CN101003021A - Catalyst for oxosynthesis of methylal by using dimethyl ether as raw material, its preparing method and application - Google Patents
Catalyst for oxosynthesis of methylal by using dimethyl ether as raw material, its preparing method and application Download PDFInfo
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- CN101003021A CN101003021A CN 200710061438 CN200710061438A CN101003021A CN 101003021 A CN101003021 A CN 101003021A CN 200710061438 CN200710061438 CN 200710061438 CN 200710061438 A CN200710061438 A CN 200710061438A CN 101003021 A CN101003021 A CN 101003021A
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Abstract
A catalyst with high activity, stability and selectivity for prepring methylal by oxidizing dimethyl ether is proportionally prepared from heteropoly acid, carrier, and the first and the second modifying components through impregnation method.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method and application, relate in particular to a kind of catalyst and preparation method and application of dimethyl ether oxo-synthesis formal.
Background technology
Dimethoxym ethane (Dimethoxymethane, DMM) be a kind of important chemical material,, can improve the combustion position of diesel oil in engine owing to have higher oxygen content and Cetane number, improve the thermal efficiency, reduce pollutant emission and be considered to a kind of diesel fuel additives that has application prospect.At present, Chinese scholars is all used oxygenatedchemicals (dimethyl carbonate, dimethyl ether, dimethoxym ethane etc.) in research and is made diesel fuel additives.In industrial application prospect then is DME and DMM preferably, and DMM is much better than DME in some aspects.Result of the test shows, adds in diesel oil that atomizing, the engine soot emissions that 5%～10% dimethoxym ethane can improve diesel oil obviously descends, significantly reduces the NOx discharging, the thermal efficiency increases, and provides a kind of new additive for reducing the harmful emission of diesel engine thing.In a single day the application of dimethoxym ethane in diesel oil promoted, and market will be huge.(methyl alcohol and formaldehyde 2006,4 methyl alcohol a new generation derived product dimethoxym ethane).
The method of Cheng Shu synthesizing dimethoxym ethane is the condensation reaction at the pure and mild formaldehyde of acid catalyst effect carapax et plastruw testudinis traditionally, adopt inorganic salts (sulfuric acid, hydrochloric acid) and lewis acid (as ferric trichloride, alchlor etc.) to make catalyst, but there is difficult separation and recycling, the strong and not high shortcoming of catalytic activity of corrosivity.Adopt cationic ion-exchange resin, solid acid catalysts such as crystalline aluminosilicate then have conversion ratio lower, weakness such as poor selectivity.Have the researcher adopting methanol oxidation method synthesizing dimethoxym ethane at present, but the dimethoxym ethane concentration that obtains is low, is not suitable for dimethoxym ethane and produces on a large scale.In addition, recent also someone has carried out co hydrogenation and has directly produced the method for dimethoxym ethane, but is in the exploratory stage.
In the future, dimethyl ether will be produced on a large scale by one-step method from syngas, because it has active chemical property, can provide CH
3, CH
3O and CH
3OCH
2Carry out chemical reaction Deng group, as a kind of important organic intermediate, it can derive the downstream product of many high values, and the synthetic DMM of dimethyl ether selective oxidation is a route that haves a great attraction.Liu Haichao (J.Phys.Chem.B2003,107,10840-10847) loading catalyst (0.1-0.3g) on microreactor such as grade adopts the dimethyl ether oxidizing process to produce dimethoxym ethane, but has deficiencies such as dimethyl ether conversion rate lower (0.5-2.5%) and dimethoxym ethane yield hang down.We have carried out the work of dimethyl ether selective oxidation synthesizing dimethoxym ethane, have obtained result preferably.And we have applied for patent (application number: 200510048219.X), be not too high deficiency but there is catalyst to the selectivity of synthesizing dimethoxym ethane to catalyst, preparation method and the application of dimethyl ether selective oxidation synthesizing dimethoxym ethane.
Summary of the invention
Purpose of the present invention provides catalyst and the preparation method and the application of the high dimethyl ether oxo-synthesis formal of a kind of dimethoxym ethane selectivity.
The percentage by weight of catalyst of the present invention consists of: heteropoly acid 20-40%, carrier 30 as one kind-60%, the first modified component 0.05%-20.00%, the second modified component 0.5-30.00%.
Aforesaid heteropoly acid is phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or silicomolybdic acid.
Aforesaid carrier is one or more in silica gel, lanthana, aluminium oxide, zirconia, titanium oxide or the molecular sieve.
Aforesaid first modified component is to contain in cerium, samarium, caesium, lanthanum, nickel, zinc, magnesium, zirconium, molybdenum, strontium, aluminium or the titanium elements one or more.
Aforesaid second modified component is to contain one or more of potassium, manganese, vanadium, tin, cadmium, iron, palladium, copper or cobalt element.
Method for preparing catalyst of the present invention is as follows:
At first, the salt of the heteropoly acid and first modified component is pressed catalyst forms with incipient impregnation behind the dissolved in distilled water to carrier, left standstill 2-24 hour, 100-130 ℃ of oven dry, 300-700 ℃ following roasting 2-8 hour, modification heteropoly acid/carrier; Secondly, the salt of second modified component press catalyst forms with incipient impregnation behind the dissolved in distilled water to modification heteropoly acid/carrier, left standstill 4-24 hour, 100-130 ℃ of oven dry, 300-700 ℃ following roasting 2-10 hour, can make the catalyst that reacts required.
Aforesaid first modified component is to contain in the salt of cerium, samarium, caesium, lanthanum, nickel, zinc, magnesium, zirconium, molybdenum, strontium, aluminium or titanium elements one or more.The salt of described first modified component is nitrate, chlorate or sulfate.
Aforesaid second modified component is to contain in the salt of potassium, manganese, vanadium, tin, cadmium, iron, palladium, copper or cobalt element one or more.The salt of described second modified component is nitrate, chlorate or sulfate.
Application of Catalyst method of the present invention is: the mol ratio of raw material dimethyl ether and oxygen is controlled at 1-8: between the 1-8, react reaction velocity 100-2000h in fixed bed reactors
-1, reaction temperature is 200-420 ℃, and reaction pressure is 0.1-5MPa, and the reaction time is 10 minutes-24 hours, promptly gets dimethoxym ethane.
Advantage of the present invention is as follows:
1, heteropolyacid catalyst is done further modification, it has acidity preferably and the difunctional effect of oxidation-reduction quality, is beneficial to dimethyl ether selective oxidation largely and produces dimethoxym ethane.Catalyst activity and stability are better.
2, technology of the present invention is simple, and is easy to operate.
3, the dimethoxym ethane selectivity height that makes with this method, the dimethyl ether conversion rate is higher, and the yield of dimethoxym ethane is higher.
The specific embodiment
Embodiment 1:
1, preparation catalyst: take by weighing the 4.0g silico-tungstic acid and the 0.33g cerous nitrate is dissolved in the distilled water, incipient impregnation left standstill 12 hours to 6.0g titanium dioxide, 110 ℃ of oven dry, 400 ℃ of roastings 4 hours, cerium modified silico-tungstic acid/titanium dioxide; Take by weighing the 0.96g manganese chloride then and be dissolved in the distilled water, incipient impregnation left standstill 4 hours to the cerium modified silico-tungstic acid/titanium dioxide that bakes, 120 ℃ of oven dry, 400 ℃ of roastings 4 hours.Can make the catalyst of the synthesizing dimethoxym ethane that contains 1%Ce, 4% manganese, 38% silico-tungstic acid and 57% titanium dioxide;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 3: 2 moles of proportionings of oxygen; Reaction pressure is 0.4MPa, reaction velocity 400h
-1, reaction temperature is 330 ℃, and the reaction time is 0.5 hour, can make selectivity at 53% dimethoxym ethane, and the dimethyl ether conversion rate is 15.0%.
Embodiment 2:
1, preparation catalyst: take by weighing samarium oxide 0.2g,, be dissolved in the distilled water with the 6.7g silico-tungstic acid then with obtaining samarium trichloride behind a small amount of diluted hydrochloric acid dissolution, incipient impregnation left standstill 6 hours to 10g silica gel, 110 ℃ of oven dry, 350 ℃ of roastings 6 hours, samarium modification silico-tungstic acid/silica gel; Take by weighing the 1.19g manganese chloride then and be dissolved in the distilled water, incipient impregnation left standstill 4 hours in the samarium modification silico-tungstic acid/silica gel that bakes, 130 ℃ of oven dry, 400 ℃ of roastings 4 hours.Can make the catalyst of the synthesizing dimethoxym ethane that contains 1% samarium, 3% manganese, 38.4% silico-tungstic acid and 57.6% silica gel;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 4: 3 moles of proportionings of oxygen; Reaction pressure is at 0.5MPa; Reaction velocity is 600h
-1Reaction temperature is 300 ℃, and the reaction time is 30min, can make selectivity and be 58.0% dimethoxym ethane, and the dimethyl ether conversion rate is 14.0%.
Embodiment 3,
1, preparation catalyst: take by weighing the 0.42g samarium oxide, use a small amount of diluted hydrochloric acid dissolution and 7.0g phosphotungstic acid to be dissolved in the distilled water, incipient impregnation left standstill 4 hours to 10.0g silica gel, 120 ℃ of oven dry, and 400 ℃ of roastings 4 hours must samarium modification phosphotungstic acid/silica gel; Taking by weighing the 1.53g zinc nitrate then is dissolved in the distilled water, incipient impregnation left standstill 3 hours in the samarium modification phosphotungstic acid/silica gel that bakes, 130 ℃ of oven dry, 400 ℃ of roastings 3 hours can make the catalyst of the synthesizing dimethoxym ethane that contains 2% samarium, 3% zinc, 38% phosphotungstic acid and 57% silica gel;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 5: 3 moles of proportionings of oxygen; Reaction pressure is 0.7 MPa; Reaction velocity is 800h
-1Reaction temperature is 290 ℃, and the reaction time is 1h, and obtaining the dimethoxym ethane selectivity is 51.0%, and the dimethyl ether conversion rate is 16.0%.
Embodiment 4,
1, preparation catalyst: take by weighing 0.83g lanthanum nitrate and 4.0g silico-tungstic acid and be dissolved in and be impregnated in the distilled water on 2g aluminium oxide and the 4g titanium oxide mixed carrier, left standstill 5 hours, 110 ℃ of oven dry, 380 ℃ of roastings 5 hours, lanthanum modification silico-tungstic acid/aluminium oxide-titanium oxide; Take by weighing the 3.23g manganese chloride then and be dissolved in the distilled water, incipient impregnation left standstill 6 hours to the lanthanum modification silico-tungstic acid/aluminium oxide-titanium oxide that bakes, 120 ℃ of oven dry, 410 ℃ of roastings 4 hours.Can make the catalyst of the synthesizing dimethoxym ethane that contains 3% lanthanum, 12% manganese, 34% silico-tungstic acid, 17% aluminium oxide and 34% titanium oxide;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 2: 1 moles of proportionings of oxygen; Reaction pressure is 0.2MPa; Reaction velocity is 400h
-1Reaction temperature is 310 ℃, and reaction time 15min gets final product to such an extent that selectivity is 54% dimethoxym ethane, and the dimethyl ether conversion rate is 18%.
Embodiment 5,
1, preparation catalyst: take by weighing the 0.3g cesium nitrate, 0.4g samarium oxide (dissolving with small amount of hydrochloric acid) and 6.7g silico-tungstic acid are dissolved in the distilled water together, incipient impregnation left standstill 8 hours to the 10g aluminium oxide, 120 ℃ of oven dry, 380 ℃ of roastings 4 hours, caesium and samarium modification silico-tungstic acid/aluminium oxide; Take by weighing the 0.8g manganese chloride then and be dissolved in the distilled water, incipient impregnation left standstill 6 hours in the caesium that bakes and samarium modification silico-tungstic acid/aluminium oxide, 130 ℃ of oven dry, 400 ℃ of roastings 4 hours.Can make the catalyst of the synthesizing dimethoxym ethane that contains 1%Cs, 2%Sm, 4% manganese, 37% silico-tungstic acid and 56% aluminium oxide;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 8: 5 moles of proportionings of oxygen; Reaction pressure is 1MPa; Reaction velocity is 800h
-1Reaction temperature is 300 ℃, and reaction time 15min gets final product to such an extent that selectivity is 62% dimethoxym ethane, and the dimethyl ether conversion rate is 16%.
Embodiment 6
1, preparation catalyst: take by weighing 1.5g nickel nitrate, 2.4g cerous nitrate and 10g silico-tungstic acid and be dissolved in the distilled water together, incipient impregnation is to the carrier that mixes with 10g silica gel and 5g titanium oxide, left standstill 24 hours, 110 ℃ of oven dry of spending the night, 360 ℃ of roastings 4 hours, nickel and cerium modified silico-tungstic acid/silica gel-titanium oxide; Take by weighing the 0.8g cobalt nitrate then and the 2.5g manganese nitrate is dissolved in the distilled water, incipient impregnation left standstill 10 hours in the nickel that bakes and cerium modified silico-tungstic acid/silica gel-titanium oxide, 130 ℃ of oven dry, 400 ℃ of roastings 6 hours.Can make the catalyst of the synthesizing dimethoxym ethane that contains 2%Ni, 4%Ce, 1%Co, 4%Mn, 35% silico-tungstic acid, 36% silica gel and 18% titanium oxide;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 7: 5 moles of proportionings of oxygen; Reaction pressure is 0.3MPa; Reaction velocity is 500h
-1Reaction temperature is 310 ℃, and reaction time 15min gets final product to such an extent that selectivity is 60% dimethoxym ethane, and the dimethyl ether conversion rate is 18%.
Embodiment 7
1, preparation catalyst: take by weighing the 0.45g strontium nitrate, 0.22g zirconium nitrate, 0.23g samarium oxide (dissolving with small amount of hydrochloric acid) and 4g silico-tungstic acid are dissolved in the medium volume of distilled water together and are impregnated on the 6g silica gel, left standstill 12 hours, 120 ℃ of oven dry of spending the night, 380 ℃ of roastings 4 hours, strontium, zirconium and samarium modification silico-tungstic acid/silica gel; Take by weighing the 0.6g butter of tin then and be dissolved in the distilled water, incipient impregnation left standstill 12 hours in the strontium that bakes, zirconium and samarium modification silico-tungstic acid/silica gel, 130 ℃ of oven dry, 360 ℃ of roastings 6 hours.Can make the catalyst of the synthesizing dimethoxym ethane that contains 2%Sr, 2%Sm, 1%Zr, 5%Sn, 36% silico-tungstic acid, 54% silica gel;
2, be reflected in the continuous fixed bed reactor and carry out; Raw material is pressed dimethyl ether and 5: 6 moles of proportionings of oxygen; Reaction pressure is 0.8MPa; Reaction velocity is 600h
-1Reaction temperature is 300 ℃, and reaction time 0.5h gets final product to such an extent that selectivity is 68% dimethoxym ethane, and the dimethyl ether conversion rate is 18%.
Claims (11)
1, a kind of catalyst of dimethyl ether oxo-synthesis formal is characterized in that the percentage by weight of catalyst consists of: heteropoly acid 20-40%, carrier 30 as one kind-60%, the first modified component 0.05%-20.00%, the second modified component 0.5-30.00%.
2, the catalyst of a kind of dimethyl ether oxo-synthesis formal as claimed in claim 1 is characterized in that described heteropoly acid is phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or silicomolybdic acid.
3, the catalyst of a kind of dimethyl ether oxo-synthesis formal as claimed in claim 1 is characterized in that described carrier is one or more in silica gel, lanthana, aluminium oxide, zirconia, titanium oxide or the molecular sieve.
4, the catalyst of a kind of dimethyl ether oxo-synthesis formal as claimed in claim 1 is characterized in that described first modified component is to contain in cerium, samarium, caesium, lanthanum, nickel, zinc, magnesium, zirconium, molybdenum, strontium, aluminium or the titanium elements one or more.
5, the catalyst of a kind of dimethyl ether oxo-synthesis formal as claimed in claim 1 is characterized in that described second modified component is to contain in the salt of potassium, manganese, vanadium, tin, cadmium, iron, palladium, copper or cobalt element one or more.
6, as the Preparation of catalysts method of each a kind of dimethyl ether oxo-synthesis formal as described in the claim 1-5, it is characterized in that comprising the steps:
At first, the salt of the heteropoly acid and first modified component is pressed catalyst forms with incipient impregnation behind the dissolved in distilled water to carrier, left standstill 2-24 hour, 100-130 ℃ of oven dry, 300-700 ℃ following roasting 2-8 hour, modification heteropoly acid/carrier; Secondly, the salt of second modified component press catalyst forms with incipient impregnation behind the dissolved in distilled water to modification heteropoly acid/carrier, left standstill 4-24 hour, 100-130 ℃ of oven dry, 300-700 ℃ following roasting 2-10 hour, can make the catalyst that reacts required.
7,, it is characterized in that described first modified component is to contain in the salt of cerium, samarium, caesium, lanthanum, nickel, zinc, magnesium, zirconium, molybdenum, strontium, aluminium or titanium elements one or more as the Preparation of catalysts method of each a kind of dimethyl ether oxo-synthesis formal as described in the claim 6.
8, the Preparation of catalysts method of a kind of dimethyl ether oxo-synthesis formal as claimed in claim 7, the salt that it is characterized in that described first modified component is nitrate, chlorate or sulfate.
9,, it is characterized in that described second modified component is to contain in the salt of potassium, manganese, vanadium, tin, cadmium, iron, palladium, copper or cobalt element one or more as the Preparation of catalysts method of each a kind of dimethyl ether oxo-synthesis formal as described in the claim 6.
10, the Preparation of catalysts method of a kind of dimethyl ether oxo-synthesis formal as claimed in claim 9, the salt that it is characterized in that described second modified component is nitrate, chlorate or sulfate.
11, as the Application of Catalyst of each a kind of dimethyl ether oxo-synthesis formal as described in the claim 1-5, it is characterized in that the mol ratio of raw material dimethyl ether and oxygen is controlled at 1-8: between the 1-8, in fixed bed reactors, react reaction velocity 100-2000h
-1, reaction temperature is 200-420 ℃, and reaction pressure is 0.1-5MPa, and the reaction time is 10 minutes-24 hours, promptly gets dimethoxym ethane.
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| CN100463719C (en) * | 2007-08-31 | 2009-02-25 | 聊城大学 | Activated charcoal laden heteropoly phosphorus molybdenum tungstic acid argentic salt catalyzer and method for preparing the same and application thereof |
| CN102188975A (en) * | 2011-03-09 | 2011-09-21 | 浙江工业大学 | Loaded nickel-base bi-component catalyst and application thereof |
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| CN105964307A (en) * | 2016-05-18 | 2016-09-28 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing dimethoxy dimethyl ether by dimethyl ether oxidization as well as preparation method for catalyst and application for catalyst. |
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| US6956134B2 (en) * | 2004-01-08 | 2005-10-18 | The Regents Of The University Of California | Oxidation of methanol and/or dimethyl ether using supported molybdenum-containing heteropolyacid catalysts |
| CN100528349C (en) * | 2005-12-21 | 2009-08-19 | 中国科学院山西煤炭化学研究所 | Catalyst for oxo-synthesis of dimethyl ether to produce methylal, preparation method and application thereof |
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| CN100463719C (en) * | 2007-08-31 | 2009-02-25 | 聊城大学 | Activated charcoal laden heteropoly phosphorus molybdenum tungstic acid argentic salt catalyzer and method for preparing the same and application thereof |
| CN102188975A (en) * | 2011-03-09 | 2011-09-21 | 浙江工业大学 | Loaded nickel-base bi-component catalyst and application thereof |
| CN102188975B (en) * | 2011-03-09 | 2013-01-23 | 浙江工业大学 | Loaded nickel-base bi-component catalyst and application thereof |
| CN102513161A (en) * | 2011-11-25 | 2012-06-27 | 湘潭大学 | Naphthalene nitration catalyst as well as preparation method and application thereof |
| CN102513161B (en) * | 2011-11-25 | 2013-10-23 | 湘潭大学 | Naphthalene nitration catalyst as well as preparation method and application thereof |
| CN106140193A (en) * | 2015-04-01 | 2016-11-23 | 浙江蓝天环保高科技股份有限公司 | A kind of preparation method of the catalyst for CFC and HCFC hydrogenation-dechlorination |
| CN105964307A (en) * | 2016-05-18 | 2016-09-28 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing dimethoxy dimethyl ether by dimethyl ether oxidization as well as preparation method for catalyst and application for catalyst. |
| CN105964307B (en) * | 2016-05-18 | 2019-04-30 | 中国科学院山西煤炭化学研究所 | Dimethyl ether aoxidizes the catalyst for producing dimethoxy dimethyl ether and preparation method and application |
| CN105779077A (en) * | 2016-05-23 | 2016-07-20 | 成都弗吉亚科技有限公司 | Coal-saving emission-reduction integrating method for coal-fired boiler |
| CN105925339A (en) * | 2016-05-23 | 2016-09-07 | 成都弗吉亚科技有限公司 | Twice combustion supporting and coal saving method for coal fired boiler |
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