CN112239218B - Preparation method of MTO catalyst, MTO catalyst and application thereof - Google Patents

Preparation method of MTO catalyst, MTO catalyst and application thereof Download PDF

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CN112239218B
CN112239218B CN201910666648.5A CN201910666648A CN112239218B CN 112239218 B CN112239218 B CN 112239218B CN 201910666648 A CN201910666648 A CN 201910666648A CN 112239218 B CN112239218 B CN 112239218B
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CN112239218A (en
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邢爱华
袁德林
田大勇
孙琦
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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National Institute of Clean and Low Carbon Energy
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or 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
    • 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
    • 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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    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
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    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention relates to the field of catalyst synthesis, and particularly relates to a preparation method of an MTO catalyst, the MTO catalyst and application thereof. The method comprises the following steps: (1) mixing an aluminum source, a phosphorus source, a silicon source, an organic template agent R and water according to a certain molar ratio, adding an additive A after mixing to obtain a mixed solution I, wherein the additive A and the aluminum source Al are mixed 2 O 3 The molar ratio of (0.1-1.5) to 1, aging and performing hydrothermal crystallization, wherein the additive A is at least one of ester substances, acidic substances, silica sol and phosphoric acid; (2) cooling the product, and then carrying out flash evaporation to remove the organic template agent R to obtain slurry a; (3) mixing the slurry a with a binder and a carrier, adding the mixture into a colloid mill, and grinding and stirring the mixture to obtain slurry b; (4) and (4) carrying out spray forming on the slurry b, and roasting to obtain the MTO catalyst. The method of the invention improves the yield of the molecular sieve and reduces the production cost of the catalyst. The prepared catalyst has higher bulk density and excellent wear resistance and catalytic performance.

Description

Preparation method of MTO catalyst, MTO catalyst and application thereof
Technical Field
The invention relates to the field of catalyst synthesis, and particularly relates to a preparation method of an MTO catalyst, the MTO catalyst and application thereof.
Background
The Methanol To Olefin (MTO) continuous fluidized bed process requires that the catalyst has good catalytic performance, higher abrasion resistance, better sphericity and particle size distribution suitable for a fluidized bed reactor.
The SAPO-34 molecular sieve is an important component of the MTO catalyst, and has a crucial influence on the performance of the MTO catalyst after being formed. The preparation process of the industrial 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. The selection of the binder and the carrier, the preparation of the slurry, the inlet and outlet temperatures of the dryer, the drying rate, the spraying state, the treatment after forming and the like all affect the shape, the particle size distribution, the abrasion resistance, the structural performance, the catalytic performance and the service performance of the catalyst.
The preparation method of the slurry comprises the following steps: (1) dispersing a molecular sieve in deionized water to form a suspension; (2) preparing adhesive sol; (3) dispersing the support material with deionized water; (4) the above suspensions or colloidal solutions are mixed to form a slurry. And (3) spray drying the obtained slurry to prepare a formed catalyst, and roasting, activating and hardening the formed catalyst at high temperature to obtain the catalyst for industrial production.
US7301065B2 discloses a forming method for improving attrition strength of SAPO-34 molecular sieve catalysts and controlling particle size distribution of the formed catalyst. The slurry solid content is too high or too low, which can reduce the abrasion resistance of the formed catalyst, and the total solid content (mass fraction) of the slurry is preferably 44-46%, wherein the molecular sieve accounts for 40-48% of the total solid content, the binder accounts for 7-15% of the total solid content, and the carrier accounts for 40-60% of the total solid content. In the scheme of optimizing the material ratio in the slurry, the optimal ratio of the adhesive to the molecular sieve is 0.15-0.40, and the abrasion index (in terms of mass fraction) of the formed catalyst is optimally (0.2% -2.0%)/h. The specific surface area of the micropores of the molded catalyst prepared according to the raw material proportion is 400-600m 2 The specific surface area of the micro-pores of the SAPO-34 molecular sieve is about 70 to 90 percent per gram.
CN1341584A discloses a catalyst for efficiently converting methanol into light olefins, which comprises a crystalline metalloaluminophosphate molecular sieve, an inorganic oxide binder and a clay-based support (such as kaolin). By keeping the mass fraction of the molecular sieve at 40% or less, i.e., by reducing the amount of SAPO-34 molecular sieve, the attrition resistance of the catalyst can be improved. The standard abrasion test data show that the abrasion index can be controlled below 1.0%/h.
US7301065B2 discloses that a catalyst formed from a partially dried molecular sieve (e.g., dried at 60 ℃ for 3 hours) has a lower attrition index than an undried, wet cake formed catalyst, the former having an attrition index of 0.75%/h and the latter having an attrition index of 1.03%/h. Particle size distribution test results show that the catalyst shaped from partially dried molecular sieve is bimodal at 0.9 μm and 5 μm. When the composition of the outer surface of the molded catalyst is basically consistent with that of the inner part, the wear-resistant strength is high; when the internal and external compositions of the catalyst are not uniform, the catalyst is easily broken or split by external force. When the mass ratio of the clay to the aluminum element in the formed catalyst is 2.2-2.6 and the mass ratio of the clay to the aluminum element at the surface is 2.1-2.8, the abrasion index of the catalyst is lower than 0.3%/h.
CN1316301A discloses a method for preparing a zeolite catalyst, which comprises mixing a suspension formed during zeolite synthesis with an oligomeric silica sol to prepare an aqueous dispersion without separating the catalyst from a slurry, and then spray-drying the aqueous dispersion.
CN101121148A A method for directly forming a fluidized reaction catalyst containing a molecular sieve. And (3) directly adding a binder and a matrix component into the molecular sieve slurry without separating a solid product obtained after the molecular sieve is crystallized, and carrying out spray drying after colloid milling to obtain the formed microsphere molecular sieve catalyst. The method omits the steps of separating, washing and drying the molecular sieve crystallization product, simplifies the operation steps, reduces the pollution, and simultaneously reduces the raw material consumption because unreacted components in the slurry can be used as the matrix of the formed catalyst, thereby greatly reducing the preparation cost of the molecular sieve catalyst.
The above patents all use the slurry of molecular sieve synthesis itself, and all directly carry out molecular sieve formation without separation.
CN101940944A relates to a method for utilizing molecular sieve crystallization slurry, which is to separate the molecular sieve crystallization slurry from a molecular sieve, mix the rest suspension with the treated molecular sieve crystal, a binder, a pore-forming agent and a matrix component according to a certain proportion, and spray-dry the mixture after uniform mixing to obtain the formed molecular sieve catalyst. The crystallized slurry is reused, so the investment is saved and the environment is protected. Meanwhile, the molecular sieve crystal is modified before the mixing step, so that the treatment mode aiming at the molecular sieve is more flexible. However, this process does not omit the molecular sieve solid-liquid separation step and only a portion of the slurry is utilized.
The above method does not recycle the template agent used in the synthesis of the molecular sieve. When the template agent is formed in the catalyst, part of the template agent is volatilized and decomposed due to the high-temperature condition, and the other part of the template agent is converted into NO in the roasting process X And CO 2 Causing serious pollution to the environment.
Disclosure of Invention
The invention aims to solve the problems of pollution caused by high-temperature roasting of a template agent in a molecular sieve and low utilization rate of raw materials in the prior art, and provides a preparation method of an MTO catalyst, the MTO catalyst and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an MTO catalyst, comprising the steps of:
(1) aluminum source, phosphorus source, silicon source, organic template agent R and water are mixed according to the molar ratio of Al 2 O 3 :(0.7-1.5)P 2 O 5 :(0.1-1)SiO 2 :(1.0-4)R:(20-100)H 2 O, mixing to obtain initial crystallization sol, adding an additive A into the initial crystallization sol, and ageing the obtained mixed solution I and then carrying out hydrothermal crystallization; wherein the additive A and the aluminum source are Al 2 O 3 The calculated molar ratio is (0.1-1.5):1, and the additive A is at least one of ester substances, acidic substances, silica sol and phosphoric acid;
(2) cooling the product obtained in the step (1), and then carrying out flash evaporation to remove the organic template agent R to obtain slurry a;
(3) mixing the slurry a with a binder and a carrier, and adding the mixture into a colloid mill for grinding and stirring to obtain slurry b;
(4) and (4) carrying out spray drying on the slurry b, and roasting to obtain the MTO catalyst.
Preferably, the aluminum source, the phosphorus source, the silicon source, the organic template agent R and the water are in a molar ratio of Al 2 O 3 :(0.85-1.2)P 2 O 5 :(0.15-0.35)SiO 2 :(2.5-3.5)R:(30-60)H 2 And mixing the O.
Preferably, the additive A and the aluminum source are Al 2 O 3 The calculated molar ratio is (0.4-1): 1.
Preferably, the additive A is an ester substance, a mixture of silica sol and phosphoric acid, or an acidic substance, a mixture of silica sol and phosphoric acid, or a mixture of an ester substance and an acidic substance.
More preferably, the additive A is an ester substance or an acidic substance.
Preferably, the acidic substance is at least one of hydrochloric acid, sulfuric acid, nitric acid, citric acid, acetic acid, ethylenediamine tetraacetic acid, tartaric acid, oxalic acid, malic acid, citric acid, benzoic acid, salicylic acid, propionic acid, and butyric acid; the ester substance is ethyl acetate and/or ethyl benzoate.
Preferably, the amount of the silica sol is 0-5wt% of the silicon source, and the amount of the phosphoric acid is 0-10wt% of the phosphorus source.
Preferably, in the step (1), the aging temperature is 10-50 ℃, and the aging time is 2-8 h; more preferably, the aging temperature is 20-40 ℃ and the aging time is 3-5 h.
Preferably, in the step (1), the hydrothermal crystallization temperature is 150-; preferably, the hydrothermal crystallization temperature is 180-210 ℃, and the hydrothermal crystallization time is 20-48 h.
Preferably, in step (2), the flash evaporation conditions include: the flash evaporation temperature is 90-108 ℃; preferably 95-100 deg.c.
Preferably, in the step (3), the weight ratio of the slurry a to the binder and the carrier is (7-10) to 1 (2-3.5); preferably, the weight ratio of the slurry a to the binder and the carrier is (7.5-8.5):1: 3.
Preferably, in the step (3), the grinding time is 1-10min, and the stirring time is 5-20 h; more preferably, the grinding time is 3-5min and the stirring time is 10-17 h.
Preferably, in the step (4), the inlet temperature is 250-500 ℃ and the outlet temperature is 90-130 ℃ in the spray drying process; preferably, the inlet temperature is 300-400 ℃ and the outlet temperature is 100-110 ℃.
In a second aspect, the present invention provides an MTO catalyst prepared by the above-mentioned preparation method.
The invention also provides a method for preparing olefin by using the MTO catalyst.
The preparation method of the MTO catalyst provided by the invention has the following beneficial effects:
1. due to the introduction of the additive, the preparation method provided by the invention can greatly improve the yield of the MTO catalyst.
2. The preparation method provided by the invention greatly improves the utilization rate of each raw material, so that the content of unreacted aluminum element and phosphorus element in crystallized slurry is reduced by about 55%, the slurry can be directly molded after the template agent is recovered by flash evaporation, the processes of washing and filtering the catalyst are reduced, and the discharge amount of wastewater is greatly reduced.
3. The yield of the catalyst prepared by the preparation method provided by the invention is greatly improved, so that the viscosity of the crystallized slurry can be obviously reduced, specifically, the viscosity of the crystallized slurry can be reduced from 4000-10000cp to 500-1000cp, and after the binder and the carrier are added, the problems of high slurry viscosity, low solid content of the formed slurry and low bulk density of the directly spray-formed catalyst caused by the existence of unreacted aluminum phosphate colloid when the catalyst yield is too low are solved. The slurry viscosity and solid content provided by the invention meet the level of the conventional method, and can be directly sprayed and formed.
4. In the invention, the molecular sieve crystallized slurry is subjected to flash evaporation, so that the template agent is recycled.
5. According to the method for directly spraying and forming the crystallized slurry, a step of separating liquid from solid by using a molecular sieve is not needed, so that washing and filtering links are reduced, and wastewater discharge is greatly reduced.
Drawings
FIG. 1 is an SEM image of a sample of example 1 at 150 times magnification;
FIG. 2 is an SEM image of a sample of example 1 at a magnification of 3000.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of an MTO catalyst, which comprises the following steps:
(1) aluminum source, phosphorus source, silicon source, organic template agent R and water are mixed according to the molar ratio of Al 2 O 3 :(0.7-1.5)P 2 O 5 :(0.1-1)SiO 2 :(1-4)R:(20-100)H 2 O is mixed to obtain initial crystallization sol, an additive A is added into the initial crystallization sol to obtain a mixed solution I, wherein the additive A and the aluminum source are Al 2 O 3 The calculated molar ratio is (0.1-1.5):1, and hydrothermal crystallization is carried out after aging, wherein, the additive A is esterAt least one of a proton, an acidic substance, a silica sol, and phosphoric acid;
(2) cooling the product obtained in the step (1), and then carrying out flash evaporation to remove the organic template agent R to obtain slurry a;
(3) mixing the slurry a with a binder and a carrier, and adding the mixture into a colloid mill for grinding and stirring to obtain slurry b;
(4) and (4) carrying out spray forming on the slurry b, and roasting to obtain the MTO catalyst.
In the invention, the organic template in the molecular sieve crystallized slurry is removed from the slurry by a flash evaporation mode, so that the template is recycled, the utilization rate of the molecular sieve raw material is improved, and the synthesis cost of the molecular sieve is reduced. Meanwhile, the pollution gas generated by subsequent high-temperature treatment of the organic template agent is reduced, and the pollution to the environment is reduced.
In the invention, the aluminum source is one or more of pseudo-boehmite, aluminum isopropoxide and aluminum oxide; the phosphorus source is one or more of phosphoric acid, phosphate, phosphorous acid and phosphite; the silicon source is one or more of silica sol and tetraethoxysilane; the template agent is one or more of diethylamine, triethylamine, tetraethyl ammonium hydroxide and morpholine.
In the invention, when the template agent is organic amine such as diethylamine, triethylamine and the like, the method provided by the invention can also avoid the pollution to the environment caused by the organic amine entering the wastewater.
According to the invention, after the aluminum source, the phosphorus source, the silicon source, the organic template agent R and the additive A are added into the water system, the yield of the SAPO-34 molecular sieve obtained by aging treatment and hydrothermal crystallization and flash evaporation is greatly improved, and the MTO catalyst with excellent performance can be obtained by one-step spray forming.
According to the invention, the aluminum source, the phosphorus source, the silicon source, the organic template agent R and the water are Al according to the molar ratio 2 O 3 :(0.85-1.2)P 2 O 5 :(0.15-0.35)SiO 2 :(2.5-3.5)R:(30-60)H 2 And mixing the O.
In the present invention, aluminumDerived from Al 2 O 3 In terms of phosphorus source, P 2 O 5 The silicon source is SiO 2 The organic template R is counted by the molecule of the template specific compound.
According to the invention, the additive A and the aluminum source are Al 2 O 3 The calculated molar ratio is (0.4-1): 1.
In the present invention, in order to obtain an MTO catalyst with more excellent performance, it is preferable that the additive a comprises an ester and/or an acidic material, and specifically, the additive a may be a mixture of an ester, a silica sol and phosphoric acid, or an acidic material, a mixture of a silica sol and phosphoric acid, or a mixture of an ester and an acidic material, and more preferably, the additive a is an ester or an acidic material.
Specifically, when the additive A contains ester substances and acidic substances, the weight ratio of the ester substances to the acidic substances is 0.05-1: 1, preferably 0.5 to 1: 1.
according to the invention, the acidic substance is at least one of hydrochloric acid, sulfuric acid, nitric acid, citric acid, acetic acid, ethylene diamine tetraacetic acid, tartaric acid, oxalic acid, malic acid, citric acid, benzoic acid, salicylic acid, propionic acid and butyric acid; the ester substance is ethyl acetate and/or ethyl benzoate.
According to the invention, the amount of the silica sol is 0-5wt% of the silicon source, and the amount of the phosphoric acid is 0-10wt% of the phosphorus source.
According to the invention, in the step (1), the aging temperature is 10-50 ℃, and the aging time is 2-8 h; preferably, the aging temperature is 20-40 ℃ and the aging time is 3-5 h.
According to the invention, in the step (1), the hydrothermal crystallization temperature is 150-; preferably, the hydrothermal crystallization temperature is 180-210 ℃, and the hydrothermal crystallization time is 20-48 h.
According to the invention, in the step (2), the flash evaporation conditions comprise that the flash evaporation temperature is 90-108 ℃; preferably 95-100 deg.C.
In the invention, the template agent can be removed from the slurry by flash evaporation of the molecular sieve crystallized slurry, so that the template agent is recycled and utilized, and the problems of environmental pollution and the like caused by the template agent in the subsequent MTO catalyst preparation process are solved. By adopting the flash evaporation condition, the recovery rate of the template agent in the slurry can reach 40-60%.
According to the invention, in the step (3), the weight ratio of the slurry a to the binder and the carrier is (7-10):1 (2-3.5).
In the present invention, the slurry a, the binder and the carrier are mixed in the above-mentioned mass ratio to prepare the MTO catalyst, and a catalyst having excellent catalytic performance and abrasion resistance and having a suitable particle size distribution can be obtained.
In the invention, the binder is aluminum sol and/or silica sol, and the carrier is kaolin and/or montmorillonite.
In order to obtain a more excellent MTO catalyst, the weight ratio of the slurry a to the binder and the carrier is preferably (7.5-8.5):1: 3.
According to the invention, the grinding time is 1-10min, and the stirring time is 5-20 h; preferably, the grinding time is 3-5min, and the stirring time is 10-17 h.
According to the invention, in the step (4), in the spray drying process, the inlet temperature is 250-500 ℃, and the outlet temperature is 90-130 ℃; preferably, the inlet temperature is 300-400 ℃ and the outlet temperature is 100-110 ℃.
In a second aspect, the present invention provides an MTO catalyst prepared by the above-described preparation method.
The third aspect of the invention provides an application of the MTO catalyst in the preparation of olefin from methanol.
The present invention will be described in detail below by way of examples.
In the following examples, the surface morphology of the MTO catalyst was characterized using a Scanning Electron Microscope (SEM). The instrument used for SEM test is a Nova Nano SEM 450 scanning electron microscope instrument of FEI company in America, and the test condition is that the accelerating voltage is 30V-30 kV;
the bulk density of the catalyst is tested by the method GB/T6286-1986;
attrition index of the catalyst an attrition tester established by ASTM D5757-2000 standard, spray plate: 3 blowing holes with the inner diameter of 0.381 +/-0.005 mm are designed. The loading of the catalyst is 50g, the compressed air is dried, the gas flow is 15L/min, and the pressure setting range is 0.1-0.4 Mpa;
the content of unreacted aluminum and phosphorus in the crystallized slurry is measured by an inductively coupled plasma atomic emission spectrometry (ICP) analysis method;
the viscosity of the slurry before spray forming was measured using a rotational viscometer.
The fixed fluidized bed catalyst evaluation conditions were: the loading of the catalyst is 10g, the reaction temperature is 450 ℃, the reaction pressure is 0.11MPa (absolute pressure), and the mass space velocity of the methanol is 1.5h -1 ，N 2 The flow rate was 70 ml/min.
Example 1
110g of pseudoboehmite was added to 310g of deionized water and stirred rapidly for 1h, labeled as solution A. 157g of analytically pure phosphoric acid (85 wt% in terms of mass fraction) was slowly added dropwise to solution A, and stirred for 1 hour to give homogeneous sol B. 28.5g of silica sol (the mass fraction is 30%) is added into the solution B, the mixture is stirred for 1h, 206g of triethylamine and 66g of diethylamine are added, and the mixture is stirred uniformly to obtain initial crystallized sol. To the initial crystallized sol was added additive a, which contained 1.2g of silica sol (30% by mass), 15g of phosphoric acid (85% by mass), 132g of citric acid (99% by mass). Putting the sol into a high-pressure reaction kettle, aging at room temperature of 30 ℃ for 4h, rotating at the speed of 200rpm, and then carrying out temperature programming to 200 ℃ for crystallization for 24 h. Wherein the molar ratio of each component is as follows: 1Al 2 O 3 :0.98P 2 O 5 :0.2SiO 2 :0.91A:2.7TEA:1.2DEA:30H 2 O。
When the temperature of the high-pressure reaction kettle is reduced to 90 ℃, removing the template agents triethylamine and diethylamine by flash evaporation, and reducing the temperature to room temperature to obtain slurry a. And (3) taking a small amount of slurry for centrifugal separation, washing, filtering and drying to calculate the yield of the molecular sieve to be 89%.
439g of the flash-evaporated slurry was poured into a colloid mill, and 324g of alumina sol (20 wt% in terms of mass fraction) was added, followed by 226g of kaolin and 150g of deionized water. Grinding with colloid mill for 3-5min, stirring at room temperature for 12 hr, and spray-forming. The inlet temperature of the spray dryer was 350 ℃ and the outlet temperature was 105 ℃. And (3) placing the spray-formed catalyst into a muffle furnace, and roasting at the constant temperature of 650 ℃ for 5 hours to obtain the MTO catalyst A1.
Tests show that the content of unreacted aluminum element and phosphorus element in the crystallized slurry is 2.2 wt% and 2.9 wt%; the viscosity of the spray-formed slurry was 500 cp. The bulk ratio of the catalyst was 0.81 g/ml. The abrasion index of the abrasion tester is 0.15 percent h -1 . The catalyst evaluation results are shown in table 1.
As can be seen from the SEM images of the figure 1 and the figure 2, the prepared catalyst MTO has good sphericity and smooth external surface appearance, the molecular sieve crystal grains can not be seen on the external surface of the catalyst, and the molecular sieve is wrapped inside by the binder.
Example 2
110g of pseudoboehmite was added to 310g of deionized water and stirred rapidly for 1h, labeled as solution A. 157g of analytically pure phosphoric acid (85 wt% in terms of mass fraction) was slowly added dropwise to solution A, and stirred for 1 hour to give homogeneous sol B. Adding 28.5g of silica sol (mass fraction of 30%) into the solution B, stirring for 1h, then adding 206g of triethylamine and 66g of diethylamine, uniformly stirring to obtain initial crystallized sol, and adding an additive A into the initial crystallized sol, wherein 1.2g of silica sol (mass fraction of 30%), 15g of phosphoric acid (mass fraction of 85 wt%), and 61g of oxalic acid (mass fraction of 99 wt%). Putting the sol into a high-pressure hydrothermal kettle, aging for 4h at the room temperature of 30 ℃, rotating at the speed of 200rpm, and then carrying out temperature programming to 200 ℃ for crystallization for 24 h. The molar ratio of each component is as follows: 1Al 2 O 3 :0.98P 2 O 5 :0.2SiO 2 :0.91A:2.7TEA:1.2DEA:30H 2 O。
When the temperature of the high-pressure reaction kettle is reduced to 90 ℃, removing the template agents triethylamine and diethylamine by flash evaporation, and reducing the temperature to room temperature to obtain slurry a. Taking a small amount of slurry for centrifugal separation, washing, filtering and drying to calculate the yield of the molecular sieve to be 85 percent.
439g of the flash-evaporated slurry was poured into a colloid mill, and 324g of alumina sol (20 wt% in terms of mass fraction) was added, followed by 226g of kaolin and 150g of deionized water. Grinding with colloid mill for 3-5min, stirring at room temperature for 12 hr, and spray-forming. The inlet temperature of the spray dryer was 350 ℃ and the outlet temperature was 105 ℃. And (3) placing the spray-formed catalyst into a muffle furnace, and roasting at the constant temperature of 650 ℃ for 5 hours to obtain the MTO catalyst A2.
The bulk ratio of the catalyst was 0.79 g/ml. The abrasion index of the abrasion tester is 0.21 percent h -1 。
Example 3
110g of pseudo-boehmite was added to 310g of deionized water and stirred rapidly for 1h, labeled as solution A. 157g of analytically pure phosphoric acid (85 wt% in terms of mass fraction) was slowly added dropwise to solution A, and stirred for 1 hour to give homogeneous sol B. 28.5g of silica sol (the mass fraction is 30%) is added into the solution B, the mixture is stirred for 1h, 206g of triethylamine and 66g of diethylamine are added, and the mixture is stirred uniformly to obtain initial crystallized sol. To the initial crystallized sol was added additive a comprising 1.2g of silica sol (30% by mass), 15g of phosphoric acid (85% by mass), 90g of ethyl acetate. Putting the sol into a high-pressure reaction kettle, aging at room temperature of 30 ℃ for 4h, rotating at the speed of 200rpm, and then carrying out temperature programming to 200 ℃ for crystallization for 24 h. The mol ratio of each component is as follows: 1Al 2 O 3 :0.98P 2 O 5 :0.2SiO 2 :0.91A：2.7TEA:1.2DEA:30H 2 O。
When the temperature of the high-pressure reaction kettle is reduced to 90 ℃, removing the template agents triethylamine and diethylamine by flash evaporation, and reducing the temperature to room temperature to obtain slurry a. And (3) taking a small amount of slurry for centrifugal separation, washing, filtering and drying to calculate the yield of the molecular sieve to be 89%.
439g of the flash-evaporated slurry was poured into a colloid mill, and 324g of alumina sol (20 wt% in terms of mass fraction) was added, followed by 226g of kaolin and 150g of deionized water. Grinding with colloid mill for 3-5min, stirring at room temperature for 12 hr, and spray-forming. The inlet temperature of the spray dryer was 350 ℃ and the outlet temperature was 105 ℃. And (3) placing the spray-formed catalyst into a muffle furnace, and roasting at the constant temperature of 650 ℃ for 5 hours to obtain the MTO catalyst A3.
The bulk ratio of the catalyst was 0.80 g/ml. The abrasion index of the abrasion tester is 0.12 percent h -1 。
Example 4
110g of pseudoboehmite was added to 310g of deionized water and stirred rapidly for 1h, labeled as solution A.157g of analytically pure phosphoric acid (85 wt% in terms of mass fraction) was slowly added dropwise to solution A, and stirred for 1 hour to give homogeneous sol B. 28.5g of silica sol (the mass fraction is 30%) is added into the solution B, the mixture is stirred for 1h, 206g of triethylamine and 66g of diethylamine are added, and the mixture is stirred uniformly to obtain initial crystallized sol. To the initial crystallized sol was added additive a, which was 132g citric acid (mass fraction 99 wt.%). Putting the sol into a high-pressure reaction kettle, aging at room temperature of 30 ℃ for 4h, rotating at the speed of 200rpm, and then carrying out temperature programming to 200 ℃ for crystallization for 24 h. Wherein the molar ratio of each component is as follows: 1Al 2 O 3 :0.98P 2 O 5 :0.2SiO 2 :0.91A:2.7TEA:1.2DEA:30H 2 O。
When the temperature of the high-pressure reaction kettle is reduced to 90 ℃, removing the template agents triethylamine and diethylamine by flash evaporation, and reducing the temperature to room temperature to obtain slurry a. And (3) taking a small amount of slurry for centrifugal separation, washing, filtering and drying to calculate the yield of the molecular sieve to be 89%.
439g of the flash-evaporated slurry was poured into a colloid mill, and 324g of alumina sol (20 wt% in terms of mass fraction) was added, followed by 226g of kaolin and 150g of deionized water. Grinding with colloid mill for 3-5min, stirring at room temperature for 12 hr, and spray-forming. The inlet temperature of the spray dryer was 350 ℃ and the outlet temperature was 105 ℃. And (3) placing the spray-formed catalyst into a muffle furnace, and roasting at the constant temperature of 650 ℃ for 5 hours to obtain the MTO catalyst A4.
The bulk ratio of the catalyst was 0.78 g/ml. The abrasion index of the abrasion tester is 0.19 percent h -1 。
Example 5
110g of pseudoboehmite was added to 310g of deionized water and stirred rapidly for 1h, labeled as solution A. 157g of analytically pure phosphoric acid (85 wt% in terms of mass fraction) was slowly added dropwise to solution A, and stirred for 1 hour to give homogeneous sol B. 28.5g of silica sol (the mass fraction is 30%) is added into the solution B, the mixture is stirred for 1h, 206g of triethylamine and 66g of diethylamine are added, and the mixture is stirred uniformly to obtain initial crystallized sol. To the initial crystallized sol was added additive a, which contained 2.0g of silica sol (30% by mass), 25g of phosphoric acid (85% by mass), 220g of citric acid (99% by mass). Placing the sol into high-pressure reactionAging at room temperature of 30 ℃ for 4h in a kettle, rotating at the speed of 200rpm, and then carrying out temperature programming to 200 ℃ for crystallization for 24 h. Wherein the molar ratio of each component is as follows: 1Al 2 O 3 :0.98P 2 O 5 :0.2SiO 2 :1.5A:2.7TEA:1.2DEA:30H 2 O。
When the temperature of the high-pressure reaction kettle is reduced to 90 ℃, removing the template agents triethylamine and diethylamine by flash evaporation, and reducing the temperature to room temperature to obtain slurry a. And (3) taking a small amount of slurry for centrifugal separation, washing, filtering and drying to calculate the yield of the molecular sieve to be 89%.
439g of the flash-evaporated slurry was poured into a colloid mill, and 324g of alumina sol (20 wt% in terms of mass fraction) was added, followed by 226g of kaolin and 150g of deionized water. Grinding with colloid mill for 3-5min, stirring at room temperature for 12 hr, and spray-forming. The inlet temperature of the spray dryer was 350 ℃ and the outlet temperature was 105 ℃. And (3) placing the spray-formed catalyst into a muffle furnace, and roasting at the constant temperature of 650 ℃ for 5 hours to obtain the MTO catalyst A5.
The bulk ratio of the catalyst was 0.82 g/ml. The abrasion index of the abrasion tester is 0.21 percent h -1 。
Example 6
110g of pseudoboehmite was added to 310g of deionized water and stirred rapidly for 1h, labeled as solution A. 157g of analytically pure phosphoric acid (85 wt% in terms of mass fraction) was slowly added dropwise to solution A, and stirred for 1 hour to give homogeneous sol B. 28.5g of silica sol (the mass fraction is 30%) is added into the solution B, the mixture is stirred for 1h, 206g of triethylamine and 66g of diethylamine are added, and the mixture is stirred uniformly to obtain initial crystallized sol. To the initial crystallized sol was added additive a, which contained 1.2g of silica sol (30% by mass), 15g of phosphoric acid (85% by mass), 61g of citric acid (99% by mass), 60.4g of ethyl acetate. Putting the sol into a high-pressure reaction kettle, aging at room temperature of 30 ℃ for 4h, rotating at the speed of 200rpm, and then carrying out temperature programming to 200 ℃ for crystallization for 24 h. Wherein the molar ratio of each component is as follows: 1Al 2 O 3 :0.98P 2 O 5 :0.2SiO 2 :0.91A:2.7TEA:1.2DEA:30H 2 O。
When the temperature of the high-pressure reaction kettle is reduced to 90 ℃, removing the template agents triethylamine and diethylamine by flash evaporation, and reducing the temperature to room temperature to obtain slurry a. And (3) taking a small amount of slurry for centrifugal separation, washing, filtering and drying to calculate the yield of the molecular sieve to be 89%.
439g of the flash-evaporated slurry was poured into a colloid mill, and 324g of alumina sol (20 wt% in terms of mass fraction) was added, followed by 226g of kaolin and 150g of deionized water. Grinding with colloid mill for 3-5min, stirring at room temperature for 12 hr, and spray-forming. The inlet temperature of the spray dryer was 350 ℃ and the outlet temperature was 105 ℃. And (3) placing the spray-formed catalyst into a muffle furnace, and roasting at the constant temperature of 650 ℃ for 5 hours to obtain the MTO catalyst A6.
The bulk ratio of the catalyst was 0.79 g/ml. The abrasion index of the abrasion tester is 0.22 percent h -1 。
Comparative example 1
An MTO catalyst was prepared by the same method as in example 1, except that: and (3) removing the template agents triethylamine and diethylamine by flash evaporation, and then washing, filtering and drying to obtain the SAPO-34 molecular sieve raw powder.
160g of kaolin was dispersed in 102g of deionized water, 323g of 20 wt% alumina sol was added, followed by 228g of molecular sieve filter cake. Grinding with colloid mill for 3-5min, stirring at room temperature for 12 hr, and spray-forming. The inlet temperature of the spray dryer was 350 ℃ and the outlet temperature was 105 ℃. And (3) placing the spray-formed catalyst into a muffle furnace, and roasting at the constant temperature of 650 ℃ for 5 hours to obtain the MTO catalyst D1.
The bulk ratio of the catalyst was 0.80 g/ml. The abrasion index of the abrasion tester is 0.20 percent h -1 . The catalyst evaluation results are shown in table 1.
Comparative example 2
An MTO catalyst was prepared by the same method as in example 1, except that: no additive A is added, and after crystallization is finished, the template agents triethylamine and diethylamine are removed by flash evaporation. After cooling to room temperature 439g of the slurry were poured into a colloid mill, 324g of 20 wt% aluminium sol was added and 226g of kaolin was added. Grinding with colloid mill for 3-5min, stirring at room temperature for 12 hr, and spray-forming. The inlet temperature of the spray dryer was 350 ℃ and the outlet temperature was 105 ℃. The spray-formed catalyst is put into a muffle furnace and roasted at the constant temperature of 650 DEG CMTO catalyst D2 was obtained in 5 h. Tests show that the content of unreacted aluminum element and phosphorus element in the crystallized slurry is 4.9 wt% and 6.6 wt%; the viscosity of the slurry before spray molding was 8000 cp. The bulk ratio of the catalyst was 0.65 g/ml. The abrasion index of the abrasion tester is 1.24 percent h -1 。
TABLE 1 stationary fluidized bed evaluation results
Figure BDA0002140336160000151
As can be seen from Table 1, the catalyst MTO provided by the present invention has a conversion rate to methanol and a conversion rate to C in the reaction of producing olefins from methanol, as compared with the catalyst MTO provided by comparative example 1 2 、C 3 Yield of (1) and C 2 And C 3 The overall yields are all significantly higher than the catalyst MTO provided in comparative example 1. The MTO catalyst provided by the invention has more excellent catalytic effect. Meanwhile, the catalyst MTO provided by the embodiment 1 of the invention has higher yield of the ethylene and the propylene, and the service life of the catalyst is longer.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (15)

1. A preparation method of an MTO catalyst comprises the following steps:
(1) aluminum source, phosphorus source, silicon source, organic template agent R and water are mixed according to the molar ratio of Al 2 O 3 :(0.7-1.5)P 2 O 5 :(0.1-1.5)SiO 2 :(1-4)R:(20-100)H 2 O, mixing to obtain initial crystallization sol, adding an additive A into the initial crystallization sol, and ageing the obtained mixed solution I and then carrying out hydrothermal crystallization; wherein the additive A and the aluminum source are Al 2 O 3 The calculated molar ratio is (0.1-1.5):1, and the additive A is at least one of hydrochloric acid, sulfuric acid, nitric acid, citric acid, acetic acid, ethylenediamine tetraacetic acid, tartaric acid, oxalic acid, malic acid, benzoic acid, salicylic acid, propionic acid, butyric acid, ethyl acetate, ethyl benzoate, silica sol and phosphoric acid;
(2) cooling the product obtained in the step (1), and then carrying out flash evaporation to remove the organic template agent R to obtain slurry a;
(3) mixing the slurry a with a binder and a carrier, and adding the mixture into a colloid mill for grinding and stirring to obtain slurry b;
(4) spray drying and roasting the slurry b to obtain an MTO catalyst;
wherein in the step (1), the aging temperature is 10-50 ℃, and the aging time is 2-8 h; the hydrothermal crystallization temperature is 150 ℃ and 250 ℃, and the hydrothermal crystallization time is 12-72 h; in the step (3), the weight ratio of the slurry a to the binder and the carrier is (7-10) to 1 (2-3.5).
2. The preparation method of claim 1, wherein the aluminum source, the phosphorus source, the silicon source, the organic template R and the water are in a molar ratio of Al 2 O 3 :(0.85-1.2)P 2 O 5 :(0.15-0.35)SiO 2 :(2.5-3.5)R:(30-60)H 2 And mixing the O.
3. The method of claim 1, wherein the additive A and the aluminum source are Al 2 O 3 The calculated molar ratio is (0.4-1): 1.
4. The production method according to any one of claims 1 to 3, wherein the silica sol is used in an amount of 0 to 5wt% based on the silicon source, and the phosphoric acid is used in an amount of 0 to 10wt% based on the phosphorus source.
5. The production process according to any one of claims 1 to 3, wherein in the step (1), the aging temperature is 20 to 40 ℃ and the aging time is 3 to 5 hours.
6. The preparation method according to any one of claims 1 to 3, wherein in the step (1), the hydrothermal crystallization temperature is 180 ℃ and 210 ℃, and the hydrothermal crystallization time is 20-48 h.
7. The production method according to any one of claims 1 to 3, wherein in the step (2), the flash evaporation conditions include: the flash temperature is 90-108 ℃.
8. The production method according to claim 7, wherein in the step (2), the conditions of the flash evaporation include: the flash evaporation temperature is 95-100 ℃.
9. The preparation method according to any one of claims 1 to 3, wherein in the step (3), the weight ratio of the slurry a to the binder and the carrier is (7.5-8.5):1: 3.
10. The production method according to any one of claims 1 to 3, wherein in the step (3), the milling time is 1 to 10min and the stirring time is 5 to 20 hours.
11. The preparation method according to claim 10, wherein in the step (3), the grinding time is 3-5min, and the stirring time is 10-17 h.
12. The preparation method according to any one of claims 1-3, wherein in step (4), the inlet temperature is 250-500 ℃ and the outlet temperature is 90-130 ℃ during the spray drying process.
13. The preparation method according to claim 12, wherein, in the step (4), the inlet temperature is 300-400 ℃, and the outlet temperature is 100-110 ℃.
14. An MTO catalyst prepared by the preparation method of any one of claims 1 to 13.
15. Use of the MTO catalyst of claim 14 in the preparation of olefins from methanol.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103418431A (en) * 2013-08-28 2013-12-04 神华集团有限责任公司 SAPO-34/SAPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound and preparation method thereof
CN103787370A (en) * 2013-12-31 2014-05-14 中国天辰工程有限公司 Recycling method for template agent in preparation process of molecular sieve
CN105439171A (en) * 2015-12-22 2016-03-30 天津众智科技有限公司 Method for preparing SAPO-34 molecular sieve by using carbonate as synthesis prompting agent, and applications thereof
CN106082253A (en) * 2016-06-06 2016-11-09 天津众智科技有限公司 The preparation method of a kind of SAPO 34 microsphere zeolite catalyst and the application of catalyst
CN107626345A (en) * 2016-07-18 2018-01-26 任丘市华北石油科林环保有限公司 A kind of high ethylene selectivity preparing low-carbon olefin by using methanol catalyst
CN108654681A (en) * 2017-03-31 2018-10-16 神华集团有限责任公司 A kind of catalyst of methanol-to-olefins and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7026267B2 (en) * 2002-12-20 2006-04-11 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its production and use in conversion processes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103418431A (en) * 2013-08-28 2013-12-04 神华集团有限责任公司 SAPO-34/SAPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound and preparation method thereof
CN103787370A (en) * 2013-12-31 2014-05-14 中国天辰工程有限公司 Recycling method for template agent in preparation process of molecular sieve
CN105439171A (en) * 2015-12-22 2016-03-30 天津众智科技有限公司 Method for preparing SAPO-34 molecular sieve by using carbonate as synthesis prompting agent, and applications thereof
CN106082253A (en) * 2016-06-06 2016-11-09 天津众智科技有限公司 The preparation method of a kind of SAPO 34 microsphere zeolite catalyst and the application of catalyst
CN107626345A (en) * 2016-07-18 2018-01-26 任丘市华北石油科林环保有限公司 A kind of high ethylene selectivity preparing low-carbon olefin by using methanol catalyst
CN108654681A (en) * 2017-03-31 2018-10-16 神华集团有限责任公司 A kind of catalyst of methanol-to-olefins and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Attrition resistance and catalytic performance of spray-dried SAPO-34 catalyst for MTO process: Effect of catalyst phase and acidic solution;Kim, M;《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》;20110513;第17卷(第3期);第621–627页 *
甲醇制烯烃催化剂开发关键问题探讨;邢爱华等;《工业催化》;20121215(第12期);第1-7页 *

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