CN100488934C - Method of preparing formaldehyde by catalytic selection oxidation of ethylene - Google Patents
Method of preparing formaldehyde by catalytic selection oxidation of ethylene Download PDFInfo
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- CN100488934C CN100488934C CNB2006101352164A CN200610135216A CN100488934C CN 100488934 C CN100488934 C CN 100488934C CN B2006101352164 A CNB2006101352164 A CN B2006101352164A CN 200610135216 A CN200610135216 A CN 200610135216A CN 100488934 C CN100488934 C CN 100488934C
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Abstract
The present invention relates to a method for preparing formaldehyde by using ethylene as raw material, using oxygen gas or air as oxygen source and adopting gas-solid multi-phase catalytic selective oxidation reaction. The chemical composition of solid catalyst is nMoO3/SiO2 or mV2O5/SiO2, and said method includes catalyst pretreatment and catalytic reaction. Besides, said invention also provides the concrete steps and requirements of said catalyst pretreatment and catalytic reaction.
Description
Technical field
The present invention relates to a kind of formaldehyde, especially relating to a kind of is raw material with ethene, and on solid catalyst, the reaction of the catalytic selective oxidation of ethene and oxygen or air is the novel method and the relevant solid catalyst of system formaldehyde directly.
Background technology
Formaldehyde is a kind of important Organic Chemicals.With formaldehyde is raw material, can produce multiple Chemicals as resins such as urea aldehyde, phenolic aldehyde, trimeric cyanamide, Resin adhesive, plastics and polyoxymethylene engineering plastics, urotropine, tetramethylolmethane, phenolic resin coating etc.In addition, formaldehyde also is used to produce some dyestuffs, agricultural chemicals, sterilizing agent etc.Domestic formaldehyde demand had surpassed 2,600,000 tons in 2002, and the year rate of rise of formaldehyde consumption in recent years is about 13%.
The main production approach of formaldehyde is methanol catalytic oxidation or catalytic dehydrogenation at present.This process has accounted for more than 40% of methyl alcohol gross production.And the indirect reformer that the main production approach of methyl alcohol is a methane in the Sweet natural gas, promptly through obtain synthetic gas by methane vapor reforming under the nickel-base catalyst effect, synthetic gas is at Cu-ZnO-Al
2O
3Synthesizing methanol under the catalyst action.Wherein steam reforming is produced the complex technical process of synthetic gas, equipment cost height.This shows that current Formaldehyde Production flow process is many, the cost of investment height.Therefore there are many research groups to be devoted to seek for a long time both at home and abroad and a kind ofly prepare the novel method of formaldehyde,, reduce cost to simplify technology from the direct catalyzed oxidation of methane.Wherein have some research groups to report higher formaldehyde yield, but the research that repeats subsequently find that all for being oxygenant with oxygen or air, in the conversion of methane that solid catalyst surface takes place, the yield of formaldehyde is difficult to surmount 4%.Up to now, the research that directly prepares formaldehyde from methane is able to far away realize that industrialization substitutes the degree of original technology.
Ethene is one of most important basic material of present petrochemical industry.Can be divided into the liquefied gas method of using the ethane, propane and the butane that come from Sweet natural gas and petroleum naphtha, gasoline, the diesel oil method that use comes from oil from the production technique differentiation.The main raw material of China's cracking of ethylene is a petroleum naphtha at present, and its ethylene yield accounts for 60% greatly.The throughput of China's ethene in 2005 has reached 7,730,000 tons/year, estimates that the ethylene production capacity of China will be above 2,000 ten thousand tons/year in 2010.Ethene maximum application in industry is polymerization, secondly is oxidation, alkylation, hydration and halogenation etc.Its oxidation products mainly contains important compound such as oxyethane, ethylene glycol, acetaldehyde, acetate and vinyl-acetic ester, and these derivatives all are important source material of development chemical industry.We can say up to the present, ethene with and derivative science and engineering all developed comparative maturity.Therefore development prepare the technology of formaldehyde from ethene can be easily with reference to these similar technology, even can directly transform original technology with comparalive ease and be used for Formaldehyde Production.Although similarly slough the reaction ubiquity that a carbon generates aldehyde, such as preparing phenyl aldehyde etc. from stupid ethene from alkene.But up to the present, the method for preparing formaldehyde from the direct selective oxidation of ethene is not seen in as yet in any report.
Summary of the invention
The object of the present invention is to provide a kind of ethene that uses to be raw material, use oxygen or air directly to prepare the method for formaldehyde as the gas-solid heterogeneous catalyst selective oxidation reaction of oxygen source.
Reaction equation of the present invention is:
Wherein the chemical constitution of solid catalyst is nMoO
3/ SiO
2Perhaps mV
2O
5/ SiO
2, nMoO
3/ SiO
2For being carried on the molybdenum oxide on the silica supports, n is the quality percentage composition of molybdenum oxide in catalyzer, and n equals 1%～30%, and the best is 10%～25%; MV
2O
5/ SiO
2For being carried on the barium oxide on the silica supports, m is the quality percentage composition of barium oxide in catalyzer, and m equals 3%～10%, and the best is 5%～7%.
SiO
2For silica mesoporous zeolite or specific surface greater than 300m
2g
-1Commercially available silica gel, silica mesoporous zeolite is SBA-15, MCM-41 etc., commercially available silica gel are Cab-O-Sil, column layer chromatography silicone rubber etc.
Catalyzer nMoO
3/ SiO
2Available immersion process for preparing, its concrete steps are as follows:
1) hydro-thermal is synthetic prepares mesoporous silicon oxide or directly adopts commodity silicon-dioxide;
2) press catalyzer and form proportioning weighing Ammonium Heptamolybdate, dissolve fully with deionized water, concentration is 0.1%～5% the Ammonium Heptamolybdate aqueous solution;
3) press catalyzer and form proportioning weighing silicon-dioxide, add in the above-mentioned aqueous solution, stir 5～10h under the room temperature after, leave standstill 5～10h, then in 60～80 ℃ water-bath, steam to the heavy-gravity paste;
4) above-mentioned paste is placed the dry 20～24h of 40～50 ℃ of vacuum, fully grind the back at 500～600 ℃ of roasting 3～6h, heat-up rate is 1 ℃/min;
5) sample after the roasting passes through compressing tablet, pulverizes, sieves, and getting 30～60 order solid particulates is catalyzer.
Catalyzer mV
2O
5/ SiO
2Available immersion process for preparing, its concrete steps are as follows:
1) hydro-thermal synthetic preparation mesoporous silicon oxide or directly commodity in use silicon-dioxide;
2) press catalyzer and form proportioning weighing ammonium meta-vanadate, dissolve fully with deionized water, concentration is 0.1%～0.5% ammonium metavanadate aqueous solution;
3) press catalyzer and form proportioning weighing silicon-dioxide, add in the above-mentioned aqueous solution, stir 5～10h under the room temperature after, leave standstill 5～10h, then in 60～80 ℃ water-bath, steam to the heavy-gravity paste;
4) above-mentioned paste is placed the dry 20～24h of 40～50 ℃ of vacuum, fully grind the back at 500～600 ℃ of roasting 3～6h, heat-up rate is 1 ℃/min;
5) sample after the roasting passes through compressing tablet, pulverizes, sieves, and getting 30～60 order solid particulates is catalyzer.
SiO
2Refer to silica mesoporous zeolite,, perhaps refer to have high-ratio surface (〉 300m as SBA-15, MCM-41 etc.
2g
-1) commercially available silica gel, as Cab-O-Sil, column layer chromatography silicone rubber etc.
The present invention includes catalyst pretreatment and catalyzed reaction, catalyzed reaction is carried out in atmospheric fixed bed reactor, the steps include:
1) catalyst pretreatment: 0.20g30～above-mentioned catalyzer of 60 purposes (5～20) wt% is packed in the reaction tubes, at N
2: O
2=1:1, overall flow rate are 20ml min
-1Atmosphere under be warming up to 600 ℃ of pre-treatment 30min;
2) catalyzed reaction: with beginning reaction behind the nitrogen purging 20min, reaction conditions is N by volume
2: O
2: C
2H
4=8:1:1, overall flow rate are 150ml min
-1, temperature of reaction is 500～600 ℃.
In preparation process, catalyzed reaction is carried out in atmospheric fixed bed microreactor, and the unstripped gas of reaction is the mixed gas of ethene and air or ethene, oxygen and nitrogen, and air speed can be controlled in 13320～133200h
-1, reaction tubes is made of quartzy, the catalyzer portion that is placed in one.The reaction bed temperature unanimity by a thermocouple measurement that places quartzy inner sleeve, is controlled the Reaktionsofen temperature automatically by full-automatic temperature controller, temperature fluctuation range ± 0.5 ℃.The reaction end gas online check and analysis of gas chromatograph.Product can be used the gas-chromatography on-line analysis.The present invention is under appropriate condition, and the transformation efficiency of ethene reaches 30%～50%, and simultaneously the selectivity of formaldehyde reaches 50%～70%, and by product is acetaldehyde, carbon monoxide and carbonic acid gas and other product on a small quantity.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
Take by weighing the 0.50g Ammonium Heptamolybdate and dissolve fully, take by weighing the 1.63g mesoporous molecular sieve SBA-15, add in the above-mentioned solution by proportioning with the 30ml deionized water, stir 8h under the room temperature, leave standstill 10h, 70 ℃ of water-baths are steamed to the heavy-gravity paste, dry 20h in 50 ℃ of vacuum drying ovens fully grinds the back with 1 ℃ of mlin
-1Heat-up rate be warming up to 600 ℃ of roasting 6h, make 20wt%MoO
3/ SBA-15 catalyzer.With the pressed powder compressing tablet after the roasting, pulverize, sieve, getting 30～60 purpose solid particulates is ethylene catalyst selective oxidation catalyst for reaction.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 20wt%MoO
3/ SBA-15 catalyzer is packed in the reaction tubes, at N
2: O
2=1:1, overall flow rate are 20ml min
-1Atmosphere under temperature programming to 600 ℃ pre-treatment 30min, with begin behind the nitrogen purging 20min reaction.Reaction conditions: N
2: O
2: C
2H
4=8:1:1 (volume ratio), overall flow rate are 150ml min
-1, normal pressure, temperature of reaction is 550 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 1.
Table 1 20wt%MoO
3The catalytic performance of/SBA-15 catalyzer (T=550 ℃)
| The transformation efficiency of ethene (%) | 15.4 |
| The selectivity of formaldehyde (%) | 71.5 |
| The selectivity of acetaldehyde (%) | 13.2 |
| The selectivity of carbon monoxide (%) | 12.2 |
| The selectivity of carbonic acid gas (%) | 2.3 |
| Other organic selectivity (%) | 0.8 |
Embodiment 2
The Preparation of Catalyst concrete steps are with embodiment 1.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 20wt%MoO
3/ SBA-15 catalyzer is packed in the reaction tubes.At N
2: O
2=1:1, overall flow rate are 20ml min
-1Atmosphere under temperature programming to 600 ℃ pre-treatment 30min, with begin behind the nitrogen purging 20min reaction.Reaction conditions: N
2: O
2: C
2H
4=8:1:1 (volume ratio), overall flow rate are 150ml min
-1, normal pressure, temperature of reaction is 590 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 2.
Table 2 20wt%MoO
3The catalytic performance of/SBA-15 catalyzer (T=590 ℃)
| The transformation efficiency of ethene (%) | 47.3 |
| The selectivity of formaldehyde (%) | 61.2 |
| The selectivity of acetaldehyde (%) | 2.7 |
| The selectivity of carbon monoxide (%) | 31.1 |
| The selectivity of carbonic acid gas (%) | 4.9 |
| Other organic selectivity (%) | 0.1 |
Embodiment 3
Take by weighing the 0.09g ammonium meta-vanadate and dissolve fully, take by weighing the 1.33g mesoporous molecular sieve SBA-15, add in the above-mentioned solution by proportioning with the 30ml deionized water, stir 8h under the room temperature, leave standstill 10h, 70 ℃ of water-baths are steamed to the heavy-gravity paste, dry 20h in 50 ℃ of vacuum drying ovens fully grinds the back with 1 ℃ of min
-1Heat-up rate be warming up to 600 ℃ of roasting 6h, make 5wt%V
2O
5/ SBA-15 catalyzer.With the pressed powder compressing tablet after the roasting, pulverize, sieve, getting 30～60 purpose solid particulates is ethylene catalyst selective oxidation catalyst for reaction.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 5wt%V
2O
5/ SBA-15 catalyzer is packed in the reaction tubes.At N
2: O
2=1:1, overall flow rate are 20ml min
-1Atmosphere under temperature programming to 600 ℃ pre-treatment 30min, with begin behind the nitrogen purging 20min reaction.Reaction conditions: N
2: O
2: C
2H
4=8:1:1 (volume ratio), overall flow rate are 150ml min
-1, normal pressure, temperature of reaction is 550 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 3.
Table 3 5wt%V
2O
5The catalytic performance of/SBA-15 catalyzer (T=550 ℃)
| The transformation efficiency of ethene (%) | 20.8 |
| The selectivity of formaldehyde (%) | 23.6 |
| The selectivity of acetaldehyde (%) | 22.0 |
| The selectivity of carbon monoxide (%) | 39.8 |
| The selectivity of carbonic acid gas (%) | 14.6 |
Embodiment 4
The Preparation of Catalyst concrete steps are with embodiment 3.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 5wt%V
2O
5/ SBA-15 catalyzer is packed in the reaction tubes.At N
2: O
2=1:1, overall flow rate are 20ml min
-1Atmosphere under temperature programming to 600 ℃ pre-treatment 30min, with begin behind the nitrogen purging 20min reaction.Reaction conditions: N
2: O
2: C
2H
4=8:1:1 (volume ratio), overall flow rate are 150ml min
-1, normal pressure, temperature of reaction is 600 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 4.
Table 4 5wt%V
2O
5The catalytic performance of/SBA-15 catalyzer (T=600 ℃)
| The transformation efficiency of ethene (%) | 40.8 |
| The selectivity of formaldehyde (%) | 12.6 |
| The selectivity of acetaldehyde (%) | 7.8 |
| The selectivity of carbon monoxide (%) | 64.1 |
| The selectivity of carbonic acid gas (%) | 15.5 |
Embodiment 5
Take by weighing the 0.50g Ammonium Heptamolybdate and dissolve fully with the 30ml deionized water, taking by weighing mesopore molecular sieve MCM-41 by proportioning is 1.63g, adds in the above-mentioned solution, stir 8h under the room temperature, leave standstill 10h, 70 ℃ of water-baths are steamed to the heavy-gravity paste, dry 20h in 50 ℃ of vacuum drying ovens fully grinds the back with 1 ℃ of min
-1Heat-up rate be warming up to 600 ℃ of roasting 6h, make 20wt%MoO
3/ MCM-41 catalyzer.With the pressed powder compressing tablet after the roasting, pulverize, sieve, getting 30～60 purpose solid particulates is ethylene catalyst selective oxidation catalyst for reaction.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 20wt%MoO
3/ MCM-41 catalyzer is packed in the reaction tubes.Pretreatment condition is with embodiment 1.Reaction conditions: N
2: O
2: C
2H
4=8:1:1 (volume ratio), overall flow rate are 150ml min
-1, normal pressure, temperature of reaction is 590 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 5.
Table 5 20wt%MoO
3The catalytic performance of/MCM-41 catalyzer (T=590 ℃)
| The transformation efficiency of ethene (%) | 31.8 |
| The selectivity of formaldehyde (%) | 58.2 |
| The selectivity of acetaldehyde (%) | 2.0 |
| The selectivity of carbon monoxide (%) | 34.2 |
| The selectivity of carbonic acid gas (%) | 4.9 |
| Other organic selectivity (%) | 0.7 |
Embodiment 6
Take by weighing the 0.50g Ammonium Heptamolybdate and dissolve fully, take by weighing 1.63g Cab-O-Sil, add in the above-mentioned solution by proportioning with the 30ml deionized water, stir 8h under the room temperature, leave standstill 10h, 70 ℃ of water-baths are steamed to the heavy-gravity paste, dry 20h in 50 ℃ of vacuum drying ovens fully grinds the back with 1 ℃ of min
-1Heat-up rate be warming up to 600 ℃ of roasting 6h, make 20wt%MoO
3/ Cab-O-Sil catalyzer.With the pressed powder compressing tablet after the roasting, pulverize, sieve, getting 30～60 purpose solid particulates is ethylene catalyst selective oxidation catalyst for reaction.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 20wt%MoO
3/ Cab-O-Sil catalyzer is packed in the reaction tubes.Pretreatment condition is with embodiment 1.Reaction conditions: N
2: O
2: C
2H
4=8:1:1 (volume ratio), overall flow rate are 150ml min
-1, normal pressure, temperature of reaction is 590 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 6.
Table 6 20wt%MoO
3The catalytic performance of/Cab-O-Sil catalyzer (T=590 ℃)
| The transformation efficiency of ethene (%) | 21.6 |
| The selectivity of formaldehyde (%) | 68.9 |
| The selectivity of acetaldehyde (%) | 3.7 |
| The selectivity of carbon monoxide (%) | 22.9 |
| The selectivity of carbonic acid gas (%) | 3.1 |
| Other organic selectivity (%) | 1.3 |
Embodiment 7
Taking by weighing the 0.50g Ammonium Heptamolybdate dissolves fully with the 30ml deionized water, take by weighing 1.63g column layer chromatography silicone rubber (Silica gel) by proportioning, add in the above-mentioned solution, stir 8h under the room temperature, leave standstill 10h, 70 ℃ of water-baths are steamed to the heavy-gravity paste, and dry 20h in 50 ℃ of vacuum drying ovens fully grinds the back with 1 ℃ of min
-1Heat-up rate be warming up to 600 ℃ of roasting 6h, make 20wt%MoO
3/ Silica gel catalyzer.With the pressed powder compressing tablet after the roasting, pulverize, sieve, getting 30～60 purpose solid particulates is ethylene catalyst selective oxidation catalyst for reaction.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 20wt%MoO
3/ Silica gel catalyzer is packed in the reaction tubes.Pretreatment condition is with embodiment 1.Reaction conditions: N
2: O
2: C
2H
4=8:1:1 (volume ratio), overall flow rate are 150ml min
-1, normal pressure, temperature of reaction is 590 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 7.
Table 7 20wt%MoO
3The catalytic performance of/Silica gel catalyzer (T=590 ℃)
| The transformation efficiency of ethene (%) | 7.3 |
| The selectivity of formaldehyde (%) | 73.9 |
| The selectivity of acetaldehyde (%) | 1.5 |
| The selectivity of carbon monoxide (%) | 20.7 |
| The selectivity of carbonic acid gas (%) | 3.2 |
| Other organic selectivity (%) | 0.7 |
Embodiment 8
The Preparation of Catalyst concrete steps are with embodiment 1.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 20wt%MoO
3/ SBA-15 catalyzer is packed in the reaction tubes.Pretreatment condition is with embodiment 1.Reaction conditions: ethylene partial pressure is 10.1kPa, and oxygen partial pressure is 3.4kPa, and as balanced gas, overall flow rate is 150ml min with nitrogen
-1, normal pressure, temperature of reaction is 575 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 8.
Table 8 20wt%MoO
3The catalytic performance of/SBA-15 catalyzer (P (O
2)=3.4kPa)
| The transformation efficiency of ethene (%) | 20.6 |
| The selectivity of formaldehyde (%) | 74.3 |
| The selectivity of acetaldehyde (%) | 5.5 |
| The selectivity of carbon monoxide (%) | 16.1 |
| The selectivity of carbonic acid gas (%) | 3.8 |
| Other organic selectivity (%) | 0.3 |
Embodiment 9
The Preparation of Catalyst concrete steps are with embodiment 1.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 20wt%MoO
3/ SBA-15 catalyzer is packed in the reaction tubes.Pretreatment condition is with embodiment 1.Reaction conditions: ethylene partial pressure is 10.1kPa, and oxygen partial pressure is 33.8kPa, and as balanced gas, overall flow rate is 150ml min with nitrogen
-1, normal pressure, temperature of reaction is 575 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 9.
Table 9 20wt%MoO
3The catalytic performance of/SBA-15 catalyzer (P (O
2)=33.8kPa)
| The transformation efficiency of ethene (%) | 48.5 |
| The selectivity of formaldehyde (%) | 51.5 |
| The selectivity of acetaldehyde (%) | 1.3 |
| The selectivity of carbon monoxide (%) | 41.0 |
| The selectivity of carbonic acid gas (%) | 5.7 |
| Other organic selectivity (%) | 0.4 |
Embodiment 10
The Preparation of Catalyst concrete steps are with embodiment 1.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 20wt%MoO
3/ SBA-15 catalyzer is packed in the reaction tubes.Pretreatment condition is with embodiment 1.Reaction conditions: oxygen partial pressure is 10.1kPa, and ethylene partial pressure is 3.4kPa, and as balanced gas, overall flow rate is 150ml min with nitrogen
-1, normal pressure, temperature of reaction is 575 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 10.
Table 10 20wt%MoO
3The catalytic performance of/SBA-15 catalyzer (P (C
2H
4)=3.4kPa)
| The transformation efficiency of ethene (%) | 39.2 |
| The selectivity of formaldehyde (%) | 68.9 |
| The selectivity of acetaldehyde (%) | 2.1 |
| The selectivity of carbon monoxide (%) | 23.2 |
| The selectivity of carbonic acid gas (%) | 5.2 |
| Other organic selectivity (%) | 0.6 |
Embodiment 11
The Preparation of Catalyst concrete steps are with embodiment 1.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing 0.20g 30～60 purpose 20wt%MoO
3/ SBA-15 catalyzer is packed in the reaction tubes.Pretreatment condition is with embodiment 1.Reaction conditions: oxygen partial pressure is 10.1kPa, and ethylene partial pressure is 23.6kPa, and as balanced gas, overall flow rate is 150ml min with nitrogen
-1, normal pressure, temperature of reaction is 575 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 11.
Table 11 20wt%MoO
3The catalytic performance of/SBA-15 catalyzer (P (C
2H
4)=23.6kPa)
| The transformation efficiency of ethene (%) | 32.8 |
| The selectivity of formaldehyde (%) | 61.8 |
| The selectivity of acetaldehyde (%) | 3.4 |
| The selectivity of carbon monoxide (%) | 29.4 |
| The selectivity of carbonic acid gas (%) | 4.8 |
| Other organic selectivity (%) | 0.6 |
Embodiment 12
The Preparation of Catalyst concrete steps are with embodiment 1.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing a certain amount of 30～60 purpose 20wt%MoO
3/ SBA-15 catalyzer is packed in the reaction tubes.Pretreatment condition is with embodiment 1.Reaction conditions: catalyst levels 0.02g, air speed is 133200h
-1, N
2: O
2: C
2H
4=8:1:1 (volume ratio) is for overall flow rate is 150ml min
-1, normal pressure, temperature of reaction is 590 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 12.
Table 12 20wt%MoO
3(air speed is 133200h to the catalytic performance of/SBA-15 catalyzer
-1)
| The transformation efficiency of ethene (%) | 1.2 |
| The selectivity of formaldehyde (%) | 39.1 |
| The selectivity of acetaldehyde (%) | 20.7 |
| The selectivity of carbon monoxide (%) | 8.5 |
| The selectivity of carbonic acid gas (%) | 1.7 |
| Other organic selectivity (%) | 0 |
Embodiment 13
The Preparation of Catalyst concrete steps are with embodiment 1.
Catalyzed reaction is carried out (quartz reaction bore 8mm) in atmospheric fixed bed reactor, take by weighing a certain amount of 30～60 purpose 20wt%MoO
3/ SBA-15 catalyzer is packed in the reaction tubes.Pretreatment condition is with embodiment 1.Reaction conditions: catalyst levels 0.20g, air speed is 13320h
-1, N
2: O
2: C
2H
4=8:1:1 (volume ratio) is for overall flow rate is 150ml min
-1, normal pressure, temperature of reaction is 590 ℃.Product gas-chromatography on-line analysis.Catalyzed reaction the results are shown in table 13.
Table 13 20wt%MoO
3(air speed is 13320h to the catalytic performance of/SBA-15 catalyzer
-1)
| The transformation efficiency of ethene (%) | 50.5 |
| The selectivity of formaldehyde (%) | 62.3 |
| The selectivity of acetaldehyde (%) | 3.2 |
| The selectivity of carbon monoxide (%) | 29.7 |
| The selectivity of carbonic acid gas (%) | 4.2 |
| Other organic selectivity (%) | 0.5 |
Claims (6)
1. one kind prepares the method for formaldehyde from the ethylene catalyst selective oxidation, it is characterized in that its reaction equation is:
Wherein the chemical constitution of solid catalyst is nMoO
3/ SiO
2Perhaps mV
2O
5/ SiO
2, nMoO
3/ SiO
2For being carried on the molybdenum oxide on the silica supports, n is the quality percentage composition of molybdenum oxide in catalyzer, and n equals 1%～30%; MV
2O
5/ SiO
2For being carried on the barium oxide on the silica supports, m is the quality percentage composition of barium oxide in catalyzer, and m equals 3%～10%.
2. as claimed in claim 1ly a kind ofly prepare the method for formaldehyde, it is characterized in that described n is 10%～25% from the ethylene catalyst selective oxidation.
3. as claimed in claim 1ly a kind ofly prepare the method for formaldehyde, it is characterized in that described m is 5%～7% from the ethylene catalyst selective oxidation.
4. as claimed in claim 1ly a kind ofly prepare the method for formaldehyde, it is characterized in that described SiO from ethylene catalytic oxidation
2For silica mesoporous zeolite or specific surface greater than 300m
2g
-1Commercially available silica gel.
5. as claimed in claim 4ly a kind ofly prepare the method for formaldehyde, it is characterized in that described silica mesoporous zeolite is SBA-15 or MCM-41 from ethylene catalytic oxidation.
6. as claimed in claim 4ly a kind ofly prepare the method for formaldehyde, it is characterized in that described commercially available silica gel is Cab-O-Sil or column layer chromatography silicone rubber from ethylene catalytic oxidation.
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|---|---|---|---|
| CNB2006101352164A CN100488934C (en) | 2006-11-08 | 2006-11-08 | Method of preparing formaldehyde by catalytic selection oxidation of ethylene |
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|---|---|---|---|
| CNB2006101352164A CN100488934C (en) | 2006-11-08 | 2006-11-08 | Method of preparing formaldehyde by catalytic selection oxidation of ethylene |
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| CN100488934C true CN100488934C (en) | 2009-05-20 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103446A (en) * | 1986-05-12 | 1987-12-09 | 加拿大原子能有限公司 | The method of oxidizing gaseous substances |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103446A (en) * | 1986-05-12 | 1987-12-09 | 加拿大原子能有限公司 | The method of oxidizing gaseous substances |
Non-Patent Citations (4)
| Title |
|---|
| . IGLESIA E.J.CATAL,Vol.208 No.1. 2002 |
| . IGLESIA E.J.CATAL,Vol.208 No.1. 2002 * |
| 负载型MoOx和VOx催化剂上二甲醚选择性氧化制备甲醛反应. 黄秀敏.催化学报，第25卷第4期. 2004 |
| 负载型MoOx和VOx催化剂上二甲醚选择性氧化制备甲醛反应. 黄秀敏.催化学报，第25卷第4期. 2004 * |
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