WO2012174678A1

WO2012174678A1 - Layered clay catalytic material and intercalation method thereof

Info

Publication number: WO2012174678A1
Application number: PCT/CN2011/001045
Authority: WO
Inventors: 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: 2011-06-23
Filing date: 2011-06-23
Publication date: 2012-12-27

Abstract

A layered clay catalytic material comprises a clay structure having one or more layers, which is prepared by intercalation upon surface-treating in acid liquid, alkaline liquid, or oxidizing solution. The clay catalytic material can be used in reactions, e.g. catalytic cracking of alkane, etc., and has high catalytic activity and long-time stability.

Description

Layered column clay catalytic material and intercalation modification treatment method thereof

Technical field:

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.

Background technique:

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. However, natural clay materials generally do not have a suitable pore structure, and 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. A multilayer clay structure with good metal exposure.

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. Aging: The pH of the slurry after the crosslinking reaction was adjusted to 4-8 with ammonia water, and aged at 55-75 ° C for 1-5 hours, then filtered, dried, and washed. 5. Calcination: The obtained solid particles were calcined at 550-750 Torr for 1-3 hours.

The preparation method of the layered clay catalytic material involved in the above patent is complicated in preparation steps and high in production cost.

Summary of the invention:

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.

In the intercalation modification treatment method of the layered column clay catalytic material of the present invention, 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;

(2) mixing the calcined clay, the treating agent and water for 0.1 to 10 hours to obtain a wet sample having a solid weight percentage of 50 to 95%;

(3) 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%. In addition, 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.

Effect comparison 1:

Take 1 kg of natural montmorillonite sample and place it in a tube furnace. After heating to 900 ° C in nitrogen, the temperature is kept for 30 minutes. Introduce the reaction gas (10% formazan, 90% nitrogen, total flow rate 3 l/min). The conversion of formazan was 15% after 10 hours, and the conversion of formazan to 100% was reduced to 3%.

1 kg of the montmorillonite sample prepared in Example 3 was placed in a tube furnace, and the temperature was raised to 900 ° C in nitrogen for 30 minutes, and the reaction gas was introduced (10% formazan, 90% nitrogen, total flow rate of 3 liters). /min), the conversion of formazan was 50% after 10 hours of reaction, and the conversion of formazan was slowly reduced to 35% at 100 hours. Effect comparison 2:

Take 1 kg of natural kaolin sample in a tube furnace, heat it to 900 ° C in nitrogen for 30 minutes, introduce the reaction gas (15% acetylene, 85% nitrogen, total flow rate 2 l / min), within 10 hours of reaction The conversion of acetylene was 35%, and the conversion of acetylene was reduced to 0% in 50 hours.

1 kg of the kaolin sample prepared in Example 5 was placed in a tube furnace, and the temperature was raised to 900 ^e C in nitrogen for 30 minutes, and a reaction gas (15% acetylene, 85% nitrogen, total flow rate of 3 liters/min) was introduced. The conversion of acetylene was 58% after 10 hours of reaction, and the conversion of acetylene was decreased to 15% after 50 hours of reaction.

detailed description:

The technical solution of the present invention will be described in detail below with reference to specific embodiments.

Example 1

5 kg of natural montmorillonite was calcined in air at 1000 ° C for 4 hours to obtain 4.8 kg of calcined montmorillonite, which was mixed with 19.5 kg of deionized water, 2 kg of concentrated hydrochloric acid, 4 kg of methanol, and mechanically stirred 0.5. After the hour, the solution was removed by filtration, and the obtained wet sample was further washed with 20 kg of deionized water to neutrality, and the obtained wet sample was dried at 100 ° C for 2 hours to obtain 4.1 kg of intercalated montmorillonite product. The specific surface area was measured to be 12 m ² /g by nitrogen physical adsorption and BET calculation.

Example 2

5 kg of natural montmorillonite was calcined in argon at 1000 ° C for 4 hours to obtain 4.8 kg of calcined montmorillonite, which was mixed with 19.5 kg of deionized water, 2 kg of acetic acid, 4 kg of ethanol, and mechanically stirred 0.5. After the hour, the solution was removed by filtration, and the obtained wet sample was further washed with 20 kg of deionized water to neutrality, and the obtained wet sample was dried at 100 ° C for 2 hours to obtain 4.0 kg of intercalated montmorillonite product. The specific surface area measured by the nitrogen physical adsorption and BET calculation method was 17 m ² /g.

Example 3

5 kg of natural montmorillonite was calcined in oxygen at 1000 ° C for 4 hours to obtain 4.8 kg of roasting The montmorillonite, mixed with 19.5 kg of deionized water, 2 kg of sodium hydroxide, 4 kg of methanol, mechanically stirred for 1 hour, filtered to remove the solution, and the resulting wet sample was further washed with 20 kg of deionized water to neutral The obtained wet sample was dried at 100 ° C for 2 hours to obtain 3.8 kg of intercalated montmorillonite product, and the specific surface area was 24 m ² /g by nitrogen physical adsorption and BET calculation method.

Example 4

5 kg of natural kaolin was calcined in nitrogen at 1000 ^Q C for 4 hours to obtain 4.7 kg of calcined kaolin, which was mixed with 19.5 kg of deionized water, 3 kg of hydrochloric acid, 6 kg of ethanol, mechanically stirred for 2.0 hours, and filtered to remove the solution. The obtained wet sample was further washed with 20 kg of deionized water to neutrality, and the obtained wet sample was dried at 100 ° C for 2 hours to obtain 3.9 kg of intercalated kaolin product, using nitrogen physical adsorption and BET calculation method. The specific surface area was measured to be 30 m ² /g.

Example 5

5 kg of natural kaolin was calcined in 10% hydrogen/argon at 1000 ° C for 4 hours to obtain 4.6 kg of calcined kaolin, which was mixed with 19.5 kg of deionized water, 1 kg of sodium hydroxide, 5 kg of ethanol, mechanical After stirring for 1.0 hour, the solution was removed by filtration, and the obtained wet sample was further washed with 20 kg of deionized water to neutrality, and the obtained wet sample was dried at 100 ° C for 2 hours to obtain 3.7 kg of intercalated kaolin product. The specific surface area measured by nitrogen physical adsorption and BET calculation method was 27 m ² /g.

Example 6

5 kg of natural bentonite was calcined in 10% oxygen/argon at 700 ° C for 4 hours to obtain 4.8 kg of calcined bentonite, which was mixed with 19.5 kg of deionized water, 3 kg of ammonia water, mechanically stirred for 1.0 hour, and filtered to remove The solution was further washed with 20 kg of deionized water to neutrality, and the obtained wet sample was dried at 100 ° C for 2 hours to obtain 4.6 kg of intercalated bentonite product, which was subjected to nitrogen physical adsorption and BET calculation. The method measured a specific surface area of 7.3 m ² /g. 5 kg of natural bentonite was calcined in 10% oxygen/argon at 700 ° C for 4 hours to obtain 4.8 kg of calcined bentonite, which was mixed with 19.5 kg of deionized water, 1 kg of potassium perrhenate, and mechanically stirred for 1.0 hour. The solution was removed by filtration, and the obtained wet sample was further washed with 20 kg of deionized water to neutrality, and the obtained wet sample was dried at 100 ° C for 2 hours to obtain 4.7 kg of intercalated bentonite product, which was adsorbed by nitrogen. The specific surface area measured with the BET calculation method was 7.9 m ² /g.

Example 8

5 kg of natural bentonite was calcined in air at 900 ° C for 1 hour to obtain 4.8 kg of calcined bentonite, which was mixed with 19.5 kg of deionized water, 3 kg of ammonia water, mechanically stirred for 1.0 hour, and the solution was removed by filtration to obtain a wet The sample was further washed with 20 kg of deionized water to neutrality, and the obtained wet sample was dried at 100 ° C for 2 hours to obtain 4.6 kg of intercalated bentonite product, and the specific surface area was measured by nitrogen physical adsorption and BET calculation method. It is 7.3 m ² /g.

Example 9

5 kg of natural bentonite was calcined in air at 900 ° C for 1 hour to obtain 4.8 kg of calcined bentonite, which was mixed with 19.5 kg of deionized water, 3 kg of acetic acid, 6 kg of methanol, mechanically stirred for 0.5 hour, and filtered to remove the solution. The obtained wet sample was further washed with 20 kg of deionized water to neutrality, and the obtained wet sample was dried at 100 ° C for 2 hours to obtain 4.7 kg of intercalated bentonite product, using nitrogen physical adsorption and BET calculation method. The specific surface area was measured to be 6.4 m ² /g.

Example 10

5 kg of natural maifan stone was calcined in air at 600 ° C for 1 hour to obtain 4.9 kg of calcined maifan stone, which was mixed with 19.5 kg of deionized water, 1 kg of concentrated hydrochloric acid, 2 kg of methanol, and mechanically stirred 0.3. After the hour, the solution was removed by filtration, and the obtained wet sample was further washed with 20 kg of deionized water to neutrality, and the obtained wet sample was dried at 100 ° C for 2 hours to obtain 4.8 kg of intercalated maifan stone. The specific surface area measured by nitrogen physical adsorption and BET calculation method is 42 m ² /gc

Claims

Rights request

A layered-clay clay catalytic material comprising one or more layers of clay structures, characterized in that the catalytic material is surface-treated by one of an acid solution, an alkali solution or an oxidizing solution, and then modified by intercalation. .

The clay catalytic material according to claim 1, wherein the layered clay catalytic material contains 0.5 to 30% by weight of an active metal component, wherein the active metal component comprises iron and cobalt. , nickel or one or more of them.

3. A method for intercalating a layered clay catalyzed material by first calcining the layered clay under a chemical atmosphere; mixing the calcined clay, treating agent and water for 0.1 to 10 hours to obtain a solid The wet sample is 50~95% by weight; the obtained wet sample is repeatedly washed to a neutral post-baking treatment to obtain a layered column clay catalytic material after intercalation treatment.

4. The method according to claim 3, wherein the treating agent is an acidic, alkaline or oxidizing substance.

5. The method according to claim 3, wherein the chemical atmosphere comprises one or more of air, oxygen, hydrogen, nitrogen, argon, helium, preferably one of air, oxygen, and nitrogen. Or several.

6. The method according to claim 3, wherein the treating agent is selected from the group consisting of hydrochloric acid, nitric acid, acetic acid, sulfuric acid, oxalic acid, phosphoric acid, sodium hydroxide, potassium hydroxide, aqueous ammonia, potassium permanganate, hydrogen peroxide, One or more of methanol, formic acid, ethanol, calcium hydroxide quaternary ammonium salt, ethylenediamine, ethyl carbonate, acetic acid.

7. The method according to claim 3, wherein the layered pillar clay is selected from one or more of natural or synthetic mineral structural clays; and the clay material in the layered clay material For montmorillonite, kaolin, bentonite, activated clay, sillimanite clay, maifanite, vermiculite, and beidellite, mica vermiculite, mica-montmorillonite, kaolin-montmorillonite; preferred mineral structure In clay Montmorillonite, kaolin, bentonite, kaolin-montmorillonite, more preferably the above-mentioned clay having an active metal component such as iron, cobalt or nickel in an amount of 0.5 to 15% by weight.

8. The method of claim 3, the specific steps are:

(1) calcining the layered column clay in a chemical atmosphere at 400 to 1100 ° C for 0.1 to 10 hours;

9. The method according to claim 7, wherein the baking temperature is 500 to 1000 ° C; and the baking time is 0. 4 hours.

10. The method according to claim 7, wherein the clay, the treating agent and the water are mixed for a period of time ranging from 0.1 to 4 hours.