CN114618576A - Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material and preparation method thereof - Google Patents

Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material and preparation method thereof Download PDF

Info

Publication number
CN114618576A
CN114618576A CN202011451791.1A CN202011451791A CN114618576A CN 114618576 A CN114618576 A CN 114618576A CN 202011451791 A CN202011451791 A CN 202011451791A CN 114618576 A CN114618576 A CN 114618576A
Authority
CN
China
Prior art keywords
sapo
composite material
phosphorus
acid
modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011451791.1A
Other languages
Chinese (zh)
Inventor
李海岩
田宏宇
姜维
谢方明
张铁珍
孙发民
郭金涛
马守涛
王东青
赵檀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN202011451791.1A priority Critical patent/CN114618576A/en
Publication of CN114618576A publication Critical patent/CN114618576A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention relates to a Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material and a preparation method thereof, wherein the preparation method mainly comprises the following steps of atomizing a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid, and carrying out spray adsorption on the Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material; and secondly, transferring the adsorbed and wetted Y/SAPO-11/amorphous silicon-phosphorus-aluminum composite material into a self-pressure kettle, and chemically modifying by using water vapor generated by the self-pressure of an acidic aqueous solution under a high-temperature condition to obtain the modified Y/SAPO-11/amorphous silicon-phosphorus-aluminum composite material. The method effectively reduces the amount of acidic wastewater generated in the acid treatment process of the composite material, and the hydrocracking catalyst prepared by adopting the modified Y/SAPO-11/amorphous silicon-phosphorus-aluminum composite material can produce more chemical raw materials, so that the total yield of the naphtha and tail oil chemical raw materials reaches more than 88%.

Description

Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material and preparation method thereof
Technical Field
The invention relates to a Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material for producing chemical raw materials in a high yield and a preparation method thereof, belonging to the field of oil refining catalysts.
Background
Y, Beta zeolite is widely used in adsorption, separation, catalysis and other fields owing to its unique pore structure, especially in petrochemical industry. With the heavy and inferior petroleum oils, conventional zeolites have failed to meet the demanding reaction-regeneration conditions of catalytic cracking; reasonably reducing the density of acid centers, improving the relative strength of the acid centers, increasing the mesoporous structure of zeolite, improving the ratio of cracking/hydrogen transfer activity, reducing the generation of catalytic coking, and improving the product distribution.
CN 201811264063.2A modified Y-type molecular sieve and its preparation method and application, disclose a preparation method of modified Y-type molecular sieve, include (1) adopt ammonium salt solution part exchange NaY-type molecular sieve sodion, then carry on the high-temperature roasting to NaNH4Y molecular sieve got; (2) exchanging sodium ions in the material in the step (1) again by adopting an ammonium salt solution, and carrying out hydrothermal treatment on the obtained material; (3) and (3) carrying out acid treatment on the material obtained in the step (2), and drying to obtain the modified Y-shaped molecular sieve. The modified Y molecular sieve prepared by the method has lower crystallinity and moderate pore volume, can provide proper reaction space for diesel oil fraction, improves the catalytic selectivity of the molecular sieve, and is simple in preparation method and suitable for industrial application.
Preparation of ammonium fluorosilicate modified HY molecular sieve/attapulgite catalyst and catalytic performance of olefin impurity removal thereof, volume 33 in 2017, page 6, 1097 and 1103, studies show that the optimum ammonium fluorosilicate modification conditions are as follows: the mass fraction of the ammonium fluosilicate solution is 2.5 percent, and the modification temperature is 70 ℃. The ammonium fluosilicate modified HY/ATP catalyst is subjected to a de-olefin experiment in a miniature batch reaction kettle, and when the reaction temperature is 170 ℃, the reaction pressure is 1.5MPa and the catalyst accounts for 5 percent (mass fraction) of the raw oil, the removal rate of olefin impurities in the reformate reaches 83.4 percent; after the catalyst is repeatedly used for 11 times, the removal rate of olefin impurities still reaches 53.1 percent.
The invention discloses a CN201410723953.0 modified Y-type molecular sieve and a preparation method thereof, and discloses a preparation method of a modified Y-type molecular sieve, which comprises the following steps: (1) preparing water solution containing fluorine and silicon; taking a low-sodium Y molecular sieve as the liquid (2), spraying and soaking the aqueous solution containing fluorine and silicon prepared in the step (1), curing for 30-240 min, drying, and carrying out hydrothermal treatment on the dried Y molecular sieve; (3) and (3) treating the molecular sieve subjected to the hydrothermal treatment in a dilute acid solution with the concentration of 0.2-2.0 mol/L for 30-240 min, washing a filter cake to be neutral after solid-liquid separation, and drying to obtain the molecular sieve product. The method can prepare the modified Y-shaped molecular sieve with high silicon-aluminum ratio, rich macroporous structure and high proper crystallinity, and the modified molecular sieve has high macromolecular hydrocarbon conversion capacity and simple preparation process.
CN201911159796.4 is a method for preparing SSZ-39 molecular sieve by taking fluorine modified Y-type molecular sieve as raw material, and the invention discloses a method for preparing SSZ-39 molecular sieve by taking fluorine modified Y-type molecular sieve as raw material. Dipping the Y-type molecular sieve in a fluorine-containing aqueous solution, drying and roasting to obtain a fluorine-doped Y-type molecular sieve; mixing deionized water, an alkali source, a template agent and a silicon source according to a ratio, uniformly stirring, and adding the fluorine-doped Y-type molecular sieve to prepare sol; transferring the sol into a crystallization kettle, after crystallization is completed, filtering, washing and drying a crystallized product, performing ion exchange, and roasting to prepare the hydrogen type SSZ-39 molecular sieve.
The influence of dealumination modification of ammonium fluosilicate of the nano NaY molecular sieve on the performance of the nano NaY molecular sieve was reported in Petroleum institute (Petroleum processing), 2 nd year 2018. The nano NaY molecular sieve with the particle size distribution below 100nm being uniform is synthesized by adopting a method without a template agent or a guiding agent. The dealuminizing modification is carried out on the nano NaY molecular sieve by adopting the dealuminizing agent of ammonium fluosilicate, and the influence of the factors such as the using amount of ammonium fluosilicate, the reaction time and the like on the physicochemical property and the catalytic performance of the nano NaY molecular sieve is examined. The result shows that the nano NaY molecular sieve pore structure after dealumination is kept complete, the thermal stability is good, the silicon/aluminum ratio (n (Si)/n (Al)) is improved, the number of acid centers is slightly reduced, and the number of strong acid centers is increased, so that the nano NaY molecular sieve pore structure shows excellent catalytic performance in the catalytic cracking reaction of 1,3, 5-triisopropylbenzene.
The research on the alkylation performance of toluene and tert-butyl alcohol catalyzed by phosphoric acid modification is carried out by carrying out gas phase catalysis on toluene and tert-butyl alcohol alkylation reaction on USY molecular sieve by phosphoric acid modification treatment on page 1467-page 1470 of No. 12 of volume 45 of Liaoning chemical industry. The experimental result shows that the crystal structure of the catalyst is not changed by ammoniation and acid modification treatment, but the number of micropores is reduced, the specific surface area is slightly increased, and the acid amount of the catalyst is increased. The USY catalytic performance of the phosphoric acid modification treatment of 0.005mol/L is the best, the highest toluene conversion rate is 25%, and the PTBT selectivity is as high as 62%. The plugging of the micropores formed by the carbon and oligomers is the main cause of the deactivation of the catalyst, which after calcination at 550 ℃ substantially reaches the activity of the fresh catalyst.
Characterization and catalytic performance of the H beta molecular sieve modified by combining phosphoric acid and water vapor, wherein physicochemical properties of the H beta molecular sieve modified by combining phosphorus and water vapor are researched in No. 14, No. 6, pages 46-49 of Industrial catalysis in 2006. Phosphorus modification causes the specific surface area of the molecular sieve to be 417m2The/g is reduced to 401m2The specific surface area of the molecular sieve treated with water vapor alone also decreases significantly with increasing treatment temperature. No new crystal phase appears before and after the modification of phosphorus and water vapor, and the H beta zeolite retains proper acid content after the combined modification, and the activity evaluation results of the samples before and after the modification show that the olefin conversion rate of the combined modified sample can still reach 42 percent under the high-temperature condition of 973K, which is far higher than the catalytic activity of the molecular sieve modified by only water vapor (the olefin conversion rate of the latter is only 33 percent), and the inhibition effect of phosphorus species on the high-temperature water vapor dealumination of the zeolite molecular sieve is shown.
Boric acid modified MCM-22 molecular sieve is used for catalyzing toluene alkylation to synthesize paraxylene, boric acid is used as a precursor and low-carbon fatty alcohol is used as a solvent in No. 36, No. 6, No. 2177 and No. 2182 of "chemical engineering progress", a series of boric acid modified MCM-22 microporous molecular sieve shape-selective catalysts are prepared by an impregnation method, and the shape-selective catalytic performance of the paraxylene synthesized by toluene and dimethyl carbonate alkylation is examined on a continuous flow fixed bed reactor. The experimental results show that: the boron modified MCM-22 catalyst prepared by taking boric acid as a precursor and n-propanol as a solvent not only shows excellent shape-selective performance in the process of alkylating p-xylene with toluene and dimethyl carbonate, but also keeps higher catalytic activity. This is probably because boric acid reacts with n-propanol during the impregnation process to form organic borate with larger molecular size, thereby realizing that the acid sites on the outer surface of the molecular sieve are covered without influencing the acid properties in the pores.
CN201911088466.0 boric acid modified molecular sieve and a preparation method and application thereof, relates to boric acid modified molecular sieve and a preparation method and application thereof, and belongs to the technical field of adsorbents. The invention aims to provide a preparation method of a boric acid modified molecular sieve. The method comprises the steps of soaking the molecular sieve by adopting a boric acid solution, carrying out solid-liquid separation, drying the solid, and roasting to obtain the boric acid modified molecular sieve. The boric acid modified molecular sieve is successfully prepared by carrying out impregnation modification on the molecular sieve, the preparation method is simple and controllable, the energy consumption is low, the cost is low, and the obtained modified molecular sieve can be used as N2/CH4、O2/CH4、(N2+O2)/CH4Selection of systemsAdsorbent, especially in the separation of N2/CH4When is CH4The adsorption capacity of the method is low, the separation ratio of nitrogen to methane is large, and the method can be applied to purifying methane in coal bed gas, oil field gas or biogas.
The method comprises the steps of catalyzing tert-butyl alcohol and isobutyraldehyde by using a citric acid modified SAPO-11 molecular sieve to synthesize 2, 5-dimethyl-2, 4-hexadiene, industrial catalysis, No. 22, No. 1, page 56-60 in 2014, using the SAPO-11 as a catalyst, and carrying out acid treatment modification on the SAPO-11 molecular sieve by using a citric acid solution, so that the catalytic activity of the molecular sieve is further improved, and the catalytic activity of the molecular sieve after acid washing modification is carried out on the SAPO-11 by using citric acid with different concentrations is investigated. The result shows that after 0.1 mol.L-1 citric acid is modified, the molecular sieve crystal particles keep better integrity, the acid amount of the medium-strength acid sites is the highest, the catalytic activity is the highest, the conversion rate reaches 78%, the yield is 66%, the molecular sieve crystal grains are reduced after the citric acid is modified, and the framework structure of the molecular sieve is damaged by high-concentration citric acid pickling.
The existing molecular sieve modification methods mainly comprise hydrofluoric acid modification, ammonium fluosilicate modification, phosphoric acid modification, boric acid modification, organic acid modification, hydrothermal treatment and other modification methods, and mainly comprise acid modification or steam modification combination of molecular sieves such as Y, Beta, MCM-22, SAPO-11 and the like.
Disclosure of Invention
The invention aims to provide a Y/SAPO-11/amorphous silica-phosphor-aluminum modified composite material for producing more chemical raw materials and a preparation method thereof, wherein the preparation method effectively reduces the amount of acidic wastewater generated in the acid treatment process of the composite material.
The preparation method of the Y/SAPO-11/amorphous silica-phosphor-aluminum modified composite material comprises the following steps:
(1) atomizing a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid, and carrying out spray adsorption on the Y/SAPO-11/amorphous silicon-phosphorus-aluminum composite material;
(2) transferring the Y/SAPO-11/amorphous silicon-phosphorus-aluminum composite material subjected to spray adsorption into a self-pressure kettle, and chemically modifying by using a superheated vapor-liquid acidic medium generated by self-pressure.
The preparation method of the Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material comprises the following steps of (50-70 wt%) Y, SAPO-11 and amorphous silicon-phosphorus-aluminum in the Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material: (1 wt% -5 wt%): (1 wt% to 45 wt%).
The preparation method of the Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material comprises the following steps of in a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid, wherein the weight ratio of hydrofluoric acid: boric acid: the phosphoric acid is (3wt percent to 10wt percent): (1 wt% -5 wt%): (1 wt% to 5 wt%).
The preparation method of the Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material comprises the following steps of mixing the Y/SAPO-11/amorphous silicon-phosphorus-aluminum composite material with a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid in a mass ratio of 1: (0.7-1.5).
The preparation method of the Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material comprises the following step of carrying out chemical modification at the modification temperature of 150-300 ℃ for 2-6 hours.
The invention also provides a Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material prepared by the preparation method, and the specific surface area of the Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material is 600-2The total pore volume is 0.78-1.00 mL/g, wherein the mesoporous pore volume is 0.40-0.45 mL/g, and the average pore diameter is 6-13 nm.
The invention can also be detailed as follows:
the invention provides a Y/SAPO-11/amorphous silica-phosphor-aluminum modified composite material for producing chemical raw materials in a large quantity, which comprises the following steps: (1) dispersing the Y/SAPO-11/amorphous silicon-phosphorus-aluminum composite material in a kneading machine; (2) according to the following steps of hydrofluoric acid: boric acid: the phosphoric acid content is 6 wt%: 2.5 wt%: preparing 2.5 wt% of water solution, and filling mixed water solution of hydrofluoric acid, boric acid and phosphoric acid with the same mass as that of the Y/SAPO-11/amorphous silicon-phosphorus-aluminum powder into a high-pressure sprayer; (3) carrying out high-pressure ultrafine atomization on a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid to form 100-200 mu m liquid drops, and carrying out spray mixing adsorption on the liquid drops and Y/SAPO-11/silicon-phosphorus-aluminum composite material powder continuously rotating in a kneading machine; (4) transferring the wetted Y/SAPO-11/silicoaluminophosphate composite material into a self-pressure kettle, and chemically modifying by using a superheated vapor-liquid acidic medium under a high-temperature condition; (5) and washing and drying to obtain the Y/SAPO-11/silicoaluminophosphate modified composite material. (6) Mixing the Y/SAPO-11/silicoaluminophosphate modified composite material with an alumina binder, extruding, forming and roasting to obtain the high-yield chemical raw material hydrocracking catalyst.
Compared with the prior art, the modification method adopting the polybasic acid combination reduces the damage degree of the framework structure of the molecular sieve, improves the secondary pore structure, increases the cracking and isomerization capabilities of the catalyst and can produce chemical raw materials and low-freezing diesel oil simultaneously while modifying the molecular sieve. By optimizing the modification process, a large amount of acidic wastewater generated in the acid treatment process of the composite material is effectively reduced, and the method is more environment-friendly. The Y/SAPO-11/amorphous silicoaluminophosphate modified composite material obtained by the preparation method has the advantages of high skeleton stability, large specific surface area and total pore volume, high proportion of mesoporous volume and large pore diameter, and has higher selectivity of chemical raw materials when raw materials such as straight-run diesel oil, coker diesel oil and catalytic diesel oil are processed, and the total yield of light naphtha, heavy naphtha and tail oil reaches 88%.
Detailed Description
The following provides a detailed description of embodiments of the invention. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and processes are given, but the scope of the invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1
(1) Dispersing 400 g of Y/SAPO-11/silicon-phosphorus-aluminum composite material powder in a kneading machine, starting a power supply, and rapidly rotating the kneading machine; (2) according to the hydrofluoric acid in the solution: boric acid: the content of phosphoric acid is 10 wt%: 3 wt%: 1 wt%, 600 g of mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid is put into a high-pressure sprayer; (3) carrying out high-pressure ultrafine atomization on a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid to form droplets of 100-200 mu m, and carrying out spray mixing adsorption on the droplets and Y/SAPO-11/silicon-phosphorus-aluminum composite material powder continuously rotating in a kneading machine until the solution is completely sprayed; (4) transferring the wetted Y/SAPO-11/silicoaluminophosphate composite material into a 1L self-pressure kettle, and utilizing the excess pressure generated by self-pressure at the high temperature of 200 DEG CCarrying out chemical modification on the hot vapor-liquid acidic medium for 2 hours; roasting at 650 ℃ to obtain the modified hierarchical pore Y/SAPO-11/silicoaluminophosphate composite material. The specific surface area of the product is kept at 600m2The total pore volume is 0.78mL/g, the mesoporous volume is 0.45mL/g, and the average pore diameter is 13 nm. Mixing the Y/SAPO-11/silicoaluminophosphate modified composite material with an alumina binder, extruding the mixture into strips, and roasting the strips at 550 ℃ to obtain the high-yield chemical raw material hydrocracking catalyst CAT 4.
Example 2
(1) Dispersing 400 g of Y/SAPO-11/silicon-phosphorus-aluminum composite material powder in a kneading machine, starting a power supply, and rapidly rotating the kneading machine; (2) according to the hydrofluoric acid in the solution: boric acid: the phosphoric acid content is 6 wt%: 3 wt%: 1 wt%, 400 g of mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid is put into a high-pressure sprayer; (3) carrying out high-pressure ultrafine atomization on a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid to form droplets of 100-200 mu m, and carrying out spray mixing adsorption on the droplets and Y/SAPO-11/silicon-phosphorus-aluminum composite material powder continuously rotating in a kneading machine until the solution is completely sprayed; (4) transferring the wetted Y/SAPO-11/silicoaluminophosphate composite material into a 1L self-pressure kettle, and chemically modifying for 6 hours at the high temperature of 150 ℃ by using a superheated vapor-liquid acidic medium generated by self-pressure; (5) washing with deionized water, drying at 120 ℃ for 1.5 hours, and roasting at 600 ℃ to obtain the modified hierarchical pore Y/SAPO-11/silicoaluminophosphate composite material. The specific surface area of the product is kept at 650m2The total pore volume is 0.85mL/g, the mesoporous volume is 0.45mL/g, and the average pore diameter is 9.0 nm. Mixing the Y/SAPO-11/silicoaluminophosphate modified composite material with an alumina binder, extruding the mixture into strips, and roasting the strips at 500 ℃ to obtain the high-yield chemical raw material hydrocracking catalyst.
Example 3
(1) Dispersing 400 g of Y/SAPO-11/silicon-phosphorus-aluminum composite material powder in a kneading machine, starting a power supply, and rapidly rotating the kneading machine; (2) according to the hydrofluoric acid in the solution: boric acid: the content of phosphoric acid is 3 wt%: 1 wt%: 5 wt%, 200 g of mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid is put into a high-pressure sprayer; (3) carrying out high-pressure ultrafine atomization on a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid to form 100-200 mu m liquid drops, and carrying out continuous rotation on the liquid drops and the Y/SAPO-11/silicon-phosphorus-aluminum composite material in a kneaderSpraying, mixing and adsorbing the powder until the solution is completely sprayed; (4) transferring the wetted Y/SAPO-11/silicoaluminophosphate composite material into a 1L self-pressure kettle, and chemically modifying for 4 hours at the high temperature of 250 ℃ by using a superheated vapor-liquid acidic medium generated by self-pressure; (5) washing with deionized water, drying at 120 ℃ for 2.0 hours, and roasting at 550 ℃ to obtain the modified hierarchical pore Y/SAPO-11/silicoaluminophosphate composite material. The specific surface area of the product is kept at 745m2The total pore volume is 1.00mL/g, wherein the mesoporous volume is 0.40mL/g, and the average pore diameter is 6.0 nm. Mixing the Y/SAPO-11/silicoaluminophosphate modified composite material with an alumina binder, extruding the mixture into strips, and roasting the strips at 450 ℃ to obtain the high-yield chemical raw material hydrocracking catalyst.
Example 4
(1) Dispersing 400 g of Y/SAPO-11/silicon-phosphorus-aluminum composite material powder in a kneading machine, starting a power supply, and rapidly rotating the kneading machine; (2) according to the hydrofluoric acid in the solution: boric acid: the content of phosphoric acid is 3 wt%: 5 wt%: 5 wt%, 600 g of mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid is put into a high-pressure sprayer; (3) carrying out high-pressure ultrafine atomization on a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid to form droplets of 100-200 mu m, and carrying out spray mixing adsorption on the droplets and Y/SAPO-11/silicon-phosphorus-aluminum composite material powder continuously rotating in a kneading machine until the solution is completely sprayed; (4) transferring the wetted Y/SAPO-11/silicoaluminophosphate composite material into a 1L self-pressure kettle, and chemically modifying for 3 hours at the high temperature of 300 ℃ by using a superheated vapor-liquid acidic medium generated by self-pressure; (5) washing with deionized water, drying at 120 ℃ for 1.5 hours, and roasting at 600 ℃ to obtain the modified hierarchical pore Y/SAPO-11/silicoaluminophosphate composite material. The specific surface area of the product is kept at 700m2The total pore volume is 0.90mL/g, the mesoporous volume is 0.42mL/g, and the average pore diameter is 7.0 nm. Mixing the Y/SAPO-11/silicoaluminophosphate modified composite material with an alumina binder, extruding into strips, and roasting at 400 ℃ to obtain the hydrocracking catalyst carrier for producing chemical raw materials by hydrocracking straight-run diesel oil. Obtain the high-yield hydrocracking catalyst for the chemical raw materials.
Example 5
Using the hydrocracking catalyst CAT4 prepared in example 1, straight-run diesel, coker diesel and catalyst diesel blends were processedRaw materials are added, under the condition that the hydrogen partial pressure is 10MPa, the volume ratio of hydrogen to oil is 700:1 and the volume space velocity is 1.5h-1Under the condition that the reaction temperature is 370 ℃, more chemical raw materials can be produced, and the total yield of naphtha and tail oil reaches 88 percent.
TABLE 1 evaluation results of catalysts
Figure BDA0002827320350000081
Figure BDA0002827320350000091
Comparative example 1
(1) Dispersing 400 g of Y/SAPO-11/silicon-phosphorus-aluminum composite material powder in a kneading machine, starting a power supply, and rapidly rotating the kneading machine; (2) according to the content of hydrofluoric acid in the solution of 14 wt%, 600 g of hydrofluoric acid aqueous solution is put into a high-pressure sprayer; (3) carrying out high-pressure ultrafine atomization on a hydrofluoric acid aqueous solution to form droplets of 100-200 mu m, and carrying out spray mixing adsorption on the droplets and Y/SAPO-11/silicon-phosphorus-aluminum composite material powder continuously rotating in a kneading machine until the solution is completely sprayed; (4) transferring the wetted Y/SAPO-11/silicoaluminophosphate composite material into a 1L self-pressure kettle, and chemically modifying for 2 hours at the high temperature of 200 ℃ by using a superheated vapor-liquid acidic medium generated by self-pressure; roasting at 550 ℃ to obtain the Y/SAPO-11/silicoaluminophosphate modified composite material. The specific surface area of the product is kept at 450m2The total pore volume is 0.60mL/g, the mesoporous volume is 0.40mL/g, and the average pore diameter is 20 nm. Mixing the Y/SAPO-11/silicoaluminophosphate modified composite material with an alumina binder, extruding the mixture into strips, and roasting the strips at 550 ℃ to obtain the high-yield chemical raw material hydrocracking catalyst CAT 1. In the method, the content of hydrofluoric acid is 14 wt%, the concentration is high, the skeleton of the product is seriously damaged, and the specific surface area and the pore volume are greatly reduced.
Comparative example 2
(1) Dispersing 400 g of Y/SAPO-11/silicon-phosphorus-aluminum composite material powder in a kneading machine, starting a power supply, and rapidly rotating the kneading machine; (2) according to the boric acid content of 14 wt% in the solution, 600 g of boric acid aqueous solution is filled into a high-pressure sprayer; (3) boric acid waterCarrying out high-pressure ultrafine atomization on the solution to form droplets of 100-200 mu m, and carrying out spray mixing adsorption on the droplets and Y/SAPO-11/silicon-phosphorus-aluminum composite material powder continuously rotating in a kneading machine until the solution is completely sprayed; (4) transferring the wetted Y/SAPO-11/silicoaluminophosphate composite material into a 1L self-pressure kettle, and chemically modifying for 2 hours at the high temperature of 200 ℃ by using a superheated vapor-liquid acidic medium generated by self-pressure; roasting at 650 ℃ to obtain the modified hierarchical pore Y/SAPO-11/silicoaluminophosphate composite material. The specific surface area of the product is kept at 720m2The total pore volume is 0.95mL/g, the mesoporous volume is 0.40mL/g, and the average pore diameter is 5 nm. Mixing the Y/SAPO-11/silicoaluminophosphate modified composite material with an alumina binder, extruding the mixture into strips, and roasting the strips at 550 ℃ to obtain the high-yield chemical raw material hydrocracking catalyst CAT 2. In the method, the boric acid content is 14 wt%, the acidity is weak, and the removal of non-framework aluminum is less, so that the proportion of mesoporous volume is reduced.
Comparative example 3
(1) Dispersing 400 g of Y/SAPO-11/silicon-phosphorus-aluminum composite material powder in a kneading machine, starting a power supply, and rapidly rotating the kneading machine; (2) according to the phosphoric acid content of 14 wt% in the solution, 600 g of phosphoric acid aqueous solution is filled into a high-pressure sprayer; (3) carrying out high-pressure ultrafine atomization on the phosphoric acid mixed aqueous solution to form 100-200 mu m liquid drops, and carrying out spray mixing adsorption on the liquid drops and Y/SAPO-11/silicon-phosphorus-aluminum composite material powder continuously rotating in a kneading machine until the solution is completely sprayed; (4) transferring the wetted Y/SAPO-11/silicoaluminophosphate composite material into a 1L self-pressure kettle, and chemically modifying for 2 hours at the high temperature of 200 ℃ by using a superheated vapor-liquid acidic medium generated by self-pressure; roasting at 650 ℃ to obtain the modified hierarchical pore Y/SAPO-11/silicoaluminophosphate composite material. The specific surface area of the product is kept at 500m2The total pore volume is 0.7mL/g, the mesoporous volume is 0.35mL/g, and the average pore diameter is 15 nm. Mixing the Y/SAPO-11/silicoaluminophosphate modified composite material with an alumina binder, extruding the mixture into strips, and roasting the strips at 550 ℃ to obtain the high-yield chemical raw material hydrocracking catalyst CAT 3. In the method, the content of phosphoric acid is 14 wt%, the concentration is high, so that the skeleton of the product is seriously damaged, and the specific surface area and the pore volume are greatly reduced.

Claims (6)

1. A preparation method of a Y/SAPO-11/amorphous silica-phosphor-aluminum modified composite material is characterized by comprising the following steps:
(1) atomizing a mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid, and carrying out spray adsorption on the Y/SAPO-11/amorphous silicon-phosphorus-aluminum composite material;
(2) transferring the Y/SAPO-11/amorphous silicon-phosphorus-aluminum composite material subjected to spray adsorption into a self-pressure kettle, and chemically modifying by using a superheated vapor-liquid acidic medium generated by self-pressure.
2. The method for preparing Y/SAPO-11/amorphous silica-aluminophosphate modified composite material according to claim 1, wherein the weight ratio of Y, SAPO-11 and amorphous silica-aluminophosphate in the Y/SAPO-11/amorphous silica-aluminophosphate composite material is (50 wt% to 70 wt%): (1 wt% -5 wt%): (1 wt% to 45 wt%).
3. The method for preparing Y/SAPO-11/amorphous silica-aluminophosphate modified composite material according to claim 1, wherein in the mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid, the ratio of hydrofluoric acid: boric acid: the phosphoric acid is (3wt percent to 10wt percent): (1 wt% -5 wt%): (1 wt% to 5 wt%).
4. The preparation method of the Y/SAPO-11/amorphous silica-phosphor-aluminum modified composite material according to claim 1, wherein the mass ratio of the Y/SAPO-11/amorphous silica-phosphor-aluminum composite material to the mixed aqueous solution of hydrofluoric acid, boric acid and phosphoric acid is 1: (0.7-1.5).
5. The preparation method of the Y/SAPO-11/amorphous silica-alumina-silica modified composite material according to claim 1, wherein the chemical modification is carried out at a modification temperature of 150-300 ℃ for 2-6 hours.
6. The Y/SAPO-11/amorphous silica-aluminophosphate modified composite material prepared by the preparation method according to any one of claims 1 to 5, wherein the specific surface area of the Y/SAPO-11/amorphous silica-aluminophosphate modified composite material is 600-745m2Per g, total poreThe volume is 0.78-1.00 mL/g, wherein the mesoporous volume is 0.40-0.45 mL/g, and the average pore diameter is 6-13 nm.
CN202011451791.1A 2020-12-10 2020-12-10 Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material and preparation method thereof Pending CN114618576A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011451791.1A CN114618576A (en) 2020-12-10 2020-12-10 Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011451791.1A CN114618576A (en) 2020-12-10 2020-12-10 Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN114618576A true CN114618576A (en) 2022-06-14

Family

ID=81895113

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011451791.1A Pending CN114618576A (en) 2020-12-10 2020-12-10 Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114618576A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4842714A (en) * 1984-11-27 1989-06-27 Uop Catalytic cracking process using silicoaluminophosphate molecular sieves
US5139989A (en) * 1991-08-28 1992-08-18 Uop Amorphous silica/alumina/phosphate composition and uses thereof
CN101058523A (en) * 2006-04-21 2007-10-24 浙江工业大学 Method of preparing linear alkylbenzene
US20100140138A1 (en) * 2006-11-23 2010-06-10 Alexandra Chaumonnot Catalyst based on a material with a hierarchical porosity comprising silicon, and a process for hydrocracking/hydroconversion and hydrotreatment of hydrocarbon feeds
CN103657714A (en) * 2012-08-29 2014-03-26 中国石油化工股份有限公司 Catalyst with hydrogenation catalysis effect, preparation method and application of catalyst and hydroisomerization method
CN105712373A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Modified Y type molecular sieve and preparation method thereof
CN109622028A (en) * 2018-12-31 2019-04-16 中海油天津化工研究设计院有限公司 A kind of high stability catalytic cracking diesel oil hydrocracking catalyst and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4842714A (en) * 1984-11-27 1989-06-27 Uop Catalytic cracking process using silicoaluminophosphate molecular sieves
US5139989A (en) * 1991-08-28 1992-08-18 Uop Amorphous silica/alumina/phosphate composition and uses thereof
CN101058523A (en) * 2006-04-21 2007-10-24 浙江工业大学 Method of preparing linear alkylbenzene
US20100140138A1 (en) * 2006-11-23 2010-06-10 Alexandra Chaumonnot Catalyst based on a material with a hierarchical porosity comprising silicon, and a process for hydrocracking/hydroconversion and hydrotreatment of hydrocarbon feeds
CN103657714A (en) * 2012-08-29 2014-03-26 中国石油化工股份有限公司 Catalyst with hydrogenation catalysis effect, preparation method and application of catalyst and hydroisomerization method
CN105712373A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Modified Y type molecular sieve and preparation method thereof
CN109622028A (en) * 2018-12-31 2019-04-16 中海油天津化工研究设计院有限公司 A kind of high stability catalytic cracking diesel oil hydrocracking catalyst and preparation method thereof

Similar Documents

Publication Publication Date Title
US11123725B2 (en) Methods for producing mesoporous zeolite multifunctional catalysts for upgrading pyrolysis oil
CN108726535B (en) Preparation method of phosphorus modified ZSM-5 molecular sieve with hierarchical pores
CN106669773A (en) Method for modifying Y-type molecular sieve
CN101884935A (en) Catalyst material and preparation method thereof
CN104549418B (en) A kind of Modified Zeolite Y and preparation method thereof
CN101147874B (en) Catalyst for preparing propylene and ethylene by C4 olefins and preparation method
EP3827898A1 (en) Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof
CN107344110A (en) Catalyst for producing low linear paraffin content hydrocracking tail oil and its preparation method and application
CN107344111A (en) Hydrocracking catalyst of maximum production low-coagulation diesel oil and its preparation method and application
CN109775718A (en) A kind of modified Y-Y isomorphous molecular sieve and its preparation method and application
CN104549417B (en) Boron modified Y-type molecular sieve and preparation method thereof
CN107344108A (en) A kind of catalyst for improving hydrocracking tail oil viscosity index (VI) and preparation method thereof
CN114618576A (en) Y/SAPO-11/amorphous silicon-phosphorus-aluminum modified composite material and preparation method thereof
CN107344115A (en) A kind of modified Y-Beta composite molecular screens and its preparation method and application
CN1234806C (en) Catalytic pyrolysis process for producing petroleum hydrocarbon of ethylene and propylene
CN114425419B (en) Catalytic cracking catalyst for increasing yield of olefin and aromatic hydrocarbon by hydrogenating LCO (liquid Crystal on gas), and preparation method and application thereof
CN107344109A (en) Produce hydrocracking catalyst of high-quality hydrocracking tail oil and preparation method thereof
CN107344112A (en) A kind of hydrocracking catalyst for producing high-quality catalytic reforming raw material and its preparation method and application
CN102863308B (en) Method for preparing olefin by catalyzing and cracking naphtha
CN107344103B (en) Hydrocracking catalyst for maximum production of high-quality ethylene raw material and preparation method and application thereof
CN116060113B (en) Catalyst for hydro-upgrading straight-run diesel oil and preparation method and application thereof
US11857955B1 (en) Processes of producing catalysts
CN114433189B (en) Aromatization catalyst and preparation method and application thereof
CN114425415B (en) Modified molecular sieve, preparation method thereof and method for producing fuel oil component
CN112538009B (en) Dimer acid, continuous production method thereof, continuous production system and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination