WO2012174678A1 - Matériau catalytique argileux stratifié et son procédé d'intercalage - Google Patents

Matériau catalytique argileux stratifié et son procédé d'intercalage Download PDF

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Publication number
WO2012174678A1
WO2012174678A1 PCT/CN2011/001045 CN2011001045W WO2012174678A1 WO 2012174678 A1 WO2012174678 A1 WO 2012174678A1 CN 2011001045 W CN2011001045 W CN 2011001045W WO 2012174678 A1 WO2012174678 A1 WO 2012174678A1
Authority
WO
WIPO (PCT)
Prior art keywords
clay
hours
layered
catalytic material
montmorillonite
Prior art date
Application number
PCT/CN2011/001045
Other languages
English (en)
Chinese (zh)
Inventor
李岩
黄淮青
扈治东
苏党生
Original Assignee
山东大展纳米材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 山东大展纳米材料有限公司 filed Critical 山东大展纳米材料有限公司
Priority to PCT/CN2011/001045 priority Critical patent/WO2012174678A1/fr
Publication of WO2012174678A1 publication Critical patent/WO2012174678A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used

Definitions

  • the invention belongs to the technical field of preparation of clay catalytic materials, and particularly relates to a layered column clay catalytic material and an intercalation modification treatment method thereof.
  • Clay and other soil materials generally contain active metal components such as iron, cobalt, and nickel.
  • the active metal component can be catalyzed to catalyze multiple chemical reactions, such as: hydrazine cracking, olefin polymerization, ammonia decomposition, methane water vapor. Reforming, heavy oil conversion, hydrogen production from ethanol.
  • active metal components generally exist in the form of oxides, hydroxides or salts, which must be chemically intercalated to obtain a pore structure and activity.
  • the method for preparing a layered column clay catalytic material in the patent ZL00130261.2 is as follows: 1. Original soil dispersion: The layered clay, the dispersing agent and the water are mixed and beaten evenly. 2. Mixing and molding: Adding the layered clay slurry to other components of the catalyst including molecular sieve, inorganic oxide binder and support, fully mixing, and then drying or forming by 280-320 ° C or spray drying . 3. Cross-linking reaction: The formed material is added to a crosslinking agent to carry out a crosslinking reaction. 4.
  • the preparation method of the layered clay catalytic material involved in the above patent is complicated in preparation steps and high in production cost.
  • the object of the present invention is to provide an intercalation modification treatment method for a layered column clay catalytic material in view of the above-mentioned defects.
  • a layered column clay catalytic material comprising one or more layers of clay structures obtained by surface treatment of one of an acid solution, an alkali solution or an oxidizing solution.
  • the layered clay catalytic material contains 0.5 to 30% by weight of an active metal component, wherein the active metal component comprises iron, cobalt, nickel or one or more of them.
  • the layered column clay is first calcined under a chemical atmosphere; the calcined clay, the treating agent and water are mixed together for 0.1 to 10 hours to obtain a solid weight.
  • the wet sample with a percentage of 50 to 95% is repeatedly washed to a neutral and then dried to obtain a layered column clay catalytic material after intercalation treatment.
  • the treating agent is an acidic, alkaline or oxidizing substance to treat the intercalated clay material.
  • the chemical atmosphere includes one or more of air, oxygen, hydrogen, nitrogen, argon, helium, preferably one or more of air, oxygen, and nitrogen.
  • the treatment agent is selected from the group consisting of hydrochloric acid, nitric acid, acetic acid, sulfuric acid, oxalic acid, phosphoric acid, sodium hydroxide, potassium hydroxide, ammonia water, potassium permanganate, hydrogen peroxide, methanol, formic acid, ethanol, calcium hydroxide quaternary ammonium salt, ethylene One or more of an amine, ethyl carbonate, and acetic acid.
  • the layered clay material contains 0.5 to 30% by weight of an iron, cobalt or nickel element in the form of a simple substance, an oxide, a hydroxide, a sulfate, a nitrate and a phosphate.
  • the layered pillar clay is selected from one or more of natural or synthetic mineral structural clay;
  • the layered clay material may be montmorillonite, kaolin, bentonite, activated clay, wollastonite clay, Maifanite, vermiculite, beidellite, mica-meteorite, mica-montmorillonite, kaolin-montmorillonite; preferably montmorillonite, kaolin, bentonite, kaolin-montmorillonite in mineral structure clay;
  • the pillar pillar clay is more preferably an iron, cobalt, nickel active metal component in an amount of 0.5 to 15% by weight of montmorillonite, kaolin, bentonite, kaolin-montmorillonite.
  • the specific steps of the present invention are: (1) calcining the layered clay in a chemical atmosphere at 400 to 1100 ° C for 0.1 to 10 hours;
  • the wet sample obtained in the step (2) is repeatedly washed to a neutral post-drying treatment for 0.1 to 10 hours to obtain a layered column clay catalytic material after the intercalation treatment.
  • the clay material is treated by soaking, stirring, or the like using a treating agent having an acidic, basic or oxidizing chemical.
  • the calcination temperature is preferably 500 to 1000 ° C; and the calcination time is preferably 0.1 to 4 hours.
  • the clay, the treating agent and water are mixed together for a period of time, preferably 0.1 to 4 hours.
  • the beneficial effects of the invention are as follows:
  • the invention provides a method for preparing a layered column clay structure catalytic material having a certain pore structure and good active metal exposure, wherein the mass percentage of the active metal component in the prepared catalyst is 0.5 ⁇ 30%, wherein the active metal component comprises iron, cobalt, nickel or one or more of them.
  • the clay catalytic material prepared by the invention has a wide preparation range, and the prepared clay catalytic material has high catalytic activity and stability, and the catalytic activity reaches 65%.
  • the preparation process is simple, no dispersant, cross-linking agent is used, and the preparation procedure of the catalyst is adjusted, the reaction step is reduced, the production time is shortened, the manufacturing cost is low, and the production cost is greatly reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un matériau catalytique argileux stratifié qui comprend une structure argileuse comprenant une ou plusieurs couches, qui est préparé par intercalage par traitement de surface dans un liquide acide, un liquide alcalin ou une solution oxydante. Le matériau catalytique argileux peut être utilisé dans des réactions, p. ex. le craquage catalytique d'alcanes, etc., et présente une activité catalytique élevée et une stabilité à long terme.
PCT/CN2011/001045 2011-06-23 2011-06-23 Matériau catalytique argileux stratifié et son procédé d'intercalage WO2012174678A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2011/001045 WO2012174678A1 (fr) 2011-06-23 2011-06-23 Matériau catalytique argileux stratifié et son procédé d'intercalage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2011/001045 WO2012174678A1 (fr) 2011-06-23 2011-06-23 Matériau catalytique argileux stratifié et son procédé d'intercalage

Publications (1)

Publication Number Publication Date
WO2012174678A1 true WO2012174678A1 (fr) 2012-12-27

Family

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Country Status (1)

Country Link
WO (1) WO2012174678A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103230797A (zh) * 2013-05-16 2013-08-07 陕西师范大学 碱活化蒙脱土载钴催化剂及其制备方法和应用
CN112374506A (zh) * 2020-11-19 2021-02-19 江苏博联新材料科技有限公司 一种复合膨润土添加剂中间料的改性工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4843052A (en) * 1982-05-21 1989-06-27 W. R. Grace & Co.-Conn. Acid-reacted metakaolin catalyst and catalyst support compositions
CN1314826A (zh) * 1998-06-30 2001-09-26 伊斯曼化学公司 用于生产二元醇—酯的碱性粘土催化剂
US6858665B2 (en) * 2001-07-02 2005-02-22 The Goodyear Tire & Rubber Company Preparation of elastomer with exfoliated clay and article with composition thereof
CN101433865A (zh) * 2007-11-15 2009-05-20 中国石油化工股份有限公司 一种渣油加氢催化剂载体及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4843052A (en) * 1982-05-21 1989-06-27 W. R. Grace & Co.-Conn. Acid-reacted metakaolin catalyst and catalyst support compositions
CN1314826A (zh) * 1998-06-30 2001-09-26 伊斯曼化学公司 用于生产二元醇—酯的碱性粘土催化剂
US6858665B2 (en) * 2001-07-02 2005-02-22 The Goodyear Tire & Rubber Company Preparation of elastomer with exfoliated clay and article with composition thereof
CN101433865A (zh) * 2007-11-15 2009-05-20 中国石油化工股份有限公司 一种渣油加氢催化剂载体及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SUN, YING: "Synthesis, Characterization and Properties of Ti02/Vermiculite Composites.", CHINESE MASTER'S THESES FULL-TEXT DATABASE, ENGINEERING SCIENCE AND TECHNOLOGY I., vol. 2, 15 February 2011 (2011-02-15), pages B020 - 8 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103230797A (zh) * 2013-05-16 2013-08-07 陕西师范大学 碱活化蒙脱土载钴催化剂及其制备方法和应用
CN112374506A (zh) * 2020-11-19 2021-02-19 江苏博联新材料科技有限公司 一种复合膨润土添加剂中间料的改性工艺

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