CN108067300B - Method for forming SAPO-34 molecular sieve catalyst - Google Patents
Method for forming SAPO-34 molecular sieve catalyst Download PDFInfo
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- 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)
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- 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)
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- 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
- B01J37/0036—Grinding
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
Abstract
The invention relates to a forming method of an SAPO-34 molecular sieve catalyst, which comprises the following steps: performing ultrasonic/colloid mill coupling treatment on the SAPO-34 molecular sieve, a silicon-aluminum material, a bonding material, water and a pore-forming material, adjusting the pH of slurry to 2-7 by using an acid or alkali pH regulator, performing spray drying on the homogeneous slurry, roasting the obtained semi-finished product in an oxygen-containing atmosphere, and cooling after roasting is finished to prepare a finished product SAPO-34 molecular sieve catalyst; the silicon-aluminum material is selected from one or more of micro silicon powder, diatomite, kaolin and bauxite; the binding material is silica sol or aluminum sol; the pore-forming material is selected from one or more of lignin powder, cellulose powder, starch, graphite and sesbania powder. According to the invention, the SAPO-34 catalyst with high forming rate and wear resistance and porosity is prepared by taking materials such as cheap industrial byproduct micro silicon powder as a silicon-aluminum material and materials such as abundant and cheap cellulose or lignin as pore-forming materials, and the requirements of MTO in a wider range are met.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a forming method of an SAPO-34 molecular sieve catalyst.
Background
In 1984, united states carbide corporation (UCC) developed a series of silicoaluminophosphate molecular sieves, known as third generation molecular sieves. It is to introduce Si element into AlPO4In the framework of the molecular sieve, the AlPO is broken4The charge of the original system is balanced, and the molecular sieve framework is chargedNegative, creating a B acid center and exchangeable cations. Most of the silicoaluminophosphate series molecular sieves have Methanol To Olefin (MTO) reaction activity, such as SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-46, SAPO-56 and the like. Of particular concern are SAPO-34 molecular sieves, which have the qualities of small pore size (0.43-0.50nm), moderate acidity, strong hydrothermal stability and the like, are suitable for MTO reaction, the methanol conversion rate is close to 100%, the low-carbon olefin selectivity is higher than 90%, and almost no products with the carbon number of more than 5 are generated.
At present, most industrial MTO reaction devices adopt a circulating fluidized bed reactor, the fluidized bed catalyst needs microspheres with the particle size of 20-150 mu m, the particle size of SAPO-34 crystal powder is generally less than 5 mu m, and the industrial catalyst suitable for the fluidized bed is prepared by processing and forming. The preparation process of the industrial SAPO-34 molecular sieve catalyst mainly comprises the steps of preparing slurry (mixing a molecular sieve, an adhesive, a carrier and the like), uniformly stirring the slurry, spray-drying and forming, and roasting and activating at high temperature.
Patent US4987110 filed by UOP corporation discloses a method for forming SAPO-34 molecular sieve with kaolin as a carrier and silica sol as a binder. Chinese patent CN101121148A discloses a method for directly forming a fluidized reaction catalyst of a molecular sieve, which does not perform solid-liquid separation after the molecular sieve is crystallized, directly adds a binder and a matrix component into a molecular sieve slurry, and performs spray drying after long-time colloid milling to obtain a formed microsphere molecular sieve catalyst.
In the patent US7271123B2 published by ExxonMobil, it is pointed out that the preferred support for the formation of SAPO-34 molecular sieve catalysts is clay, such as kaolin, kaolinite, montmorillonite, talc and bentonite, and the binder comprises essentially Al (OH)3、AlPO4、Al2O3、SiO2、SiO2-Al2O3Or MgO, ZrO2、TiO2And mixtures thereof. The mixing treatment of the slurry reported in the company US7301065B2 patent is beneficial to the uniform dispersion of the molecular sieve and carrier particles in the slurry and the formation of a good spherical catalyst by spray drying, in order to make the particles formed by spray drying uniform and avoid agglomeration of solid particles contained in the slurryThe slurry must be thoroughly mixed to ensure uniform slurry composition, and depending on the average particle size of the agglomerated molecular sieve crystals in the slurry, the slurry can be milled by a colloid mill to break up the agglomerates, reduce the size of the agglomerated particles or to obtain a narrower particle size distribution, with a milling time of 0.5 to 5.0 hours.
Sonochemistry is an edge discipline that uses ultrasonic energy to accelerate and control chemical reactions, increase reaction yields, and initiate new chemical reactions. The ultrasound action results from ultrasonic "cavitation". For a solid-liquid heterogeneous system, nuclear oscillation and micro-jet generated by cavitation can impact fluid, which is represented by fluid turbulence and strong mutual collision of particles, so that large particles are crushed, and the component interpenetration is facilitated (J.Am.chem.Soc.,1983,60: 1494). The ultrasonic wave is used in the preparation process of the catalyst, so that the permeability of the active component can be increased and uniformly dispersed, and the obtained catalyst has excellent performances of uniform dispersion of active species, high activity and the like (J.mol.Catal.,1981,1: 253).
The micro silicon powder is also called as silicon ash or condensed silicon ash, which is a large amount of SiO with strong volatility produced in an ore-smelting electric furnace when ferroalloy is used for smelting ferrosilicon and industrial silicon (metallic silicon)2And Si gas, the gas is quickly oxidized, condensed and precipitated with air after being discharged, and the material has the characteristics of high fluidity, fine granularity, high density, high strength and the like, and can obviously improve the abrasion strength and the high-temperature resistance of a product when being added to refractory and building materials.
According to the relevant information of SAPO-34 molecular sieve catalyst forming, the carrier used in the prior forming is mainly kaolin, slurry is obtained by long-time repeated colloid milling, the process is complex, the consumed time is long, the slurry uniformity is not too good, the abrasion resistance index and the forming rate of the catalyst are influenced, meanwhile, a large amount of catalyst active ingredients prepared in the process are wrapped in microspheres, a large amount of active centers cannot play catalytic activity, the waste of catalyst raw materials is caused, in addition, the distance from reactants to the active centers of the catalyst is increased, the diffusion resistance in the reaction process is increased, the selectivity of target products is reduced, especially for the chemical reaction of a large amount of heat release such as MTO, if the reaction heat in the microspheres is not timely removed, serious carbon deposition can be caused, and the catalyst is inactivated.
Based on the defects of pore channel deficiency, low utilization rate of active components, easy inactivation, low abrasion strength, time-consuming forming process and the like of the conventional SAPO-34 catalyst, the invention aims to develop the SAPO-34 catalyst with simple process and better performance by using cheap industrial byproduct, namely micro-silica powder as a carrier, abundant and cheap materials such as cellulose or lignin as pore-forming materials and using ultrasonic and rubber grinding coupling as a strategy in the conventional process, so that the large-scale application of MTO is met, and the SAPO-34 catalyst has great practical application value and prospect.
Disclosure of Invention
The invention aims to provide a method for forming an SAPO-34 molecular sieve catalyst, which overcomes the defects in the prior art, adopts a strategy of coupling ultrasonic and colloid milling, takes materials such as cheap industrial byproduct silicon micropowder and the like as silicon-aluminum materials and abundant and cheap materials such as cellulose or lignin and the like as pore-forming materials, shortens the colloid milling time, prepares the SAPO-34 catalyst which has high forming rate, wear resistance and porosity, and meets the requirement of MTO in a larger range.
In order to achieve the purpose, the invention adopts the following technical scheme:
a forming method of a SAPO-34 molecular sieve catalyst comprises the following steps: performing ultrasonic/colloid mill coupling treatment on the SAPO-34 molecular sieve, a silicon-aluminum material, a bonding material, water and a pore-forming material, adjusting the pH of slurry to 2-7 by using an acid or alkali pH regulator, performing spray drying on the homogeneous slurry, roasting the obtained semi-finished product in an oxygen-containing atmosphere, and cooling after roasting is finished to prepare a finished product SAPO-34 molecular sieve catalyst; the microscopic form of the SAPO-34 molecular sieve is a cube, a sheet or a hollow shell; the ultrasonic/colloid mill coupling treatment is auxiliary ultrasonic in the colloid mill process; the silicon-aluminum material is selected from one or more of micro silicon powder, diatomite, kaolin and bauxite; the binding material is silica sol or aluminum sol; the spray drying is airflow drying, pressure drying or centrifugal drying; the pore-forming material is selected from one or more of lignin powder, cellulose powder, starch, graphite and sesbania powder.
The forming method of the SAPO-34 molecular sieve catalyst comprises the following steps:
1) stirring and uniformly mixing the SAPO-34 molecular sieve, the silicon-aluminum material, the pore-forming material and water to form a suspension A, and stirring and mixing the bonding material and the water to form a suspension B;
2) mixing the suspension B and the suspension A in the step 1), stirring to form slurry, and adjusting the pH of the slurry to 2-7 by using an acid or alkali pH regulator, wherein the slurry comprises 40-60% by mass of total solids, the total solids comprise 30-60% by mass of SAPO-34 molecular sieves, 10-40% by mass of silicon-aluminum materials, 10-40% by mass of bonding materials calculated by silicon oxide or aluminum oxide, and 5-20% by mass of pore-forming materials;
3) injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment to form homogeneous slurry;
4) and (3) inputting the homogeneous slurry into spraying equipment through a pump, carrying out spray drying treatment, roasting the obtained semi-finished product in an oxygen-containing atmosphere, and cooling after roasting is finished to prepare the finished product catalyst.
Mixing the suspension B and the suspension A in the step 2) of the invention to form a suspension B, and adding the suspension B into the suspension A.
The silicon-aluminum material in the invention is selected from one or more of micro silicon powder, diatomite, kaolin or bauxite.
The silicon-aluminum material in the invention is preferably one or two of silica fume or diatomite.
The ultrasonic power of the ultrasound in the ultrasonic/colloid mill coupling treatment is 20W-300W, preferably 50W-150W, and the ultrasonic time is 0.2-1 h.
The pore-forming material selected in the invention is one or more selected from lignin powder, cellulose powder, starch, graphite and sesbania powder.
The pore-forming material selected in the present invention is preferably one or both of lignin powder and cellulose powder.
The pH regulator of the acid or alkali is selected from phosphoric acid, nitric acid, diethylamine, ammonia water, triethylamine or tetraethyl ammonium hydroxide.
The roasting in the oxygen-containing atmosphere is carried out in the mixed gas of oxygen and nitrogen with the oxygen-containing atmosphere of 5-10% of the volume fraction of the oxygen, the roasting temperature is 450-650 ℃, the roasting time is kept for 5-10h, and the heating rate is 3-5 ℃/min.
Compared with the prior art, the forming method of the SAPO-34 molecular sieve catalyst provided by the invention has the following advantages:
1) according to the invention, cheap silica fume, diatomite and the like are adopted as silicon-aluminum materials, the materials have the characteristics of good fluidity, fine granularity, high density, high strength and the like, and the formed catalyst has excellent wear-resisting index and high forming rate;
2) the invention controls the roasting atmosphere and the roasting condition, ensures the structural integrity of the catalyst and improves the wear resistance of the catalyst;
3) according to the invention, an ultrasonic/colloid milling combined process is adopted, and micro-jet released by ultrasonic waves can break up blocky particles, so that the collision probability of different components is accelerated, the fusion degree of the different components is improved, and the colloid milling time is shortened;
4) according to the invention, the pore-forming is carried out by adopting materials such as abundant and cheap lignin or cellulose, the formed SAPO-34 catalyst has high specific surface area, and the defects that the utilization rate of active components of the SAPO-34 catalyst prepared by the existing process is low, the catalyst is easy to inactivate and the like are overcome.
Detailed Description
The tests concerning the particle size (20-150 μm) distribution ratio, abrasion index, specific surface area of the samples were carried out as follows:
analyzing the particle Size distribution of the catalyst by adopting a Better Size2000 type laser particle Size analyzer;
according to the industry standard (RIPP29-90), the abrasion rate of the synthesized catalyst is tested by an abrasion index analyzer: putting a certain amount of samples into a wear index measuring device, blowing and grinding under constant airflow, discarding the samples blown out in the first hour, collecting the samples blown out, and calculating the average wear percentage per hour to be used as the wear index of the samples;
the specific surface area is measured by an ASAP2020 type full-automatic adsorption instrument.
In the present embodiment, the total solid content in the slurry is calculated, and the contents of the silica sol and the alumina sol as the binders are calculated as the contents of silica and alumina, respectively;
the invention is illustrated below with reference to specific examples. It is to be understood, however, that these examples are illustrative only and are not to be construed as limiting the scope of the present invention.
Example 1:
step 1): 1.2kg of SAPO-34 molecular sieve, 1.6kg of silica fume, 0.4kg of lignin and 4kg of water are stirred and uniformly mixed to form a suspension A, 2.66kg of alumina sol (containing 30 mass percent of alumina) and 0.14kg of water are stirred and mixed to form a suspension B, wherein the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, adjusting the pH of the slurry to 6 by diethylamine, stirring for 1h to form slurry, wherein the total solid content in the slurry is 40 mass percent, the mass percent of the SAPO-34 molecular sieve is 30 percent, the mass percent of the silica fume is 40 percent, the mass percent of the alumina is 20 percent, and the mass percent of the lignin is 10 percent;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 100W and the ultrasonic/colloid mill coupling treatment time of 1h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a centrifugal spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 450 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphere containing 5 vol.% of oxygen, and keeping the temperature for 5h to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 2:
step 1): 3.0kg of SAPO-34 molecular sieve, 0.5kg of diatomite, 1kg of cellulose and 3kg of water are stirred and uniformly mixed to form a suspension A, 1.67kg of alumina sol (containing 30 mass percent of alumina) and 0.83kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is sheet-shaped;
step 2): adding the suspension B into the suspension A, adjusting the pH of the slurry to 6 by diethylamine, stirring for 1h to form slurry, wherein the total solid content in the slurry is 50 mass percent, the mass percent of the SAPO-34 molecular sieve is 60 percent, the mass percent of the diatomite is 10 percent, the mass percent of the alumina is 10 percent, and the mass percent of the cellulose is 20 percent;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 150W and the ultrasonic/colloid mill coupling treatment time of 0.5h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a pressure type spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 550 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere containing 10 vol.% of oxygen, and keeping the temperature for 4 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 3:
step 1): 2.4kg of SAPO-34 molecular sieve, 0.6kg of silica fume, 0.6kg of cellulose and 1.5kg of water are stirred and mixed uniformly to form a suspension A, 4.8kg of alumina sol (containing 50 mass percent of alumina) and 0.1kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is hollow shell-shaped;
step 2): adding the suspension B into the suspension A, adjusting the pH of the slurry to 4 by phosphoric acid, and stirring for 1h to form slurry, wherein the total solid content in the slurry is 60 mass percent, the mass percent of the SAPO-34 molecular sieve is 40%, the mass percent of the silica fume is 10%, the mass percent of the alumina is 40%, and the mass percent of the cellulose is 10%;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 20W and the ultrasonic/colloid mill coupling treatment time of 0.2h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a pressure spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 650 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere containing 8 vol.% of oxygen, and keeping the temperature for 10 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 4:
step 1): 2.0kg of SAPO-34 molecular sieve, 1.2kg of silica fume, 0.2kg of cellulose and 4kg of water are stirred and mixed uniformly to form a suspension A, 2kg of alumina sol (containing 30 mass percent of alumina) and 0.6kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, adjusting the pH value of the slurry to 5 by triethylamine, and stirring for 1h to form slurry, wherein the total solid content in the slurry is 40 mass percent, the mass percent of the SAPO-34 molecular sieve is 50%, the mass percent of the silica fume is 30%, the mass percent of the alumina is 15%, and the mass percent of the cellulose is 5%;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 300W and the ultrasonic/colloid mill coupling treatment time of 0.3h to form homogeneous slurry;
step 4): and (2) inputting the homogeneous slurry into a centrifugal spraying device through a pump, carrying out spray drying treatment, keeping the obtained semi-finished product at 100 ℃ for 8h, then heating to 650 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere containing 8 vol.% of oxygen, and keeping for 10h to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 5:
step 1): 2.0kg of SAPO-34 molecular sieve, 1.2kg of diatomite, 0.2kg of starch and 4kg of water are stirred and uniformly mixed to form a suspension A, 2kg of alumina sol (containing 30 mass percent of alumina) and 0.6kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, adjusting the pH of the slurry to 5 by nitric acid, stirring for 1h to form slurry, wherein the total solid content in the slurry is 40 mass percent, the mass percent of the SAPO-34 molecular sieve is 50%, the mass percent of the diatomite is 30%, the mass percent of the alumina is 15%, and the mass percent of the starch is 5%;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 100W and the ultrasonic/colloid mill coupling treatment time of 0.3h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a centrifugal spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 650 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere containing 8 vol.% of oxygen, and keeping the temperature for 10 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 6:
step 1): 2.25kg of SAPO-34 molecular sieve, 1.25kg of kaolin, 0.75kg of sesbania powder and 2.25kg of water are stirred and mixed uniformly to form a suspension A, 2.5kg of silica sol (containing 30 mass percent of silica) and 1kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, adjusting the pH value of the slurry to 6 by ammonia water, and stirring for 1h to form slurry, wherein the total solid content in the slurry is 50 mass percent, the mass percent of the SAPO-34 molecular sieve is 50%, the mass percent of the kaolin is 30%, the mass percent of the silicon oxide is 15%, and the mass percent of the sesbania powder is 5%;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 70W and the ultrasonic/colloid mill coupling treatment time of 0.3h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a centrifugal spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 650 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere containing 8 vol.% of oxygen, and keeping the temperature for 10 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 7:
step 1): 2.25kg of SAPO-34 molecular sieve, 1.25kg of kaolin, 0.75kg of graphite and 2.25kg of water are stirred and mixed uniformly to form a suspension A, 2.5kg of silica sol (containing 30 mass percent of silica) and 1kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, adjusting the pH value of the slurry to 5 by triethylamine, and stirring for 1h to form slurry, wherein the total solid content in the slurry is 50 wt% percent, the mass percent of the SAPO-34 molecular sieve is 50%, the mass percent of the kaolin is 30%, the mass percent of the silicon oxide is 15%, and the mass percent of the graphite is 5%;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 120W and the ultrasonic/colloid mill coupling treatment time of 1h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a centrifugal spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 650 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere containing 8 vol.% of oxygen, and keeping the temperature for 10 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 8:
step 1): 2.25kg of SAPO-34 molecular sieve, 1.25kg of bauxite, 0.75kg of graphite and 2.25kg of water are stirred and mixed uniformly to form a suspension A, 2.5kg of silica sol (containing 30 mass percent of silica) and 1kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, adjusting the pH value of the slurry to 7 by tetraethylammonium hydroxide, stirring for 1h to form slurry, wherein the total solid content in the slurry is 50 mass percent, the mass percent of the SAPO-34 molecular sieve is 50%, the mass percent of the bauxite is 30%, the mass percent of the silicon oxide is 15%, and the mass percent of the graphite is 5%;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 100W and the ultrasonic/colloid mill coupling treatment time of 1h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a centrifugal spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 650 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere containing 8 vol.% of oxygen, and keeping the temperature for 10 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 9:
step 1): 2.64kg of SAPO-34 molecular sieve, 1.65kg of silica fume, 0.385kg of sesbania powder and 2.075kg of water are stirred and mixed uniformly to form a suspension A, 2.75kg of silica sol (containing 30 mass percent of silica) and 0.5kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, adjusting the pH value of the slurry to 5 by triethylamine, and stirring for 1h to form slurry, wherein the total solid content in the slurry is 55 mass percent, the mass percent of the SAPO-34 molecular sieve is 48%, the mass percent of the silica fume is 30%, the mass percent of the silicon oxide is 15%, and the mass percent of the sesbania powder is 7%;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 150W and the ultrasonic/colloid mill coupling treatment time of 0.5h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a centrifugal spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 550 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere containing 8 vol.% of oxygen, and keeping for 8 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 10:
step 1): 2.64kg of SAPO-34 molecular sieve, 1.65kg of silica fume, 0.385kg of lignin and 2.075kg of water are stirred and uniformly mixed to form a suspension A, 2.75kg of alumina sol (containing 30 mass percent of alumina) and 0.5kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, adjusting the pH value of the slurry to 5 by triethylamine, and stirring for 1h to form slurry, wherein the total solid content in the slurry is 55 mass percent, the mass percent of the SAPO-34 molecular sieve is 48%, the mass percent of the silica fume is 30%, the mass percent of the alumina is 15%, and the mass percent of the lignin is 7%;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 100W and the ultrasonic/colloid mill coupling treatment time of 0.5h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into airflow type spraying equipment through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 550 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere containing 8 vol.% of oxygen, and keeping the temperature for 8 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Example 11:
step 1): 2.64kg of SAPO-34 molecular sieve, 1.65kg of silica fume + kaolin, 0.385kg of lignin and 2.075kg of water are stirred and mixed uniformly to form a suspension A, 2.75kg of alumina sol (containing 30 mass percent of alumina) and 0.5kg of water are stirred and mixed to form a suspension B, and the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, adjusting the pH value of the slurry to 5 by triethylamine, and stirring for 1h to form slurry, wherein the total solid content in the slurry is 55 mass percent, the mass percent of the SAPO-34 molecular sieve is 48%, the mass percent of the silica fume and the kaolin is 30%, the mass percent of the alumina is 15%, and the mass percent of the lignin is 7%;
step 3): injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment with the ultrasonic power of 150W and the ultrasonic/colloid mill coupling treatment time of 0.5h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a centrifugal spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 550 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere containing 8 vol.% of oxygen, and keeping for 8 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Comparative example 1:
step 1): weighing 1.2kg of SAPO-34 molecular sieve and 1.6kg of silica fume, uniformly stirring and mixing with 4kg of water to form a suspension A, stirring and mixing 2.67kg of alumina sol (containing 30 mass percent of alumina) and 0.13kg of water to form a suspension B, wherein the microscopic form of the SAPO-34 molecular sieve is cubic;
step 2): adding the suspension B into the suspension A, stirring for 1h to form slurry, wherein the total solid content in the slurry is 37.5 mass percent, the mass percent of the SAPO-34 molecular sieve is 33.3 percent, the mass percent of the silica fume is 44.4 percent, and the mass percent of the alumina is 22.3 percent;
step 3): injecting the slurry into a colloid mill, and carrying out colloid milling treatment for 3h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a centrifugal spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 450 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere containing 8 vol.% of oxygen, and keeping the temperature for 5h to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Comparative example 2:
step 1): weighing 1.5kg of SAPO-34 molecular sieve and 1.0kg of kaolin, uniformly stirring the mixture and 1.1kg of water to form a suspension A, stirring 3.3kg of silica sol (containing 30 mass percent of silica) and 0.1kg of water to form a suspension B, wherein the micro-morphology of the SAPO-34 molecular sieve is sheet-shaped;
step 2): adding the suspension B into the suspension A, and stirring to form slurry, wherein the total solid content in the slurry is 50 mass percent, the mass percent of the SAPO-34 molecular sieve is 42.8%, the mass percent of the kaolin is 28.6%, and the mass percent of the silicon oxide is 28.6%;
step 3): injecting the slurry into a colloid mill, and carrying out colloid milling treatment for 3h to form homogeneous slurry;
step 4): and (3) inputting the homogeneous slurry into a pressure type spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 550 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere containing 5 vol.% of oxygen, and keeping the temperature for 5h to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Comparative example 3:
as in example 1, only step 3 was changed to: injecting the slurry into a colloid mill, and carrying out colloid milling treatment for 1h to form homogeneous slurry;
the results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
Comparative example 4:
as in example 1, only step 4 was changed to: and (3) inputting the homogeneous slurry into a pressure type spraying device through a pump, carrying out spray drying treatment, heating the obtained semi-finished product to 550 ℃ at a heating rate of 10 ℃/min in an air atmosphere, and keeping the temperature for 5 hours to obtain the finished product catalyst.
The results of measurement of the particle diameter distribution (20 to 150 μm), abrasion index and specific surface area of the sample are shown in Table 1.
TABLE 1 measurement of particle diameter (20-150 μm) distribution, abrasion ratio and specific surface area of shaped catalyst
| Abrasion Rate (%/h) | Specific surface area (m)2/g) | Distribution ratio% | |
| Example 1 | 0.5 | 380 | 99.2 |
| Example 2 | 0.6 | 375 | 99.5 |
| Example 3 | 0.6 | 346 | 98.5 |
| Example 4 | 0.7 | 340 | 98.6 |
| Example 5 | 0.7 | 355 | 97.9 |
| Example 6 | 0.8 | 365 | 98.6 |
| Example 7 | 0.7 | 358 | 98.2 |
| Examples8 | 0.8 | 340 | 98.6 |
| Example 9 | 0.6 | 348 | 98.5 |
| Example 10 | 0.6 | 350 | 98.7 |
| Example 11 | 0.7 | 355 | 98.9 |
| Comparative example 1 | 2.1 | 250 | 92.2 |
| Comparative example 2 | 2.8 | 242 | 82.5 |
| Comparative example 3 | 3.1 | 291 | 89.2 |
| Comparative example 4 | 2.8 | 330 | 85.6 |
According to the results of the particle size (20-150 μm) distribution rate, the attrition index and the specific surface area of the sample shown in Table 1, the attrition indexes of the prepared finished catalysts are all lower than 1%/h by adopting the forming technology of the invention, and meet the limit requirement of the attrition index of the fluidized bed, while the attrition indexes of the finished catalysts prepared in the comparative examples are all higher than 2%/h; for the specific surface area, the finished catalyst prepared by the technology has higher specific surface area, the utilization rate of active components is increased, and the service life of the catalyst is expected to be prolonged; in addition, the grain diameter of various finished catalysts of the invention is more than 98 percent in the range of 20-150 mu m, thereby meeting the fluidization requirement.
In conclusion, the invention not only can provide the finished catalyst meeting the requirements of the MTO reaction process, but also has convenient and efficient preparation process and shows good application prospect and theoretical research value.
Claims (7)
1. A forming method of an SAPO-34 molecular sieve catalyst is characterized by comprising the following steps: performing ultrasonic/colloid mill coupling treatment on the SAPO-34 molecular sieve, a silicon-aluminum material, a bonding material, water and a pore-forming material, adjusting the pH of slurry to 2-7 by using an acid or alkali pH regulator, performing spray drying on the homogeneous slurry, roasting the obtained semi-finished product in an oxygen-containing atmosphere, and cooling after roasting is finished to prepare a finished product SAPO-34 molecular sieve catalyst; the microscopic form of the SAPO-34 molecular sieve is a cube, a sheet or a hollow shell; the ultrasonic/colloid mill coupling treatment is auxiliary ultrasonic in the colloid mill process; the silicon-aluminum material is micro silicon powder; the binding material is silica sol or aluminum sol or a mixture thereof; the spray drying is one of airflow drying, pressure drying or centrifugal drying; the pore-forming material is selected from one or more of lignin powder, cellulose powder, starch, graphite and sesbania powder.
2. The method for forming a SAPO-34 molecular sieve catalyst of claim 1, comprising the steps of:
1) stirring and uniformly mixing the SAPO-34 molecular sieve, the silicon-aluminum material, the pore-forming material and water to form a suspension A, and stirring and mixing the bonding material and the water to form a suspension B;
2) mixing the suspension B and the suspension A in the step 1), stirring to form slurry, and adjusting the pH of the slurry to 2-7 by using an acid or alkali pH regulator, wherein the slurry comprises 40-60% by mass of total solids, the total solids comprise 30-60% by mass of SAPO-34 molecular sieves, 10-40% by mass of silicon-aluminum materials, 10-40% by mass of bonding materials calculated by silicon oxide or aluminum oxide, and 5-20% by mass of pore-forming materials;
3) injecting the slurry into a colloid mill with ultrasonic equipment, and performing ultrasonic/colloid mill coupling treatment to form homogeneous slurry;
4) and (3) inputting the homogeneous slurry into spraying equipment through a pump, carrying out spray drying treatment, roasting the obtained semi-finished product in an oxygen-containing atmosphere, and cooling after roasting is finished to prepare the finished product catalyst.
3. The method for forming the SAPO-34 molecular sieve catalyst according to claim 2, wherein the suspension B and the suspension A in the step 2) are mixed to form a suspension B, and the suspension B is added into the suspension A.
4. The method for forming the SAPO-34 molecular sieve catalyst according to claim 1 or 2, wherein the ultrasonic power of the ultrasound in the ultrasound/colloid mill coupling treatment is 20W-300W, and the ultrasonic time is 0.2-1 h.
5. The method for forming the SAPO-34 molecular sieve catalyst according to claim 1 or 2, wherein the pore-forming material is selected from one or both of lignin powder and cellulose powder.
6. The method for forming a SAPO-34 molecular sieve catalyst according to claim 1 or 2, wherein the acid or base pH modifier is selected from phosphoric acid, nitric acid, diethylamine, ammonia, triethylamine or tetraethylammonium hydroxide.
7. The method for forming the SAPO-34 molecular sieve catalyst as claimed in claim 1 or 2, wherein the calcination under the oxygen-containing atmosphere is performed under the mixed gas of oxygen and nitrogen with the oxygen volume fraction of 5-10% under the oxygen-containing atmosphere, the calcination temperature is 450-650 ℃, the calcination temperature is maintained for 5-10h, and the temperature rise rate is 3-5 ℃/min.
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