CN103785375B - A kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application - Google Patents

A kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application Download PDF

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CN103785375B
CN103785375B CN201210427647.3A CN201210427647A CN103785375B CN 103785375 B CN103785375 B CN 103785375B CN 201210427647 A CN201210427647 A CN 201210427647A CN 103785375 B CN103785375 B CN 103785375B
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sio
catalyst
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CN103785375A (en
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张信伟
张舒东
方向晨
尹泽群
张喜文
刘全杰
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The present invention discloses a kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst, the SiO after adopting Nb, Ce to modify 2for carrier, with Mo, Sb for active component, by the weight content of final catalyst, Mo? 5% ~ 11%; Sb? 7% ~ 20%; Nb? 1% ~ 3.5%; Ce? 1% ~ 3.5%; Surplus is SiO 2.A preparation method for methane selectively oxidizing synthesizing methanol and formaldehyde catalyst, adopts infusion process load Nb, Ce to obtain the SiO of Nb, Ce modification 2; Then load active component Sb, Mo; Finally by shaping, the obtained final catalyst of screening.This catalyst can under low pressure in methane selectively oxidizing methyl alcohol and formolite reaction, has the advantages such as high methane conversion and high methanol and formaldehyde be selective.

Description

A kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application
Technical field
The present invention relates to a kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application, relate in particular to a kind of the methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application that are carrier with multiple-addition agent modified silica.
Background technology
Along with the shortage increasingly of the fossil resource such as oil and coal, take natural gas as the great attention that high-quality, clean energy resource and industrial chemicals cause various countries more and more widely.The main component of natural gas is methane, the technology of the direct methanol of exploitation methane, formaldehyde, compared with current industrialized indirect method, have that route is simple, low cost and other advantages, therefore Shell, Sasol, Exxon-Mobil, BP Deng Ge major oil companies successively drop into huge fund and study.Methane selectively oxidizing synthesizing methanol, formaldehyde challenge one of maximum problem in catalyticing research, and this reaction has two difficult points: the first, and methane molecule is difficult to activation, because methane molecule passes through sp by four c h bonds of equal value 3hydridization forms positive tetrahedron structure, and its macroscopic property is highly stable; The second, object selectivity of product is poor, because methyl alcohol, formaldehyde are more active than methane, is easily CO or CO by deep oxidation 2.Therefore, how to reduce methane activation condition, improve formaldehyde, methanol product selective, be one of primary key issue solved in this area research.
The people such as Aoki at CatalysisToday, 1998, report MoO on 29 3/ SiO 2catalyst, prepares in methyl alcohol, formaldehyde at methane selectively oxidizing and shows excellent performance, and methyl alcohol and the selective of formaldehyde have had large increase, and the once through yield of methyl alcohol and formaldehyde is maximum reaches 3.8%.US6294701 adopts silicon dioxide carried silicon-molybdenum heteropoly acid to be catalyst, is formaldehyde by directly oxidizing methane.The activity and selectivity of these catalyst still needs further raising, to meet industrial requirement.
CN1621150A discloses a kind of silicon dioxide carried antimony oxide catalysts for methane selectively oxidizing formaldehyde and preparation method thereof, embodiment to show at 600 DEG C the highest formaldehyde of reaction selective be 30.2%, now methane conversion is only 0.7%, but reaction temperature is too high, to catalyst activity and stability requirement higher.It is carrier with mesopore molecular sieve that CN101618327A discloses a kind of, the multiple element compound catalyst being primary activity component with Mo, V, and at 4 ~ 5MPa, at 400 ~ 500 DEG C, methane conversion remains on more than 8 ~ 15%, and methyl alcohol, formaldehyde yield are 5 ~ 10%.But the reaction pressure in this patent is too high, higher to the security requirement of equipment.
In a word, the above catalyst ubiquity that methane conversion needs to improve further, formaldehyde and methyl alcohol selective lower, one of reaction pressure is higher etc. or more than one are not enough.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application.This catalyst with multiple-addition agent modified silica for carrier, with Mo, Sb for active component, can under low pressure in methane selectively oxidizing methyl alcohol and formolite reaction, there is the advantages such as high methane conversion and high methanol and formaldehyde be selective.
A kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst, the SiO after adopting Nb, Ce to modify 2for carrier, with Mo, Sb for active component, by the weight content of final catalyst, Mo5% ~ 11%; Sb7% ~ 20%; Nb1% ~ 3.5%; Ce1% ~ 3.5%; Surplus is SiO 2.
A preparation method for methane selectively oxidizing synthesizing methanol and formaldehyde catalyst, adopts infusion process load Nb, Ce to obtain the SiO of Nb, Ce modification 2; Then load active component Sb, Mo; Finally by shaping, the obtained final catalyst of screening.
In the inventive method, preferred Nb, Ce adopt co-impregnation to load to SiO 2on.Active component Sb, Mo preferably adopt first load Sb, then the step impregnation method of load Mo load to Nb, Ce modify after SiO 2on carrier, the load of Sb preferably adopts the precipitation method.Specifically comprise the following steps:
(1) by a certain percentage by niobium oxalate and Ce (NO 3) 36H 2o is dissolved in the water completely, by SiO 2carrier immerses in this solution, leaves standstill 10 ~ 12 hours, rotary evaporation removing moisture, and dry 9-15 hour at 100 ~ 120 DEG C, roasting 5 ~ 10 hours at 500 ~ 550 DEG C, can obtain the SiO modified through Nb, Ce 2carrier;
(2) by a certain percentage by SbCl 5be dissolved in completely in ethanol, the SiO that incipient impregnation Nb, Ce modify 23 ~ 10 hours, add in ammoniacal liquor carry out stirring, filter, wash and with 100 ~ 120 DEG C at dry 12 ~ 24 hours;
(3) by (NH 4) 6mo 7o 24.4H 2o is dissolved in the water, by the SiO that this solution incipient impregnation is modified to Nb, Ce containing active component Sb that step (2) is obtained 2on carrier, put into baking oven dry 20-28 hour at 100 ~ 120 DEG C, roasting 5 ~ 10 hours at 550 ~ 650 DEG C;
(4) by the sample compressing tablet after roasting, pulverize, screening 20 ~ 40 object particles are as final catalyst.
An application for methane selectively oxidizing synthesizing methanol and formaldehyde catalyst, reaction temperature is 500 ~ 600 DEG C, and reaction pressure is 0.5 ~ 2MPa, and feed gas molar consists of CH 4: O 2: H 2o=2:0.5 ~ 1.5:0.5 ~ 1.5, air speed is 2000 ~ 2800h -1.
Compared with prior art, a kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application tool of the present invention has the following advantages:
(1) SiO that modifies with Nb, Ce of catalyst of the present invention 2for carrier, with Mo, Sb for active component, the SiO that Nb, Ce modify 2carrier can strengthen oxygen storage capacity and the electron transfer capacity of carrier, improve the decentralization of active component Mo, Sb, the synergy of Nb, Ce, Mo, Sb various ingredients, ensure that higher Methane Activation ability, also effectively can suppress the deep oxidation of methyl alcohol and formaldehyde, improve the selective of object product;
(2) in the preparation method of catalyst of the present invention, adopt first total immersion stain Nb, Ce, then step impregnation Sb, Mo can improve the decentralization of active component further, promotes the synergy of Nb, Ce, Mo, Sb various ingredients, improves the selective of the conversion ratio of methane and methyl alcohol and formaldehyde;
(3) catalyst of the present invention can use under 0.5 ~ 2MPa lower pressure, keep methane conversion be 10 ~ 16%, methyl alcohol and formaldehyde selective be 78 ~ 86%.
Detailed description of the invention
Further illustrate the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited in following example.
embodiment 1
Take 1.9g niobium oxalate and 1.6gCe (NO 3) 36H 2o is dissolved in the water, by 20.0gSiO 2carrier immerses in this solution, and room temperature leaves standstill 12 hours, and rotary evaporation removing moisture at 60 DEG C, drying 12 hours at 120 DEG C, roasting 5 hours at 500 DEG C, can obtain the SiO that Nb, Ce modify 2carrier.
By 4.9gSbCl 5add in ethanol in proper amount, to be dissolved completely after, add the SiO that Nb, Ce prepared by back modify 2carrier incipient impregnation 4 hours, drying at room temperature 12 hours, is added in 100mL ammoniacal liquor and is stirred 2 hours, and filter, being washed to pH value is 6 ~ 7, drying at room temperature 24 hours, puts into baking oven at 120 DEG C dry 24 hours.
Take 2.8g (NH 4) 6mo 7o 24.4H 2o is dissolved in suitable quantity of water completely; Then by this solution incipient impregnation on the obtained carrier of previous step, leave standstill 4 hours, put into baking oven at 120 DEG C dry 24 hours, then roasting 6 hours at 600 DEG C; Finally by the sample compressing tablet after roasting, be crushed to 20 ~ 40 orders, by weight percentage, the catalyst of preparation has following composition: Mo6.2%, Sb8.1%, Nb1.7%, Ce2.1% and SiO 2surplus.
Evaluating catalyst carries out in continuous-flow micro fixed-bed reactor, and wherein reaction temperature is 580 DEG C; Reaction pressure is 0.5MPa; Feed gas molar consists of CH 4: O 2: H 2o=2:1.5:1.5, air speed is 2000h -1, obtain methane conversion 11.0%, methyl alcohol and formaldehyde selective be 85.0%.
embodiment 2
Take 1.9g niobium oxalate and 1.6gCe (NO 3) 36H 2o is dissolved in the water, by 20.0gSiO 2carrier immerses in this solution, and room temperature leaves standstill 12 hours, and rotary evaporation removing moisture at 60 DEG C, drying 12 hours at 120 DEG C, roasting 5 hours at 500 DEG C, can obtain the SiO that Nb, Ce modify 2carrier.
By 4.9gSbCl 5add in ethanol in proper amount, to be dissolved completely after, add the SiO that Nb, Ce prepared by back modify 2carrier incipient impregnation 4 hours, drying at room temperature 12 hours, is added in 100mL ammoniacal liquor and is stirred 2 hours, and filter, being washed to pH value is 6 ~ 7, drying at room temperature 24 hours, puts into baking oven at 120 DEG C dry 24 hours.
Take 2.8g (NH 4) 6mo 7o 24.4H 2o is dissolved in suitable quantity of water completely; Then by this solution incipient impregnation on the obtained carrier of previous step, leave standstill 4 hours, put into baking oven at 120 DEG C dry 24 hours, then roasting 6 hours at 600 DEG C; Finally by the sample compressing tablet after roasting, be crushed to 20 ~ 40 orders, by weight percentage, the catalyst of preparation has following composition: Mo5.8%, Sb14.3%, Nb1.6%, Ce2.0% and SiO 2surplus.
Evaluating catalyst is with embodiment 1, and difference is that reaction temperature is 550 DEG C, and reaction pressure is 1MPa, and feed gas molar consists of CH 4: O 2: H 2o=2:1:1, air speed is 2500h -1; Obtain methane conversion 9.6%, methyl alcohol and formaldehyde selective be 86.6%.
embodiment 3
Take 1.9g niobium oxalate and 1.6gCe (NO 3) 36H 2o is dissolved in the water, by 20.0gSiO 2carrier immerses in this solution, and room temperature leaves standstill 12 hours, and rotary evaporation removing moisture at 60 DEG C, drying 12 hours at 120 DEG C, roasting 5 hours at 500 DEG C, can obtain the SiO that Nb, Ce modify 2carrier.
By 4.9gSbCl 5add in ethanol in proper amount, to be dissolved completely after, add the SiO that Nb, Ce prepared by back modify 2carrier incipient impregnation 4 hours, drying at room temperature 12 hours, is added in 100mL ammoniacal liquor and is stirred 2 hours, and filter, being washed to pH value is 6 ~ 7, drying at room temperature 24 hours, puts into baking oven at 120 DEG C dry 24 hours.
Take 2.8g (NH 4) 6mo 7o 24.4H 2o is dissolved in suitable quantity of water completely; Then by this solution incipient impregnation on the obtained carrier of previous step, leave standstill 4 hours, put into baking oven at 120 DEG C dry 24 hours, then roasting 6 hours at 600 DEG C; Finally by the sample compressing tablet after roasting, be crushed to 20 ~ 40 orders, by weight percentage, the catalyst of preparation has following composition: Mo5.4%, Sb19.6%, Nb1.5%, Ce1.9% and SiO 2surplus.
Evaluating catalyst is with embodiment 1, and difference is that reaction temperature is 520 DEG C, and reaction pressure is 1.5MPa, and feed gas molar consists of CH 4: O 2: H 2o=2:0.5:0.5, air speed is 2800h -1; Obtain methane conversion 8.5%, methyl alcohol and formaldehyde selective be 87.5%.
embodiment 4
Take 2.3g niobium oxalate and 2.6gCe (NO 3) 36H 2o is dissolved in the water, by 20.0gSiO 2carrier immerses in this solution, and room temperature leaves standstill 12 hours, and rotary evaporation removing moisture at 60 DEG C, drying 12 hours at 120 DEG C, roasting 5 hours at 500 DEG C, can obtain the SiO that Nb, Ce modify 2carrier.
By 4.9gSbCl 5add in ethanol in proper amount, to be dissolved completely after, add the SiO that Nb, Ce prepared by back modify 2carrier incipient impregnation 4 hours, drying at room temperature 12 hours, is added in 100mL ammoniacal liquor and is stirred 2 hours, and filter, being washed to pH value is 6 ~ 7, drying at room temperature 24 hours, puts into baking oven at 120 DEG C dry 24 hours.
Take 3.3g (NH 4) 6mo 7o 24.4H 2o is dissolved in suitable quantity of water completely; Then by this solution incipient impregnation on the obtained carrier of previous step, leave standstill 4 hours, put into baking oven at 120 DEG C dry 24 hours, then roasting 6 hours at 600 DEG C; Finally by the sample compressing tablet after roasting, be crushed to 20 ~ 40 orders, by weight percentage, the catalyst of preparation has following composition: Mo7.1%, Sb7.9%, Nb2.0%, Ce3.3% and SiO 2surplus.
Evaluating catalyst and process conditions are with embodiment 1, and difference is that reaction temperature is 550 DEG C; Obtain methane conversion 12.3%, methyl alcohol and formaldehyde selective be 83.3%.
embodiment 5
Take 3.1g niobium oxalate and 2.4gCe (NO 3) 36H 2o is dissolved in the water, by 20.0gSiO 2carrier immerses in this solution, and room temperature leaves standstill 12 hours, and rotary evaporation removing moisture at 60 DEG C, drying 12 hours at 120 DEG C, roasting 5 hours at 500 DEG C, can obtain the SiO that Nb, Ce modify 2carrier.
By 4.9gSbCl 5add in ethanol in proper amount, to be dissolved completely after, add the SiO that Nb, Ce prepared by back modify 2carrier incipient impregnation 4 hours, drying at room temperature 12 hours, is added in 100mL ammoniacal liquor and is stirred 2 hours, and filter, being washed to pH value is 6 ~ 7, drying at room temperature 24 hours, puts into baking oven at 120 DEG C dry 24 hours.
Take 4.1g (NH 4) 6mo 7o 24.4H 2o is dissolved in suitable quantity of water completely; Then by this solution incipient impregnation on the obtained carrier of previous step, leave standstill 4 hours, put into baking oven at 120 DEG C dry 24 hours, then roasting 6 hours at 600 DEG C; Finally by the sample compressing tablet after roasting, be crushed to 20 ~ 40 orders, by weight percentage, the catalyst of preparation has following composition: Mo8.7%, Sb7.7%, Nb2.6%, Ce3.1% and SiO 2surplus.
Evaluating catalyst and process conditions, with embodiment 4, obtain methane conversion 13.6%, methyl alcohol and formaldehyde selective be 81.7%.
embodiment 6
Take 3.8g niobium oxalate and 1.1gCe (NO 3) 36H 2o is dissolved in the water, by 20.0gSiO 2carrier immerses in this solution, and room temperature leaves standstill 12 hours, and rotary evaporation removing moisture at 60 DEG C, drying 12 hours at 120 DEG C, roasting 5 hours at 500 DEG C, can obtain the SiO that Nb, Ce modify 2carrier.
By 4.9gSbCl 5add in ethanol in proper amount, to be dissolved completely after, add the SiO that Nb, Ce prepared by back modify 2carrier incipient impregnation 4 hours, drying at room temperature 12 hours, is added in 100mL ammoniacal liquor and is stirred 2 hours, and filter, being washed to pH value is 6 ~ 7, drying at room temperature 24 hours, puts into baking oven at 120 DEG C dry 24 hours.
Take 5.0g (NH 4) 6mo 7o 24.4H 2o is dissolved in suitable quantity of water completely; Then by this solution incipient impregnation on the obtained carrier of previous step, leave standstill 4 hours, put into baking oven at 120 DEG C dry 24 hours, then roasting 6 hours at 600 DEG C; Finally by the sample compressing tablet after roasting, be crushed to 20 ~ 40 orders, by weight percentage, the catalyst of preparation has following composition: Mo10.5%, Sb7.7%, Nb3.2%, Ce1.4% and SiO 2surplus.
Evaluating catalyst and process conditions, with embodiment 4, obtain methane conversion 15.0%, methyl alcohol and formaldehyde selective be 80.0%.
comparative example 1
With not modified SiO 2for carrier loaded active component Mo, Sb, the mode of loading of active component, active component content in the final catalyst and appreciation condition are with embodiment 4.The evaluation result of catalyst is: methane conversion 5.8%, methyl alcohol and formaldehyde selective be 71.2%.

Claims (3)

1. a preparation method for methane selectively oxidizing synthesizing methanol and formaldehyde catalyst, is characterized in that: first adopt infusion process load Nb, Ce to obtain the SiO of Nb, Ce modification 2; Then load active component Sb, Mo; Finally by shaping, the obtained final catalyst of screening, by the weight content of final catalyst, Mo5% ~ 11%; Sb7% ~ 20%; Nb1% ~ 3.5%; Ce1% ~ 3.5%; Surplus is SiO 2, concrete preparation process comprises the steps:
(1) by a certain percentage by niobium oxalate and Ce (NO 3) 36H 2o is dissolved in the water, by SiO 2carrier immerses in this solution, leaves standstill 10 ~ 12 hours, rotary evaporation removing moisture, and dry 9-15 hour at 100 ~ 120 DEG C, roasting 5 ~ 10 hours at 500 ~ 550 DEG C, can obtain the SiO modified through Nb, Ce 2carrier;
(2) by a certain percentage by SbCl 5be dissolved in ethanol, the SiO that incipient impregnation Nb, Ce modify 23 ~ 10 hours, add in ammoniacal liquor carry out stirring, filter, wash and with 100 ~ 120 DEG C at dry 12 ~ 24 hours;
(3) by (NH 4) 6mo 7o 24.4H 2o is dissolved in the water, by the SiO that this solution incipient impregnation is modified containing Nb, Ce of active component Sb 2on carrier, put into baking oven dry 20-28 hour at 100 ~ 120 DEG C, roasting 5 ~ 10 hours at 550 ~ 650 DEG C.
2. method according to claim 1, is characterized in that: screening 20 ~ 40 object particles are as final catalyst.
3. the application of the methane selectively oxidizing synthesizing methanol prepared of method described in claim 1 and formaldehyde catalyst, reaction temperature is 500 ~ 600 DEG C, and reaction pressure is 0.5 ~ 2MPa, and feed gas molar consists of CH 4: O 2: H 2o=2:0.5 ~ 1.5:0.5 ~ 1.5, air speed is 2000 ~ 2800h -1.
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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
CN107739297B (en) * 2017-09-27 2019-12-17 厦门大学 Method for preparing methanol, formaldehyde and CO by directly and selectively oxidizing methane
CN112876338B (en) * 2019-11-29 2022-03-29 中国科学院大连化学物理研究所 Method for preparing methanol and formic acid by catalyzing methane with ruthenium catalyst

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