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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- hours
- sio
- catalyst
- formaldehyde
- carrier
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
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
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210427647.3A CN103785375B (en) | 2012-11-01 | 2012-11-01 | A kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210427647.3A CN103785375B (en) | 2012-11-01 | 2012-11-01 | A kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103785375A CN103785375A (en) | 2014-05-14 |
CN103785375B true CN103785375B (en) | 2015-12-16 |
Family
ID=50661681
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201210427647.3A Active CN103785375B (en) | 2012-11-01 | 2012-11-01 | A kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103785375B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6294701B1 (en) * | 1999-03-26 | 2001-09-25 | President Of Shizuoka University | Method of producing formaldehyde directly from methane |
CN102476050A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院大连化学物理研究所 | Preparation method of catalysts Mo-V-M-O for alkane selective oxidation reaction |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2856398B1 (en) * | 2003-06-17 | 2007-08-31 | Atofina | PROCESS FOR THE PRODUCTION OF FORMALDEHYDE BY SELECTIVE OXIDATION OF METHANE |
-
2012
- 2012-11-01 CN CN201210427647.3A patent/CN103785375B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6294701B1 (en) * | 1999-03-26 | 2001-09-25 | President Of Shizuoka University | Method of producing formaldehyde directly from methane |
CN102476050A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院大连化学物理研究所 | Preparation method of catalysts Mo-V-M-O for alkane selective oxidation reaction |
Non-Patent Citations (2)
Title |
---|
Mo/SiO2及V改性的Mo/SiO2催化剂的微孔特征及其对甲烷部分氧化合成甲醛反应的影响;王承学等;《催化学报》;19970930;第18卷(第5期);373-377 * |
锑氧化物及锑钒复合氧化物催化剂上的甲烷选择氧化研究;张海东;《中国优秀博硕士学位论文全文数据库(博士) 工程科技I辑》;20070415(第4期);正文第87-88页 * |
Also Published As
Publication number | Publication date |
---|---|
CN103785375A (en) | 2014-05-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106365995A (en) | Methyl acetate production method | |
CN101264451A (en) | Preparation of catalyst for synthesizing ethyl acetate | |
CN102658165A (en) | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof | |
CN102962071A (en) | Catalyst for preparing alcohol from acetate through hydrogenation as well as preparation method and application thereof | |
CN103785375B (en) | A kind of methane selectively oxidizing synthesizing methanol and formaldehyde catalyst and its preparation method and application | |
CN102698761A (en) | Preparation method of catalyst for hexone synthesis by acetone hydrogenation and application | |
CN109574798A (en) | A kind of method that synthesis gas directly produces ethyl alcohol | |
CN101601995B (en) | Aluminum oxide catalyst used for preparing dimethyl ether by gas-phase dehydration of methanol and preparation method thereof | |
CN101817731B (en) | Method for preparing polymethoxy dimethyl ether by converting methanol | |
CN106944050B (en) | A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol | |
CN104549339B (en) | A kind of methane selectively oxidizing catalyst and its preparation method and application | |
CN102211036A (en) | Modified molecular sieve catalyst, and precursor and preparation method thereof | |
CN106890669B (en) | A kind of catalyst producing methyl acetate, preparation method and application | |
CN101704716A (en) | Method for directly preparing methanol by partially oxidizing methane | |
CN109603837B (en) | Preparation method of Cu/Ce/Co catalyst for furfural liquid-phase hydrogenation | |
CN104707646A (en) | Catalyst for toluene preparation through oxidative dehydrogenation of dimethyl ether, preparation method and applications thereof | |
CN105642351A (en) | Heteropolyacid ammonium salt catalyst and preparation method thereof | |
CN106944143A (en) | heteropoly acid ammonium type catalyst and its preparation method | |
CN102911693A (en) | Fischer-Tropsch synthesis method by employing mixed catalyst | |
CN103709018A (en) | Method for preparing guaiacol | |
CN106890670B (en) | A kind of Dimethyl ether carbonylation produces catalyst and its application of methyl acetate | |
CN104549223A (en) | Catalyst for synthesizing methanol and methanal by methane selective oxidation as well as preparation method and application of catalyst | |
CN108586247B (en) | Method for preparing methyl acetate by carbonylation of dimethyl ether | |
CN107876040B (en) | Catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof | |
CN105642352A (en) | Preparation method of heteropolyacid ammonium salt catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |