an aqueous solution of ammonium carbonate, ammonium sulfate, ammonium chloride or ammonium nitrate; the concentration of the inorganic ammonium salt solution is 0.5-1 mol/L.
11. The preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 1, wherein in the step (5), the roasting temperature is 400-650 ℃ and the roasting time is 4-7 h.
12. The preparation method of the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 1, wherein the prepared micro-mesoporous SBA-15/ZSM-5 composite molecular sieve has a mesoporous specific surface area of 600-800 m2A specific surface area of the micropores is 100 to 200m2The mesoporous aperture is 8-12 nm.
13. A micro-mesoporous SBA-15/ZSM-5 composite molecular sieve, characterized in that it is prepared by the method of any of claims 1-12 for preparing the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve.
14. A sulfur-tolerant double-branched chain isomerization catalyst, which comprises a carrier and an active component, wherein the carrier is the micro-mesoporous SBA-15/ZSM-5 composite molecular sieve of claim 13; the active component is one or more of Ni, Mo, W, Co and Fe, and the content of the active component is 0.1-10% of the total mass of the catalyst in terms of mass fraction of oxides.
15. Use of the sulfur tolerant double-branched isomerization catalyst of claim 14 in the hydrogenation of FCC gasoline.
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| CN115770613B (en) * | 2022-12-02 | 2024-03-12 | 江西省科学院应用化学研究所 | Molecular sieve catalyst and preparation method thereof |
| CN116216739A (en) * | 2023-02-22 | 2023-06-06 | 中国石油大学(北京) | ZSM-5-SBA-15 Composite Molecular Sieve and Its Preparation Method, Hydrofining Catalyst and Its Application |
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Application publication date: 20210413 |