CN105080591A

CN105080591A - Preparation method of catalyst through methanation of coke oven gas

Info

Publication number: CN105080591A
Application number: CN201410192407.9A
Authority: CN
Inventors: 黄先亮; 吴学其; 蔡进; 蔡成伟; 张�杰; 吴�琳; 徐本刚; 朱艳芳; 魏士新; 檀结东; 孟建; 陈长新
Original assignee: China Petroleum and Chemical Corp; Research Institute of Nanjing Chemical Industry Group Co Ltd
Current assignee: China Petroleum and Chemical Corp; Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
Priority date: 2014-05-08
Filing date: 2014-05-08
Publication date: 2015-11-25
Anticipated expiration: 2034-05-08
Also published as: CN105080591B

Abstract

The invention discloses a preparation method of a catalyst through the methanation of coke oven gas, and belongs to the technical field of catalysis. The preparation method of the catalyst through the methanation of the coke oven gas is characterized by being prepared through the following steps of: 1) performing heat treatment on an HY molecular sieve so as to obtain a molecular sieve USY; 2) mixing the USY molecular sieve with one or more than one kind of gamma-aluminum oxide, stearic acid, sodium stearate and aluminum stearate so as to obtain a mixture, then adding water to the mixture, and uniformly kneading the mixture and the water so as to obtain kneaded materials; 3) pelletizing the kneaded materials so as to obtain particles, and baking the particles; 4) adding graphite to the baked particles to, uniformly mixing the baked particles and the graphite so as to obtain a second mixture, and flattening the second mixture so as to form tablets; 5) baking the tablets, and roasting the baked tablets once more so as to obtain a catalyst carrier; 6) compounding a solution containing one or more than one kind of nickel nitrate, lanthanum nitrate, potassium nitrate (or potassium carbonate), and cerium nitrate (or cerous nitrate), and immersing the prepared catalyst carrier into the solution; and 7) drying the catalyst carrier immersed into the solution, and roasting the dried catalyst carrier so as to obtain the catalyst. The methanation catalyst prepared by the method has favorable hydrothermal stability and carbon deposition resistance.

Description

A kind of preparation method of coke-oven gas methanation catalyst

Technical field

The invention belongs to catalysis technical field, be specifically related to a kind of new method preparing coke-oven gas methanation catalyst.

Background technology

Along with the continuous increase of natural gas demand and import volume, China will face the challenge of natural gas supply safety, and China produces about 1,200 hundred million Nm in recent years every year ³oven gas, a part is used for generating, and a part is used for hydrogen from methyl alcohol processed, also have quite a few directly to discharge, its utilization rate is about 55%, therefore utilizes oven gas preparing natural gas project effectively can recycle resource, produce higher economic benefit, contribute to forming good circulation industrial chain.Compressed natural gas (CNG) or liquefied natural gas (LNG) is produced again further by methanation production synthetic natural gas (SNG) with oven gas, its capacity usage ratio can reach more than 80%, and its flow process is relatively simple, investment is lower, good in economic efficiency, has the very strong market competitiveness.Along with rising steadily of crude oil price, gas price is also constantly rising violently, and CNG is as alternative motor fuels, especially for the field such as taxi and bus, has larger price advantage.Therefore, coke-oven gas methanation synthetic natural gas has important economy and social effect.

Methanation catalyst is usually with Al ₂o ₃for carrier, disclosed in patent US3933833, methanation catalyst is with high-purity gamma-Al ₂o ₃for carrier, load active component nickel oxide and cobalt oxide.Disclosed in patent CN1043639A, methanation catalyst is with Al ₂o ₃for carrier, nickel is active component, and with rare earth metal or alkaline-earth metal, or alkaline-earth metal is co-catalyst.Methanation catalyst disclosed in patent CN1043449A, nickel is active component, and rare earth metal and magnesium are co-catalyst, and all the other are aluminium oxide.These methanation catalysts take aluminium oxide as carrier, use in the methanation reaction of trace amounts of CO x, and reaction temperature is not high, and in reacting gas, steam partial pressure is lower, and catalyst has good stability.But the carrier hydrothermal stability of these catalyst is poor, and be faced with the carbon distribution problem in methanation reaction.HY molecular sieve is heat-treated and is obtained super stable molecular sieve USY at 120 DEG C ~ 700 DEG C temperature, has good heat endurance and hydrothermal stability.

Summary of the invention

The invention provides a kind of method preparing coke-oven gas methanation preparing natural gas catalyst.The methanation catalyst utilizing the method to obtain has good hydrothermal stability and anti-carbon.

A preparation method for coke-oven gas methanation catalyst, is characterized in that catalyst obtains as follows: 1) heat-treated by HY molecular sieve, obtains molecular sieve USY; 2) USY molecular sieve is mixed with one or more in gama-alumina, stearic acid, odium stearate, aluminum stearate, then add water, mediate evenly; 3) by the material granulation after kneading, then particle is dried; 4) particle of drying adds graphite and mixes, shaping; 5) tablet is through drying, then roasting obtains catalyst carrier; 6) preparation is containing nickel nitrate and lanthanum nitrate, potassium nitrate (or potash), one or more solution of cerous nitrate (or cerous nitrate), is immersed in solution by the catalyst carrier of above-mentioned preparation; 7) through super-dry, roasting and obtained catalyst.

Usually, in method for preparing catalyst of the present invention, HY molecular sieve is carried out to the heat treatment of 1h ~ 3h at 120 DEG C ~ 700 DEG C; At 700 DEG C ~ 1200 DEG C, roasting 1h ~ 3h obtains catalyst carrier; Carrier floods 0.5h ~ 3h in mixed solution, takes out and dries at 120 DEG C; The sintering temperature of catalyst 400 DEG C ~ 600 DEG C.

The preparation method of described catalyst, carrier can repeated impregnations repeatedly, until the NiO content in catalyst reaches 10 ~ 25%.

Adopt methanation catalyst mechanical strength prepared by the present invention high, the good stability of catalyst, good hydrothermal stability, be adapted at methanation reaction under higher CO content and higher reaction temperature, effectively can prevent carbon deposit.

Detailed description of the invention

Below in conjunction with embodiment, the present invention is described in detail:

Embodiment 1:

1) get 600gHY molecular sieve, heat-treat at 120 DEG C, heat treatment time is 1h; 2) add 18g gama-alumina and 300g deionized water in the HY molecular sieve after heat treatment, mediate evenly; 3) particle diameter is become to be about the particle of 1.2mm, at 120 DEG C of dry 3h the uniform material granulation of kneading; 4) particle of drying adds 12g graphite and mixes, and is become the cylinder particle of Ф 5 × 5 by tabletting machine; 5) tablet obtains required for Kaolinite Preparation of Catalyst through 700 DEG C of DEG C of roastings carrier; 6) carrier is immersed 0.5h in nickel nitrate solution, take out at 120 DEG C dry, then at 400 DEG C roasting 2h; 7) repeat step 6), to make NiO load capacity reach 10%, obtain catalyst I.

Embodiment 2:

1) get 600gHY molecular sieve, heat-treat at 700 DEG C, heat treatment time is 3h; 2) add 18g gama-alumina and 300g deionized water in the HY molecular sieve after heat treatment, mediate evenly; 3) particle diameter is become to be about the particle of 1.2mm, at 120 DEG C of dry 5h the uniform material granulation of kneading; 4) particle of drying adds 12g graphite and mixes, and is become the cylinder particle of Ф 5 × 5 by tabletting machine; 5) tablet obtains required for Kaolinite Preparation of Catalyst through 1200 DEG C of roastings carrier; 6) carrier is immersed 3h in the solution of nickel nitrate and lanthanum nitrate, take out at 120 DEG C dry, then at 600 DEG C roasting 4h; 7) repeat step 6), to make NiO load capacity reach 25%, obtain catalyst II.

Embodiment 3:

1) get 600gHY molecular sieve, heat-treat at 500 DEG C, heat treatment time is 2h; 2) add 18g gama-alumina and 300g deionized water in the HY molecular sieve after heat treatment, mediate evenly; 3) particle diameter is become to be about the particle of 1.2mm, at 120 DEG C of dry 4h the uniform material granulation of kneading; 4) particle of drying adds 12g graphite and mixes, and is become the cylinder particle of Ф 5 × 5 by tabletting machine; 5) tablet obtains required for Kaolinite Preparation of Catalyst through 1100 DEG C of roastings carrier; 6) carrier is immersed 2h in the solution of nickel nitrate, potassium nitrate (or potash) and lanthanum nitrate, take out at 120 DEG C dry, then at 550 DEG C roasting 3h; 7) repeat step 6), to make NiO load capacity reach 15%, obtain catalyst III.

Embodiment 4:

1) get 600gHY molecular sieve, heat-treat at 700 DEG C, heat treatment time is 2h; 2) add 18g gama-alumina and 300g deionized water in the HY molecular sieve after heat treatment, mediate evenly; 3) particle diameter is become to be about the particle of 1.2mm, at 120 DEG C of dry 3h the uniform material granulation of kneading; 4) particle of drying adds 12g graphite and mixes, and is become the cylinder particle of Ф 5 × 5 by tabletting machine; 5) tablet obtains required for Kaolinite Preparation of Catalyst through 700 DEG C of roastings carrier; 6) carrier is immersed 3h in the solution of nickel nitrate, potassium nitrate, cerous nitrate (or cerous nitrate) and lanthanum nitrate, take out at 120 DEG C dry, then at 400 DEG C roasting 2h; 7) repeat step 6), to make NiO load capacity reach 25%, obtain catalyst IV.

Embodiment 5:

1) get 600gHY molecular sieve, heat-treat at 700 DEG C, heat treatment time is 2h; 2) add 18g stearic acid and 300g deionized water in the HY molecular sieve after heat treatment, mediate evenly; 3) particle diameter is become to be about the particle of 1.2mm, at 120 DEG C of dry 3h the uniform material granulation of kneading; 4) particle of drying adds 12g graphite and mixes, and is become the cylinder particle of Ф 5 × 5 by tabletting machine; 5) tablet obtains required for Kaolinite Preparation of Catalyst through 700 DEG C of roastings carrier; 6) carrier is immersed 3h in the solution of nickel nitrate, potassium nitrate, cerous nitrate (or cerous nitrate) and lanthanum nitrate, take out at 120 DEG C dry, then at 400 DEG C roasting 2h; 7) repeat step 6), to make NiO load capacity reach 25%, obtain catalyst V.

Embodiment 6:

1) get 600gHY molecular sieve, heat-treat at 700 DEG C, heat treatment time is 2h; 2) add 18g odium stearate and 300g deionized water in the HY molecular sieve after heat treatment, mediate evenly; 3) particle diameter is become to be about the particle of 1.2mm, at 120 DEG C of dry 3h the uniform material granulation of kneading; 4) particle of drying adds 12g graphite and mixes, and is become the cylinder particle of Ф 5 × 5 by tabletting machine; 5) tablet obtains required for Kaolinite Preparation of Catalyst through 700 DEG C of roastings carrier; 6) carrier is immersed 3h in the solution of nickel nitrate, potassium nitrate, cerous nitrate (or cerous nitrate) and lanthanum nitrate, take out at 120 DEG C dry, then at 400 DEG C roasting 2h; 7) repeat step 6), to make NiO load capacity reach 25%, obtain catalyst VI.

Embodiment 7:

1) get 600gHY molecular sieve, heat-treat at 700 DEG C, heat treatment time is 2h; 2) add 18g aluminum stearate and 300g deionized water in the HY molecular sieve after heat treatment, mediate evenly; 3) particle diameter is become to be about the particle of 1.2mm, at 120 DEG C of dry 3h the uniform material granulation of kneading; 4) particle of drying adds 12g graphite and mixes, and is become the cylinder particle of Ф 5 × 5 by tabletting machine; 5) tablet obtains required for Kaolinite Preparation of Catalyst through 700 DEG C of roastings carrier; 6) carrier is immersed 3h in the solution of nickel nitrate, potassium nitrate, cerous nitrate (or cerous nitrate) and lanthanum nitrate, take out at 120 DEG C dry, then at 400 DEG C roasting 2h; 7) repeat step 6), to make NiO load capacity reach 25%, obtain catalyst VII.

Methanation catalyst I, II, III, IV, V, VI, VII is seated in fixed-bed tube reactor respectively, and reaction condition is: pressure 2.0MPa, oven gas gas composition H ₂39.12, CH ₄53.08, CO1.18, CO ₂6.30, N ₂1.13, C ₂h ₆1.93, gas space velocity is 5000 ~ 30000h ^-1, after 600 DEG C of reaction 500h, the activity of catalyst keeps good, and wherein CO conversion ratio is 100%, and methane selectively is 100%, and the catalytic mechanical intensity removed is still very high, and the surface of catalyst does not have carbon distribution.

By the standby catalyst of patent system of the present invention through high temperature, for a long time methanation reaction, the methanation activity of still doing well and stability, the carbon analysis drawing off rear sample after test shows, sample does not have obvious carbon distribution to occur.

Claims

1. a preparation method for coke-oven gas methanation catalyst, is characterized in that catalyst obtains as follows: 1) heat-treated by HY molecular sieve, obtains molecular sieve USY; 2) USY molecular sieve is mixed with one or more in gama-alumina, stearic acid, odium stearate, aluminum stearate, then add water, mediate evenly; 3) by the material granulation after kneading, then particle is dried; 4) particle of drying adds graphite and mixes, shaping; 5) tablet is through drying, then roasting obtains catalyst carrier; 6) one or more the solution of preparation containing nickel nitrate and lanthanum nitrate, potassium nitrate (potash), cerous nitrate (cerous nitrate), is immersed in solution by the catalyst carrier of above-mentioned preparation; 7) through super-dry, roasting and obtained catalyst.

2. the preparation method of catalyst according to claim 1, is characterized in that HY molecular sieve heat treatment temperature is at 120 DEG C ~ 700 DEG C.

3. the preparation method of catalyst according to claim 1, is characterized in that HY molecular sieve heat treatment time is at 1h ~ 3h.

4. the preparation method of catalyst according to claim 1, is characterized in that catalyst carrier is 700 DEG C ~ 1200 DEG C roastings.

5. the preparation method of catalyst according to claim 1, is characterized in that catalyst carrier roasting 1h ~ 3h.

6. the preparation method of catalyst according to claim 1, is characterized in that carrier floods 0.5h ~ 3h in mixed solution.

7. the preparation method of catalyst according to claim 1, is characterized in that the sintering temperature 400 DEG C ~ 600 DEG C of catalyst.

8. the preparation method of catalyst according to claim 1, is characterized in that repeated impregnations repeatedly, until the NiO content in catalyst reaches 10% ~ 25%.