WO2008095359A1 - Procédé de recyclage d'un catalyseur à microbille sur lit fluidisé - Google Patents

Procédé de recyclage d'un catalyseur à microbille sur lit fluidisé Download PDF

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Publication number
WO2008095359A1
WO2008095359A1 PCT/CN2007/002319 CN2007002319W WO2008095359A1 WO 2008095359 A1 WO2008095359 A1 WO 2008095359A1 CN 2007002319 W CN2007002319 W CN 2007002319W WO 2008095359 A1 WO2008095359 A1 WO 2008095359A1
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Prior art keywords
catalyst
microsphere
spray drying
weight
molecular sieve
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PCT/CN2007/002319
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English (en)
Chinese (zh)
Inventor
Peng Tian
Zhongmin Liu
Lei Xu
Lixin Yang
Cuiyu Yuan
Zhihui Lv
Shuanghe Meng
Yue Qi
Changqing He
Yingxu Wei
Xiangao Wang
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Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
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Publication of WO2008095359A1 publication Critical patent/WO2008095359A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J29/83—Aluminophosphates [APO compounds]
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for recovering a microsphere catalyst for a fluidized bed and a catalytic application of the recovered catalyst for the conversion of an oxide-containing olefin to an olefin.
  • Ethylene and propylene are important basic chemical raw materials. At present, China is mainly prepared by light oil cracking method. With the shortage of petroleum resources and rising prices, the technology for producing low-carbon olefins from non-oil routes is becoming more and more urgent. The research and development of ethylene and propylene has become a hot spot for domestic and foreign research institutions and international companies. The single-series, large-scale industrialization technology for natural gas or coal to produce methanol is very mature, so the research on the production of olefins (MTO) from methanol has become a key technology for the production of low-carbon olefins from non-oil routes.
  • MTO olefins
  • the small pore phosphorus silica gel molecular sieve has better MTO catalytic performance, but has the characteristics of rapid carbon deposition in the fixed bed reaction process, thereby causing rapid deactivation and selective reduction of the catalyst, and cannot meet the requirements of industrial continuous production.
  • Fluidized bed is a common form of reactor used in the chemical industry.
  • the MTO process of a fluidized bed reactor with continuous reaction-regeneration can avoid the above problems.
  • Catalysts suitable for use in fluidized bed reactors should be microspheres with a suitable strength and particle size distribution while maintaining high catalytic performance.
  • a fluidized bed microsphere catalyst is prepared by a spray drying method.
  • the microsphere catalyst is composed of an active component such as a molecular sieve and a binder, and the binder functions to disperse the active component and increase the strength of the catalyst.
  • the presence of inactive components in the catalyst can also act to dilute the molecular sieve to reduce the heat of reaction.
  • USP 5,126,298 reports the preparation of a high-strength cracking catalyst which is prepared by spray drying two different clays, zeolite molecular sieves and phosphorus-containing compounds into a slurry having a pH of ⁇ 3; USP 5248647 reports the molecular hoof of SAPO-34.
  • a method for spray drying a slurry made of kaolin and silica sol USP6153552 discloses a method for preparing a microsphere catalyst containing a SAPO molecular sieve, which is obtained by mixing SAPO molecular sieve, inorganic oxide sol, and phosphorus-containing compound by spray drying.
  • USP6787501 reports spray-drying SAPO-34 molecular sieves, binders and matrix materials to catalysts for methanol conversion;
  • CN01132533A reports the preparation of wear-resistant index catalysts for methanol conversion by reducing the quality of molecular sieves in the catalyst The content serves to increase the catalyst wear index.
  • the catalyst When the catalyst is produced by spray drying, two different particle size distributions of coarse powder and fine powder are obtained at the same time.
  • the particle size distribution of the catalyst used in the fluidized bed is certain, and the coarse powder and the fine powder are generally mixed and formulated in proportion. If the catalyst is prepared at a different ratio than the ratio of coarse to fine in the production process, a portion of the catalyst will remain. Recycling the remaining catalyst not only causes a loss in production, but also increases production costs.
  • the catalyst wears out in the circulating fluidized bed unit, and most of the powdered catalyst can be recovered by cyclone separation equipment. If these powdered catalysts still maintain the original excellent reaction performance, their recycling will also reduce the production cost of the catalyst, and have certain economic value.
  • Patent CN1516177A reports a method for reusing a molecular sieve-containing catalyst by mixing a molecular sieve microsphere catalyst with a large amount of deionized water, grinding to reduce the particle size of the particles in the slurry, and then re-spray drying to prepare a lower wear index. And a catalyst suitable for particle size distribution. It should be noted, however, that the catalyst used for recovery must be a fresh, uncalcined sample, i.e., the molecular sieve contains an organic templating agent.
  • the method for preparing a fluidized bed microsphere catalyst by recycling a post-reaction catalyst (carbon-containing sample or calcined sample) has not been reported in the literature. Summary of the invention
  • any catalyst that cannot be directly used in a fluidized bed reactor that is, fresh uncalcined catalyst, freshly calcined catalyst, post-reaction carbon-containing catalyst, and reaction Thereafter, the carbon-depleted catalyst is calcined, and the fluidized bed microsphere catalyst prepared to have a lower wear index and a suitable wear index is recycled.
  • the fresh microsphere catalyst for the conversion of oxygenates to olefins referred to in this patent see our patent application (Application No. 200610089171.1).
  • One of the objects of the present invention is to provide a method for recovering a microsphere catalyst for a fluidized bed.
  • the catalyst to be recovered is mixed with each raw material for preparing a fresh microsphere catalyst in a certain ratio, and the slurry is gel-milled, spray-dried and calcined at a high temperature to obtain a microsphere catalyst having a lower wear index and a suitable particle size distribution.
  • the above recovery method of the present invention is characterized in that the microsphere catalyst referred to is prepared by using SAPO/MeAPSO molecular sieve as an active component, adding a binder, an auxiliary agent and a pore former.
  • the elemental composition (mass content) of the catalyst is 2 to 60% of silicon oxide, 8 to 50% of phosphorus oxide, 20 to 70% of alumina, 0 to 10% of alkaline earth metal oxide, 0 to 20% of transition metal oxide, and satisfy The sum of the total mass contents is 100%.
  • the indicated SAPO/MeAPSO molecular sieve is in the form of its original powder, that is, the molecular sieve contains the organic template introduced during the synthesis, and the pore diameter is less than 0.5 nm;
  • the metal contained in the MeAPSO molecular sieve is titanium, vanadium, chromium, manganese, iron, a mixture of one or any of cobalt, nickel, copper, zinc, zirconium, etc.
  • the binder is kaolin;
  • the auxiliary is one of oxides, inorganic salts or organic salts of calcium, barium, strontium and zirconium
  • the mixture may be a mixture of one or more of phosphoric acid, diammonium hydrogen phosphate, ammonium hydrogen phosphate;
  • the pore forming agent is an organic compound, preferably a natural product such as phthalocyanine powder.
  • the invention is characterized in that the catalyst to be recovered may be a fresh microsphere catalyst (calcined or uncalcined sample), a reaction catalyst (carbon-containing or calcined carbon-removed sample), or a cyclone separation through a fluidized bed.
  • the device recovers the obtained catalyst powder (carbon-containing or calcined carbon-removed sample).
  • the content of the sub-sieve in the catalyst obtained by cyclone separation is similar to that of the fresh catalyst.
  • the preparation process of the microsphere catalyst recovery method of the present invention comprising a molecular sieve as an active component is as follows:
  • the slurry is passed through a colloid mill, so that the solid particles contained therein have a diameter of less than 20 ⁇ m, 90% of the particles have a diameter smaller than ⁇ , and 70% of the particles have a diameter of less than 5 ⁇ m ;
  • the microsphere sample is obtained by calcining the microsphere sample in a 500-80 atmosphere in an oxygen atmosphere.
  • the recovered catalyst has an oxide dry basis content in the total furnish of not more than 80% by weight, preferably 10% to 80% by weight;
  • the recovered catalyst and molecular sieve raw powder is SAPO/MeAPSO molecular sieve and is in the total batching
  • the oxide dry basis content is 20-50% by weight ;
  • the binder has an oxide dry basis content of 10 to 75% by weight in the total furnish ;
  • the auxiliary agent has an oxide dry basis content of 0-30% by weight in the total furnish.
  • the pore former (Tianjing powder) is contained in the total furnish in an amount of 0 to 2% by weight.
  • the invention is characterized in that the microsphere catalyst has an abrasion index of less than 2.
  • Another object of the present invention is to directly apply the above prepared microsphere catalyst to a circulating fluidized bed in which an oxygenate is converted to an olefin.
  • the MC sample was industrially amplified by the method of Example 1, and used in a circulating fluidized bed for industrial testing (catalyst loading 4 tons, methanol treatment amount 50 tons/day), and methanol conversion to olefin reaction. After the device was operated smoothly for 30 days, the collected catalyst powder was taken out from the cyclone sampling port, which was recorded as XM. A small amount of catalyst sample was taken from the sampling port of the reactor and recorded as FM.
  • the M sample was respectively used for MC, XM, XMC, FM,
  • the FMC sample was replaced by catalyst preparation.
  • the obtained spray-dried product was calcined in air at 650 ° C for 3 hours to obtain a microsphere catalyst, which was designated as MC-1S, XM-1S, XMC-1S FM-1S, and FMC-1S, respectively.
  • the moisture content is 15wt%, the content of SiO 2 in the solid after burning 53%% and 2.11kg of SAPO-34 molecular sieve raw powder (according to the method of patent CN1131845, sequentially added to 9.18kg of deionized water, stirred.
  • the grinding is performed by grinding, so that the diameter of the solid particles in the finally obtained slurry is 70% less than 5 ⁇ m (the particle size distribution test is carried out by using the ⁇ -9300 laser particle size distribution meter produced by Dandong Baite Instrument Co., Ltd.).
  • the slurry is spray dried (pressure type) Nebulizer device)
  • the obtained spray-dried product was calcined in air at 650 ° C for 3 h to obtain a microsphere catalyst, which was designated as M-2S.
  • the SAPO-34 molecular sieve was replaced with a ZnAPSO-34 molecular sieve (synthesis method ZrAPSO-34 in the same manner as in Example 4) to prepare a microsphere catalyst.
  • the obtained spray-dried product was designated as N, and calcined in air at 650 ° C for 3 hours to obtain a microsphere catalyst, which was designated as NC.
  • the M sample was replaced with MC, NC, XMC, FM, FMC samples, respectively, to prepare the catalyst.
  • the obtained spray-dried product was calcined in air at 650 ° C for 3 hours to obtain microsphere catalysts, which were respectively recorded as MC-2S, NC-1S, XMC-2S, FM-2S, and FMC-2S.
  • Abrasion Index Determination Method Approximately 7 g of the catalyst sample was placed in a gooseneck having an inner diameter of about 2.5 cm, and humid air was passed through the tube at a flow rate of 20 min to provide a fluidized environment. The fine catalyst powder blown out from the catalyst was collected in a special filter bag and tested for 4 hours. The wear index is calculated as the mass percentage of the average amount of catalyst lost per hour of initial charge.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

Procédé de recyclage d'un catalyseur à microbille sur lit fluidisé dans lequel le mélange des catalyseurs à recycler avec les matières premières pour la préparation de catalyseurs à microbilles frais dans une certaine proportion, le broyage avec colle de la pâte, puis le séchage par vaporisation et la calcination sous haute température, permettent d'obtenir un catalyseur à microbilles ayant un faible indice d'abrasion et une répartition de taille de particules adaptée. Le procédé comprend les phases suivantes : 1) mélange des catalyseurs à recycler avec un tamis moléculaire vierge, un liant, un promoteur, un agent porogène, et de l'eau désionisée, sur la base du poids d'oxydes secs, réduction en pâte, le pourcentage en poids des catalyseurs à recycle ne dépassant pas 80% du total des oxydes secs des mélanges; 2) broyage avec colle de la pâte par un broyeur à colle pour obtenir le diamètre des particules solides inférieur à 20μm, le diamètre de particule de 90% des particules solides étant inférieur à 10μm, le diamètre de particule de 70% des particules solides étant inférieur à 5μm; 3) séchage par vaporisation pour préparer un échantillon de microbilles; 4) calcination de l'échantillon de microbilles à 500-800° C dans une atmosphère contenant de l'oxygène pour obtenir un catalyseur à microbille sur lit fluidisé. Le catalyseur préparé est adapté pour une utilisation dans la conversion d'oxygénates en oléfines.
PCT/CN2007/002319 2007-02-07 2007-08-01 Procédé de recyclage d'un catalyseur à microbille sur lit fluidisé WO2008095359A1 (fr)

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CN200710063693.9 2007-02-07
CN2007100636939A CN101157051B (zh) 2007-02-07 2007-02-07 流化床用微球催化剂的回收方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110038631A (zh) * 2019-05-22 2019-07-23 陕西煤化工技术工程中心有限公司 一种甲醇制烯烃催化剂细粉的回用方法
CN113797946A (zh) * 2020-06-15 2021-12-17 中国石油化工股份有限公司 芳烃氨氧化催化剂及其制备方法
CN114452662A (zh) * 2021-10-26 2022-05-10 中国石油化工股份有限公司 一种喷雾干燥废料回收利用装置及应用方法
CN116371463A (zh) * 2023-03-13 2023-07-04 中触媒新材料股份有限公司 一种低磨损率sapo-34分子筛催化剂及其制备方法和应用

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102085468B (zh) * 2009-12-04 2013-02-20 中国科学院大连化学物理研究所 一种流化床用预流化剂
CN102179251B (zh) * 2011-03-17 2013-01-30 清华大学 流化床合成甲醇用催化剂及其制备方法
CN103611581B (zh) * 2013-11-22 2015-09-23 中国天辰工程有限公司 一种回收催化剂细粉用于重新造粒的方法
CN106540744A (zh) * 2015-09-22 2017-03-29 正大能源材料(大连)有限公司 一种硅铝磷分子筛催化剂的回用方法
CN112774726B (zh) * 2020-12-29 2022-09-13 上海华谊新材料有限公司 球形钛硅分子筛催化剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1419477A (zh) * 2000-04-26 2003-05-21 埃克森美孚化学专利公司 用无水液体或蒸气使sapo和/或alpo分子筛复原
CN1455701A (zh) * 2000-07-17 2003-11-12 埃克森美孚化学专利公司 分子筛催化剂的合成

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5248647A (en) * 1991-02-28 1993-09-28 Uop Sapo catalysts and use thereof in methanol conversion processes
CN1060100C (zh) * 1997-02-26 2001-01-03 中国石油化工总公司 含分子筛裂化催化剂的再活化方法
AU9805598A (en) * 1997-10-29 1999-05-17 Exxon Chemical Patents Inc. Method for making catalysts containing silicoaluminophosphate molecular sieve and catalyst thus prepared
US6710008B2 (en) * 2002-01-17 2004-03-23 Exxonmobil Chemical Patents Inc. Method of making molecular sieve catalyst
DE60218699D1 (de) * 2001-07-02 2007-04-19 Exxonmobil Chem Patents Inc Inhibierung der katalysatorverkokung bei der herstellung eines olefins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1419477A (zh) * 2000-04-26 2003-05-21 埃克森美孚化学专利公司 用无水液体或蒸气使sapo和/或alpo分子筛复原
CN1455701A (zh) * 2000-07-17 2003-11-12 埃克森美孚化学专利公司 分子筛催化剂的合成

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110038631A (zh) * 2019-05-22 2019-07-23 陕西煤化工技术工程中心有限公司 一种甲醇制烯烃催化剂细粉的回用方法
CN113797946A (zh) * 2020-06-15 2021-12-17 中国石油化工股份有限公司 芳烃氨氧化催化剂及其制备方法
CN114452662A (zh) * 2021-10-26 2022-05-10 中国石油化工股份有限公司 一种喷雾干燥废料回收利用装置及应用方法
CN114452662B (zh) * 2021-10-26 2023-09-19 中国石油化工股份有限公司 一种喷雾干燥废料回收利用装置及应用方法
CN116371463A (zh) * 2023-03-13 2023-07-04 中触媒新材料股份有限公司 一种低磨损率sapo-34分子筛催化剂及其制备方法和应用

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