CN101618327B - Catalyst for synthesizing methanol and formaldehyde by oxidizing methane, preparation method and application thereof - Google Patents

Catalyst for synthesizing methanol and formaldehyde by oxidizing methane, preparation method and application thereof Download PDF

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Publication number
CN101618327B
CN101618327B CN2009101504226A CN200910150422A CN101618327B CN 101618327 B CN101618327 B CN 101618327B CN 2009101504226 A CN2009101504226 A CN 2009101504226A CN 200910150422 A CN200910150422 A CN 200910150422A CN 101618327 B CN101618327 B CN 101618327B
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catalyst
formaldehyde
molecular sieve
methane
carrier
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CN2009101504226A
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Chinese (zh)
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CN101618327A (en
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赵亮富
崔海涛
张晔
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中国科学院山西煤炭化学研究所
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a catalyst for synthesizing methanol and formaldehyde by oxidizing methane, which is a multiplex compound catalyst. The multiplex compound catalyst takes a mesoporous molecular sieve as a carrier and comprises four active components including Mo and V as basic active components and any two active components of Fe, La, Co and Bi, wherein the weight proportion of mesoporous molecular sieve: Mo: V: any two active components of Fe, La, Co and Bi is 100:1 to 40:1 to 40:0.5 to 30: 5 to 30. The catalyst for synthesizing methanol and formaldehyde by oxidizing methane has higher methane conversion rate, higher selectivity and yield of methanol and formaldehyde, good mechanical strength and high stability.

Description

The catalyst of a kind of methane oxidation synthesizing methanol and formaldehyde and method for making and application

The application number of original application case is 200710185470.X, and the applying date is on December 21st, 2007.

Technical field

The present invention relates to the Catalysts and its preparation method and the application of a kind of methane oxidation synthesizing methanol and formaldehyde.

Background technology

Along with the depletion of petroleum resources, coal utilization causes serious environmental to pollute, and natural gas more and more is subject to people's attention as a kind of fuel and important chemical material of cleaning.But, make that the transportation of natural gas and storage are very inconvenient under room temperature and atmospheric pressure because natural gas exists with gas form.With respect to expensive traditionally tubing transportation or with the natural gas liquefaction technology of liquid nitrogen condensation technology, changing into liquid fuel such as methyl alcohol and formaldehyde and important chemical material on the spot at the natural gas resource enrichment region obviously is one of most economical effective and efficient manner.

The main component of natural gas is a methane, the technology of exploitation directly oxidizing methane synthesizing methanol and formaldehyde, compare with present industrialized indirect method, it is low to have investment cost, advantages such as the simple and production cost of process route is low, therefore for many years, many researchers have dropped into a large amount of energy and have carried out extensive studies work.B.Michalkiewicz is at the last report of Applied Catalysis A:General 277 (2004) 147-153, adopt the Fe-HZSM-5 catalyst, when Si/Fe is 22, obtain higher methane conversion, be 31.51%, this moment, the selectivity of methyl alcohol and formaldehyde was respectively 10.79% and 17.06%.People such as X.Wang adopt the FePO of MCM-41 load at Journal ofCatalysis 217 (2003) 457-467 report 4Catalyst, formaldehyde are primary products, work as FePO 4Load capacity be 40% o'clock, obtain the selectivity of higher formaldehyde, be 79.3%, but methane conversion is very low.Generally speaking, though in the past the catalyst of report respectively had characteristics, all exist or methane conversion low, perhaps the selectivity of methyl alcohol and formaldehyde is low, and then the low result of the yield that causes methyl alcohol and formaldehyde, and the catalyst mechanical strength is not high, the bad deficiency that waits of stability.

Summary of the invention

The objective of the invention is to propose a kind of mechanical strength high and the methane oxidation synthesizing methanol of good stability and the Catalysts and its preparation method and the application of formaldehyde, make this catalyst be used for the reaction of directly oxidizing methane synthesizing methanol and formaldehyde, can obtain the selectivity of higher methane conversion and methyl alcohol and formaldehyde simultaneously.

A kind of methane oxidation synthesizing methanol that the present invention proposes and the catalyst of formaldehyde adopt immersion process for preparing, with the mesopore molecular sieve is carrier, with Mo, V is the primary activity component, add Fe in addition, La, Co, any two active components among the Bi, the multiple element compound catalyst of forming by four kinds of active components altogether, the catalyst weight ratio consists of, mesopore molecular sieve carrier: Mo:V:Fe, La, Co, any two active components among four kinds of the Bi are: 100: (1~40): (1~40): (0.5~30): (0.5~30), mesopore molecular sieve carrier are MCM-41 or SBA-15.

Above-mentioned Preparation of catalysts method may further comprise the steps: with (NH 4) 6Mo 7O 244H 2O, NH 4VO 3Primary activity component and Fe (NO 3) 39H 2O, La (NO 3) 36H 2O, Co (NO 3) 26H 2O, Bi (NO 3) 35H 2In the O active component any two, totally four kinds of compounds are pressed and are used dissolved in distilled water after catalyst is formed mixing, make solution A; Then the solution A that makes is impregnated on the carrier, left standstill 3~7 hours, 100~120 ℃ of oven dry, 500~700 ℃ of roastings 6~8 hours.At last, the sample extruded moulding with after the roasting is crushed to suitable granularity, can make the required catalyst of reaction.

The mesopore molecular sieve carrier of above-mentioned catalyst is SBA-15 or MCM-41.

The mol ratio that Application of Catalyst method of the present invention is methane, oxygen and nitrogen is controlled at (8~10): 1: (1~5), in fixed bed reactors, 400~500 ℃ of reaction temperatures, reaction pressure 4~5MPa reacts under the condition of gas space velocity 8000~15000ml/ (gh).Promptly obtain the methyl alcohol and the formaldehyde of higher yields.

The present invention has following advantage:

1. catalyst of the present invention is because other any two elements that add among Fe, La, Co, the Bi, there is multiple variable valency metal, because interaction and acting in conjunction between the multiple metal, make this catalyst have the performance of higher activation methane, also have the performance that suppresses purpose product methyl alcohol and oxidation of formaldehyde simultaneously.

2. catalyst of the present invention is owing to adopt active constituent loading on the mesopore molecular sieve carrier with bigger specific area, pore volume and high-sequential pore passage structure, owing to the interaction between metal and the carrier, further improved the catalytic activity and the purpose product selectivity of catalyst.Reduce coke content simultaneously, improved the mechanical strength and the stability of catalyst.

3. catalyst of the present invention, the preparation method is simple, and is easy to operate.

4. catalyst of the present invention is guaranteeing that methane conversion remains on 8~15% higher bases, obtains selectivity and 5.0~10% higher methyl alcohol and the yield of formaldehyde of 40~80% higher methyl alcohol and formaldehyde.

The specific embodiment

Embodiment 1

(1) Preparation of catalysts: take by weighing 1.2g NH respectively 4VO 3, 2.5gFe (NO 3) 39H 2O, 17.2g (NH 4) 6Mo 7O 244H 2O and 2.1g La (NO 3) 36H 2O makes solution A with being dissolved in an amount of distilled water after its mixing; Take by weighing the 20.0g mesoporous molecular sieve SBA-15 then, the solution A that will contain active component is impregnated on the mesoporous molecular sieve SBA-15, left standstill 4 hours, and 110 ℃ of oven dry, 600 ℃ of roastings 7 hours; At last, the sample extruded moulding with after the roasting is crushed to 20~40 orders, and can make and consist of SBA-15: Mo: V: Fe: the La weight ratio was respectively 100: 10: 9: 5: 8 catalyst.

(2) Application of Catalyst: be reflected in the stainless steel fixed bed reactors of liner quartz ampoule of continuous-flow and carry out, the mol ratio 10: 1: 2 of methane, oxygen and nitrogen in unstripped gas, reaction pressure 4MPa, 400 ℃ of reaction temperatures, under air speed 10000ml/ (g*h) reaction condition, obtain methane conversion 11%, the selectivity of methyl alcohol and formaldehyde is 80%, the yield 9.0% of methyl alcohol and formaldehyde.

Embodiment 2

(1) Preparation of catalysts: take by weighing 1.2g NH respectively 4VO 3, 2.5gFe (NO 3) 39H 2O, 17.2g (NH 4) 6Mo 7O 244H 2O and 2.1g La (NO 3) 36H 2O makes solution A with being dissolved in an amount of distilled water after its mixing; Take by weighing 20.0g mesopore molecular sieve MCM-41 then, the solution A that will contain active component is impregnated on the mesopore molecular sieve MCM-41, left standstill 4 hours, and 110 ℃ of oven dry, 600 ℃ of roastings 7 hours; At last, the sample extruded moulding with after the roasting is crushed to 20~40 orders, and can make and consist of MCM-41: Mo: V: Fe: the La weight ratio was respectively 100: 10: 9: 5: 8 catalyst.

(2) Application of Catalyst: be reflected in the stainless steel fixed bed reactors of liner quartz ampoule of continuous-flow and carry out, the mol ratio 10: 1: 2 of methane, oxygen and nitrogen in the unstripped gas, at reaction pressure 4.0MPa, 420 ℃ of reaction temperatures, under air speed 10000ml/ (g*h) reaction condition, obtain methane conversion 10%, the selectivity of methyl alcohol and formaldehyde is 73%, the yield 7.3% of methyl alcohol and formaldehyde.

Embodiment 3

(1) Preparation of catalysts: take by weighing 1.2g NH respectively 4VO 3, 2.1g Co (NO 3) 26H 2O, 17.2g (NH 4) 6Mo 7O 244H 2O and 1.9gBi (NO 3) 35H 2O makes solution A with being dissolved in an amount of distilled water after its mixing; Take by weighing 20.0g mesopore molecular sieve MCM-41 then, the solution A that will contain active component is impregnated on the mesopore molecular sieve MCM-41, left standstill 3 hours, and 110 ℃ of oven dry, 600 ℃ of roastings 8 hours; At last, the sample extruded moulding with after the roasting is crushed to 20~40 orders, and can make and consist of MCM-41: Mo: V: Co: the Bi weight ratio was respectively 100: 10: 9: 6: 9 catalyst.

(2) catalyst is used: be reflected in the stainless steel fixed bed reactors of liner quartz ampoule of continuous-flow and carry out, the mol ratio 8: 1: 1 of methane, oxygen and nitrogen in unstripped gas, reaction pressure 5MPa, 410 ℃ of reaction temperatures, under air speed 12000ml/ (g*h) reaction condition, obtain methane conversion 9%, the selectivity of methyl alcohol and formaldehyde is 76%, the yield 7.0% of methyl alcohol and formaldehyde.

Embodiment 4

(1) Preparation of catalysts: take by weighing 1.2g NH respectively 4VO 3, 2.1g Co (NO 3) 26H 2O, 17.2g (NH 4) 6Mo 7O 244H 2O and 1.9gBi (NO 3) 35H 2O makes solution A with being dissolved in an amount of distilled water after its mixing; Take by weighing the 20.0g mesoporous molecular sieve SBA-15 then, the solution A that will contain active component is impregnated on the mesoporous molecular sieve SBA-15, left standstill 3 hours, and 110 ℃ of oven dry, 600 ℃ of roastings 8 hours; At last, the sample extruded moulding with after the roasting is crushed to 20~40 orders, and can make and consist of SBA-15: Mo: V: Co: the Bi weight ratio was respectively 100: 10: 9: 6: 9 catalyst.

(2) Application of Catalyst: be reflected in the stainless steel fixed bed reactors of liner quartz ampoule of continuous-flow and carry out, the mol ratio 10: 1: 2 of methane, oxygen and nitrogen in unstripped gas, reaction pressure 5MPa, 400 ℃ of reaction temperatures, under air speed 10000ml/ (g*h) reaction condition, obtain methane conversion 12%, the selectivity of methyl alcohol and formaldehyde is 80%, the yield 9.6% of methyl alcohol and formaldehyde.

Claims (3)

1. the catalyst of methane oxidation synthesizing methanol and formaldehyde, it is characterized in that being is carrier with the mesopore molecular sieve, the multiple element compound catalyst with Mo, V, Co and four kinds of active components compositions of Bi, the catalyst weight ratio consists of, mesopore molecular sieve carrier: Mo: V: Co: Bi=100: 1~40: 1~40: 0.5~30: 0.5~30;
Described mesopore molecular sieve carrier is MCM-41 or SBA-15.
2. Preparation of catalysts method as claimed in claim 1 is characterized in that may further comprise the steps: with (NH 4) 6Mo 7O 244H 2O, NH 4VO 3, Co (NO 3) 26H 2O and Bi (NO 3) 35H 2O uses dissolved in distilled water after totally four kinds of compounds are pressed the mixing of catalyst composition, makes solution A; Then the solution A that makes is impregnated on the carrier, left standstill 3~7 hours, 100~120 ℃ of oven dry, 500~700 ℃ of roastings 6~8 hours, last, with the sample extruded moulding after the roasting, pulverize, make catalyst.
3. Application of Catalyst as claimed in claim 1, it is characterized in that application process is that the mol ratio of methane, oxygen and nitrogen is controlled at 8~10: 1: 1~5, in fixed bed reactors, 400~500 ℃ of reaction temperatures, reaction pressure 4~5MPa reacts under the condition of gas space velocity 8000~15000ml/ (gh).
CN2009101504226A 2007-12-21 2007-12-21 Catalyst for synthesizing methanol and formaldehyde by oxidizing methane, preparation method and application thereof CN101618327B (en)

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CN104549223B (en) * 2013-10-23 2017-07-28 中国石油化工股份有限公司 A kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4833112A (en) * 1984-12-28 1989-05-23 Gaz De France Thioresistant catalyst for methane production
CN1267236A (en) * 1997-08-20 2000-09-20 巴斯福股份公司 Method for producing multi-metal oxide masses contg. Mo, V and Cu
CN1287879A (en) * 1999-09-15 2001-03-21 罗姆和哈斯公司 Catalyst for oxidation of paraffine
CN1649669A (en) * 2002-02-26 2005-08-03 拜尔材料科学股份公司 Catalyst
CN1810358A (en) * 2005-01-26 2006-08-02 中国石油化工股份有限公司 Acrylonitrile fluid bed catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4833112A (en) * 1984-12-28 1989-05-23 Gaz De France Thioresistant catalyst for methane production
CN1267236A (en) * 1997-08-20 2000-09-20 巴斯福股份公司 Method for producing multi-metal oxide masses contg. Mo, V and Cu
CN1287879A (en) * 1999-09-15 2001-03-21 罗姆和哈斯公司 Catalyst for oxidation of paraffine
CN1649669A (en) * 2002-02-26 2005-08-03 拜尔材料科学股份公司 Catalyst
CN1810358A (en) * 2005-01-26 2006-08-02 中国石油化工股份有限公司 Acrylonitrile fluid bed catalyst

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