CN104043442A - Titanium aluminum base catalyst synthesis and application thereof to dimethoxy methane production from methanol oxidation - Google Patents

Titanium aluminum base catalyst synthesis and application thereof to dimethoxy methane production from methanol oxidation Download PDF

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CN104043442A
CN104043442A CN201410222214.3A CN201410222214A CN104043442A CN 104043442 A CN104043442 A CN 104043442A CN 201410222214 A CN201410222214 A CN 201410222214A CN 104043442 A CN104043442 A CN 104043442A
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CN104043442B (en
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巩金龙
孟亚利
王拓
马新宾
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Tianjin University
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Abstract

The invention relates to titanium aluminum base catalyst synthesis and application thereof to dimethoxy methane production from methanol oxidation. A composite carrier is alumina and titania, and an active component is molybdenum oxide and vanadium oxide in the mass ratio with the carrier of 5%-50%; and TiO2 account for the 10%-90% of the carrier. A ball milling method for preparing the composite carrier employs industrial alumina and industrial titanium dioxide for high-energy ball milling in a ball mill. Compared with the existing catalyst systems, the catalyst has simple preparation process, low cost and low requirement on the preparation method; at the same time, DMM prepared from methanol through selective oxidation has little by-products and is clean and pollution-free; and the process line is short and simple for operation, has low reaction temperature, mild conditions and low energy consumption. The catalyst provided by the invention has broader in industrial application prospects in methanol oxidation into DMM.

Description

Titanium aluminium-based catalyst synthesizes and the application in methanol oxidation dimethoxymethane processed
Technical field
The invention belongs to-kind of TiO 2-Al 2o 3what complex carrier was catalyst based synthesizes with and synthesizes in dimethoxymethane and apply at methanol oxidation.
Background technology
Face now petroleum resources worsening shortages, oil price grows to even greater heights, and methyl alcohol, as C1 chemistry foundation stone product, replaces petrochemical materials source to become a kind of trend.And the comprehensive utilization of methyl alcohol becomes the representative of carbon one development of chemical industry, it is the potentiality approach that solves the problems such as the raw material problem of petrochemical industry and Clean Fuel Production technology.Dimethoxymethane (DMM), as the downstream product of methanol oxidation, is having great potential application foreground aspect energy and environment protection.Dimethoxymethane is colourless, nontoxic, of many uses, it is environment amenable industrial chemicals, be the organic solvent that medical cosmetics industry is good, what is more important can be used as a kind of novel fuel additive, replaces part diesel oil, reduce crude oil import amount, can improve the combustibility of diesel oil, be conducive to reduce the discharge capacity of diesel engine vent gas nitrogen oxide and particle, the thermal efficiency also can significantly improve simultaneously.Therefore develop simple environment protection, economic and practical DMM synthetic route is the inexorable trend of current era development.
In traditional handicraft method, to could be generally DMM by methanol conversion through two steps, first using silver or the iron-molybdic catalyst with oxidation-reducibility is formaldehyde by methyl alcohol selective oxidation, and then formaldehyde and methyl alcohol will generate DMM through condensation reaction again on acid catalyst.Although this route process conditions comparative maturity, energy consumption is higher, and equipment investment is larger, and pollution is simultaneously also more serious, so limited the cheap of DMM, produces and is widely used.At present both at home and abroad in the research of synthetic dimethoxymethane, because of methyl alcohol direct oxidation method, to have technological process short, the advantage that cost is low, receive increasing concern and research, it is the new technology of a kind of synthetic DMM, the catalyst using requires to have concurrently acidity and redox property, and the coupling of surface acidity and redox property is the key that obtains methyl alcohol high conversion and DMM high selectivity.
Reported at present multiple catalyst systems, as noble metal support type ReO x(Journal of Physical Chemistry B, 2002,106 (17): 4441-4449), carried heteropoly acid (Journal of Physical Chemistry B, 2003,107 (39): 10840-10847), the V that modifies of surface acidity 2o 5/ TiO 2(Chemical Communications, 2007, (21): 2172-2174), iron-molybdic catalyst (Applied Catalysis B:Environmental, 2014, (145): 126 – 135) and amorphous MoV base composite oxidate (Chemical Communications, 2008, (7): 865-867) etc., in above catalyst system and catalyzing, unformed MoV base composite oxidate have higher methanol conversion and DMM selective, but its catalyst forms and preparation method is complicated, is unfavorable for DMM suitability for industrialized production.Noble metal catalyst is selectively good simultaneously, but because noble metal is expensive, and the high oxide of Re is at high temperature volatile, may have difficulties in actual use, has restricted the application of this kind of catalyst.Catalyst based on current Methanol DMM and technological reaction conditional request harshness, the important content that the selective high catalyst of the therefore methyl alcohol direct oxidation process of the applicable suitability for industrialized production of exploitation, and methanol conversion and DMM is current research.
In the design of methanol oxidation DMM catalyst processed, the coupling of surface acidity and redox property is the key that obtains methyl alcohol high conversion and DMM high selectivity.The catalytic performance of molybdenum oxide and vanadium oxide is all very excellent, is all important industrial catalyst, and the catalytic reaction of their application is very extensive, and it is widely used in the oxidative dehydrogenation of alcohols and hydro carbons, hydrodesulfurization catalysis, NO xselective catalytic reduction reaction.γ-Al 2o 3be a kind of common acidity of catalyst carrier, there is high-specific surface area and good mechanical performance, the tetrahedron that it has and octahedral voids, the research that can be vanadium oxide and molybdenum oxide catalytic effect provides good basis.And TiO 2as auxiliary agent, be entrained in the γ-Al of Large ratio surface 2o 3after carrier, produced more significant result.Literature research is in the past pointed out TiO 2-Al 2o 3compound in photocatalysis field than independent TiO 2there is better photocatalytic activity, have benefited from TiO 2-Al 2o 3compound makes catalyst have abundanter photocatalytic activity site to promote the transmittance process of electronics.
Therefore utilize vanadium oxide and the good oxidation catalytic property of molybdenum oxide, selective oxidation vanadium or molybdenum oxide are as the oxidation activity site of catalyst.And by the good electronics transmission capacity of titanium oxide, by TiO 2mix acid carrier aluminium oxide (γ-Al 2o 3) in, obtain the TiO that there is special catalyst structure and can regulate and control acid amount 2-Al 2o 3complex carrier.Novel V is prepared in exploitation thus 2o 5/ TiO 2-Al 2o 3and MoO 3/ TiO 2-Al 2o 3complex carrier is catalyst based.
Summary of the invention
The present invention is devoted to provide a kind of take methyl alcohol and makes the process application of DMM as the direct selective oxidation of raw material, for the deficiency of existing technique, the present invention prepares TiO a kind of cheap and easy to get, applicable suitability for industrialized production, the directly synthetic dimethoxymethane of low-temp methanol oxidation 2-Al 2o 3the application that complex carrier is catalyst based.By preparation method's control, the catalyst of acquisition has specific structure, and catalytic performance is good, has higher methanol conversion and DMM selective.
Technical scheme of the present invention is as follows:
A titanium aluminum-base composite carried catalyst, complex carrier is aluminium oxide and titanium oxide, active component is molybdenum oxide or vanadium oxide; Take carrier as 100% calculating, and the mass ratio that active component molybdenum oxide or vanadium oxide are carrier is 5%-50%; TiO 2the mass percent that accounts for carrier is 10%-90%.
The preparation method of catalyst of the present invention, adopts ball-milling method, and step is as follows:
1) using water or ethanol as solvent, commercial alumina and industrial titanium dioxide are evenly mixed to TiO 2-Al 2o 3mass ratio is 1:9-9:1;
2) mixture is put into high energy ball mill; Set Ball-milling Time 10-48h, ball milling method is that 15-30min replaces clockwise with counterclockwise, rotating speed 100-600r/min;
3) after ball milling, mixture is dried, roasting, obtain TiO 2-Al 2o 3complex carrier;
4) presoma ammonium metavanadate or the ammonium molybdate of active component are dissolved in the water, dipping TiO 2-Al 2o 3complex carrier, obtains MoO 3/ TiO 2-Al 2o 3or V 2o 5/ TiO 2-Al 2o 3catalyst.
Catalyst of the present invention is for the synthetic dimethoxymethane of methyl alcohol selective oxidation, TiO prepared by ball-milling method 2-Al 2o 3complex carrier is that the raw material adopting is commercial alumina (γ-Al 2o 3) and titanium dioxide (TiO for common industrial 2).In ball mill, carry out high-energy ball milling, titanium oxide is fully contacted with aluminium oxide.Between titanium oxide and aluminium oxide, exist and interact, titanium oxide is mixed in the lattice of aluminium oxide, destroy the feature structure of a part of aluminium oxide, weaken the diffraction maximum of aluminium oxide, have a large amount of anatase TiO 2diffraction maximum, and induction produces more vacancy position; There is certain interaction in active component vanadium oxide or molybdenum oxide and titanium oxide simultaneously, and produce a small amount of V 2ti 7o 17crystal formation, as shown in Figure 1.
The present invention is applied to the synthetic dimethoxymethane of the direct selective oxidation of methyl alcohol: in fixed bed reactors, to loading catalyst in reactor; Before reaction starts, catalyst is first processed 0-12h at 373-873K in oxygen atmosphere.First lead to nitrogen to reaction temperature, more logical oxygen and methyl alcohol; Reaction pressure is normal pressure, and the reaction time is 3-120h; Combined feed air speed 4000-80000h -1, oxygen and methyl alcohol volume ratio are 1:2-6:1, and oxygen and nitrogen volume ratio are 1:5～1:1, and reaction temperature 90-300 ℃ can obtain DMM.Product is by gas-chromatography on-line analysis.
Compare with existing catalyst, catalyst provided by the invention, make the higher more stable reactivity of dimethoxymethane and selective for methyl alcohol selective oxidation, can reach respectively 60% and 94%, is better than current diplomatic most of catalyst system and catalyzing.
The invention has the advantages that: compare with existing catalyst system and catalyzing, catalyst preparation process is simple, and cost is little, and to preparation method require lowly, the simple catalytic performance of ball-milling method is good, convenient application on a large scale; Methyl alcohol is that raw material selective oxidation makes in DMM simultaneously, and accessory substance is few, cleanliness without any pollution; Processing line is short out, simple to operate, low-temp reaction, and mild condition, energy consumption is little; Catalyst of the present invention is that DMM has more wide prospects for commercial application for methanol oxidation.
Accompanying drawing explanation
The XRD figure of the catalyst of the different Ball-milling Times of Fig. 1;
●-γ-Al 2o 3, all the other peaks are anatase TiO 2diffraction maximum.
The specific embodiment
By following examples, illustrate that catalyst of the present invention applies, but the present invention is not limited to following examples.
Embodiment 1:
Ball-milling method is prepared MoO 3/ TiO 2-Al 2o 3and V 2o 5/ TiO 2-Al 2o 3catalyst:
First using water or ethanol as solvent, by commercial alumina (γ-Al 2o 3) and industrial titanium dioxide (P25) mix, wherein, TiO 2with Al 2o 3mass ratio is 1:2, solvent: the mass ratio of mixture is 1:1.Thick mixture is put into the high energy ball mill of polytetrafluoro, set Ball-milling Time 12h, ball milling method is that 15min replaces clockwise with counterclockwise, rotating speed 200r/min, set after major parameter, carry out high-energy ball milling, titanium oxide is fully contacted with aluminium oxide.After ball milling, mixture is dried, roasting (sintering temperature is 773K), obtain TiO 2-Al 2o 3complex carrier.Adopt again infusion process that presoma ammonium metavanadate or the ammonium molybdate of a certain amount of active component are dissolved in the water, remove to flood TiO 2-Al 2o 3complex carrier, obtains 10MoO 3/ TiO 2-Al 2o 3and 10V 2o 5/ TiO 2-Al 2o 3catalyst.
Embodiment 2:
Adopt the preparation method in embodiment 1, regulate Ball-milling Time to be respectively 0,3,6,10,12,48h, make the V of a series of different Ball-milling Times 2o 5/ TiO 2-Al 2o 3and MoO 3/ TiO 2-Al 2o 3catalyst.
Embodiment 3:
Adopt the method for embodiment 1 to carry out catalyst preparation, difference is the mass ratio 1:9 of titanium oxide and aluminium oxide.Rotational speed of ball-mill is 100r/min.
Embodiment 4:
Adopt the method for embodiment 1 to carry out catalyst preparation, difference is that rotational speed of ball-mill is 600r/min.The mass ratio 9:1 of titanium oxide and aluminium oxide.
Embodiment 5:
Adopt the method for embodiment 1 to carry out catalyst preparation, difference is that the sintering temperature of catalyst is 973K; Solvent: the mass ratio of complex carrier mixture is 1:2; Ball milling method is to replace clockwise with counterclockwise every 30min.
Embodiment 6:
Adopt the method for embodiment 1 to carry out catalyst preparation, difference is that the sintering temperature of catalyst is 673K; Solvent: the mass ratio of complex carrier mixture is 2:1.
Embodiment 7:
Adopt the preparation method of the catalyst in embodiment 1, by regulating the addition of vanadium oxide presoma, obtain respectively the catalyst of 5%, 15%, 20%, 30% vanadium oxide or molybdenum oxide load capacity.
Embodiment 8:
Catalytic reaction is carried out in fixed bed reactors.Catalyst compressing tablet screening by preparing, takes a certain amount of catalyst (bed height/reactor bed diameter=0.5) and puts into reaction tube, first by catalyst 500 ℃ of pretreatment 4h in oxygen atmosphere.First lead to nitrogen, more logical oxygen and methyl alcohol, low temperature for material benzenemethanol (15 ℃) bubbling charging, O 2flow velocity be 9ml/min, 120 ℃ of reaction temperatures, reaction pressure is normal pressure, 12 hours reaction time.O 2/ N 2=1:3, oxygen is with methyl alcohol than being 2.5:1, cumulative volume air speed is 8000h -1.Product forms with gas chromatographic analysis, and it is selective to calculate methanol conversion and dimethoxymethane (DMM).
Embodiment 9:
Adopt the method for embodiment 8 to react, difference is that first first 300 ℃ of reaction is carried out pre-oxidation 8h to catalyst.
Embodiment 10:
Adopt embodiment 8 methods to react, difference is that Pre oxidation changes 500 ℃ of processing 8h into.
Embodiment 11:
Adopt the method for embodiment 8 to react, difference is 300 ℃ of Pre oxidations, 12h.
Embodiment 12:
Adopt the method for embodiment 8 to react, difference is 500 ℃ of Pre oxidations, 12h.
Embodiment 13:
Adopt embodiment 8 methods to react, difference is logical oxygen: nitrogen=1:5 before reaction.
Embodiment 14:
Adopt embodiment 8 methods to react, difference is logical oxygen: nitrogen=1:1 before reaction.
Embodiment 15:
Adopt embodiment 8 methods to react, difference is that reaction temperature is 150 ℃.
Embodiment 16:
Adopt embodiment 8 methods to react, difference is that reaction temperature is 180 ℃.
Embodiment 17:
Adopt embodiment 8 methods to react, difference is that reaction temperature is 200 ℃.
Embodiment 18:
Adopt embodiment 8 methods to react, difference is that reaction temperature is 300 ℃.
Embodiment 19:
Adopt embodiment 9 methods to react, difference is to be 48h in the reaction time.
Embodiment 20:
Adopt embodiment 8 methods to react, difference is to be 72h in the reaction time.
Embodiment 21:
Adopt embodiment 8 methods to react, difference is that reaction feed cumulative volume air speed is 4000h -1.
Embodiment 22:
Adopt embodiment 8 methods to react, difference is that reaction feed cumulative volume air speed is 12000h -1.
Embodiment 23:
Adopt embodiment 8 methods to react, difference is that reaction feed cumulative volume air speed is 80000h -1.
Embodiment 24:
Adopt embodiment 8 methods to react, difference is logical oxygen: methyl alcohol=1:2 before reaction.
Embodiment 25:
Adopt embodiment 8 methods to react, difference is logical oxygen: methyl alcohol=6:1 before reaction.
Embodiment 26:
Different Pre oxidations and preoxidation time optionally affect reactivity and DMM: reaction condition is with embodiment 8-12.The results are shown in Table 1.
The different Pre oxidations of table 1 and oxidization time optionally affect reactivity and DMM
Embodiment 27:
The impact of different feeds oxygen nitrogen comparison reactivity.Reaction condition is with embodiment 8,13,14.The results are shown in Table 2.
Table 2 charging oxygen nitrogen comparison 10V 2o 5/ TiO 2-Al 2o 3 (mil)the impact of catalyst reaction activity
Embodiment 28:
At differential responses temperature to 10V 2o 5/ TiO 2-Al 2o 3 (mil)catalyst reaction activity and DMM optionally affect, and reaction condition adopts 8,15,16,17,18.The results are shown in Table 3.
10V at table 3 differential responses temperature 2o 5/ TiO 2-Al 2o 3 (mil)catalyst reaction is active
Embodiment 29:
The overall air speed of different feeds is to 10V 2o 5/ TiO 2-Al 2o 3 (mil)catalyst reaction activity and DMM optionally affect, and reaction condition adopts 8,21,22,23.The results are shown in Table 4.
Table 4 charging cumulative volume air speed is to 10V 2o 5/ TiO 2-Al 2o 3 (mil)the impact of catalyst reaction activity
Embodiment 30:
Different feeds oxygen methyl alcohol comparison 10V 2o 5/ TiO 2-Al 2o 3 (mil)the impact of catalyst reaction activity.Reaction condition is with embodiment 8,24,25.The results are shown in Table 5.
Table 5 charging oxygen methyl alcohol comparison 10V 2o 5/ TiO 2-Al 2o 3 (mil)the impact of catalyst reaction activity
Embodiment 31:
Adopt the reaction condition in embodiment 8 to carry out activity rating to the catalyst of different loads amount in embodiment 1 and 7, the catalytic performance of acquisition is as shown in table 6.
The different vanadium of table 6 or molybdenum load capacity complex carrier are catalyst based optionally to be affected reactivity and DMM
Embodiment 32:
The sign of the catalyst of different Ball-milling Times in embodiment 1 and 2 being carried out to XRD, result as shown in Figure 1.
As can be seen from Figure 1, when Ball-milling Time is less than 10h, there is the diffraction maximum of obvious aluminium oxide, along with the prolongation of Ball-milling Time, γ-Al 2o 3characteristic diffraction peak weaken gradually.When Ball-milling Time is more than or equal to 10h, can't see γ-Al 2o 3characteristic diffraction peak, only have the diffraction maximum of titanium oxide to exist.Explanation is along with the prolongation of Ball-milling Time, and aluminium oxide skeleton structure is destroyed gradually, and titanium oxide is incorporated in the lattice of aluminium oxide, produces specific microstructure.A series of catalyst particle sizes are added up and obtained average grain diameter by XRD collection of illustrative plates, and result is as shown in table 7.From scheming, Ball-milling Time is longer, and the average grain diameter of catalyst is less is decreased to 14.2nm from 26.4nm.And when Ball-milling Time surpasses 10h, average grain diameter has reducing by a larger margin.
Embodiment 33:
Adopt the reaction condition in embodiment 8 to carry out activity rating to the catalyst of different Ball-milling Times in embodiment 1 and 2, the catalytic performance of acquisition is as shown in table 7.
The 10V of the different Ball-milling Times of table 7 2o 5/ TiO 2-Al 2o 3-milcatalyst optionally affects reactivity and DMM
As known from Table 7, under the identical condition of amount of active ingredients, along with the prolongation of Ball-milling Time, 10V 2o 5/ TiO 2-Al 2o 3catalyst catalytic performance improves constantly, and illustrates that mechanical milling process changes the microstructure of catalyst, may make the particle diameter of catalyst diminish, and the particle diameter calculating from Fig. 1 is along with Ball-milling Time extends, and particle diameter is constantly reducing.As can be seen from Figure 1, mechanical milling process promotes to interact between titanium and aluminium simultaneously, and aluminium oxide itself is destructurized, produces more electron hole, is conducive to the transmission of electronics, and then promotes the conversion of methyl alcohol.
Embodiment 34:
Adopt the reaction condition in embodiment 8 to carry out activity rating to the catalyst of different titanium oxide and alumina ration in embodiment 1,3 and 4, catalytic performance is as shown in table 8.
The V of the different titanium oxide of table 8 and alumina ration 2o 5/ TiO 2-Al 2o 3the catalytic performance of catalyst
Embodiment 35:
To the 10V in embodiment 1 2o 5/ TiO 2-Al 2o 3 (mil)catalyst carries out macrocyclic reactivity and DMM optionally investigates, and reaction process condition adopts embodiment 8.The results are shown in Table 9.
The table 9 differential responses time optionally affects catalyst reaction activity and DMM
As known from Table 9,10V 2o 5/ TiO 2-Al 2o 3 (mil)the reactivity of catalyst reaction is relatively stable, and through 72 hours, obvious inactivation did not appear in catalyst, so this catalyst possesses the potentiality of DMM industrialization production requirements.
By above each embodiment, further illustrate TiO in methyl alcohol selective oxidation dimethoxymethane processed 2-Al 2o 3the effect excellence that complex carrier is catalyst based.With simple V 2o 5/ TiO 2catalyst system and catalyzing is compared, 20V 2o 5/ TiO 2-Al 2o 3the conversion ratio of catalyst methyl alcohol be 60.2%, DMM be selectively 95%, far away higher than V 2o 5/ TiO 2catalytic performance (being respectively 30% and 75%) (Journal of Catalysis311 (2014) 59 – 70; Catalysis Today152 (2010) 70 – 77).The performance of vanadium titanium Al catalysts is better than most of catalyst activities of current bibliographical information.Meanwhile, V 2o 5/ TiO 2-Al 2o 3the DMM of catalyst is selectively all more than 80%, and V 2o 5/ Al 2o 3the DMM of catalyst is selectively no more than 68% (Catal Lett (2013) 143:624 – 629).Visible under suitable reaction process condition, TiO 2-Al 2o 3complex carrier is catalyst based has excellent catalytic performance in the synthetic DMM of methanol oxidation.
The V that adopts ball-milling method to prepare 2o 5/ TiO 2-Al 2o 3and MoO 3/ TiO 2-Al 2o 3catalyst, at 120 ℃, O 2/ N 2=1:3, oxygen is with methyl alcohol than being 2.5:1, cumulative volume air speed is 8000h -1reaction condition under, catalytic activity and DMM are selectively very high, good stability; And catalyst preparation process is simple, cost is low, is convenient to large-scale manufacture; The catalyst that simultaneously prepared by ball-milling method, because there being certain interaction between titanium oxide and aluminium oxide, and produces a small amount of V 2ti 7o 17crystal formation, this specific catalyst microstructure, the conversion and the DMM that are conducive to methyl alcohol generate.Finally it is emphasized that whole reaction process environmental protection, energy-saving source, simple for process.So TiO 2-Al 2o 3complex carrier base catalyst system and catalyzing has good industrial applications prospect in methanol oxidation DMM processed.

Claims (3)

1. a titanium aluminum-base composite carried catalyst, is characterized in that complex carrier is aluminium oxide and titanium oxide, and active component is molybdenum oxide or vanadium oxide; Take carrier as 100% calculating, and the mass ratio that active component molybdenum oxide or vanadium oxide are carrier is 5%-50%; TiO 2the mass percent that accounts for carrier is 10%-90%.
2. the preparation method of catalyst as claimed in claim 1, is characterized in that adopting ball-milling method:
1) using water or ethanol as solvent, commercial alumina and industrial titanium dioxide are evenly mixed to TiO 2-Al 2o 3mass ratio is 1:9-9:1;
2) mixture is put into high energy ball mill; Set Ball-milling Time 10-48h, ball milling method is that 15-30min replaces clockwise with counterclockwise, rotating speed 100-600r/min;
3) after ball milling, mixture is dried, roasting, obtain TiO 2-Al 2o 3complex carrier;
4) presoma ammonium metavanadate or the ammonium molybdate of active component are dissolved in the water, dipping TiO 2-Al 2o 3complex carrier, obtains MoO 3/ TiO 2-Al 2o 3or V 2o 5/ TiO 2-Al 2o 3catalyst.
3. the catalyst of claim 1 is for the synthetic dimethoxymethane of methanol oxidation.
CN201410222214.3A 2014-05-23 2014-05-23 The synthesis of titanium aluminium-based catalyst and the application in methanol oxidation dimethoxymethane processed Active CN104043442B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113649079A (en) * 2020-05-12 2021-11-16 中国石油化工股份有限公司 Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030166972A1 (en) * 2002-02-20 2003-09-04 Regents Of The University Of California Office Of Technology Licensing Process for production of formaldehyde from dimethyl ether
CN1634655A (en) * 2004-11-26 2005-07-06 南京大学 Catalyst for producing methylal by selective oxidation of methanol and preparation method and use thereof
US20060266673A1 (en) * 2005-05-25 2006-11-30 Rende Dean E Layered composition and processes for preparing and using the composition
CN101224431A (en) * 2008-01-30 2008-07-23 中国科学院山西煤炭化学研究所 Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof
CN102284283A (en) * 2010-06-18 2011-12-21 上海牛翼新能源科技有限公司 Flue gas denitrification titanium oxide load-type vanadium-tungsten composite oxide integral-type catalyst
CN102824906A (en) * 2012-09-07 2012-12-19 天津大学 Loaded type molybdenum oxide catalyst for selectively oxidizing methanol to synthesize dimethoxymethane (DMM) and application
CN104148060A (en) * 2014-07-14 2014-11-19 天津大学 Platinum catalyst supported on double-oxide composite carrier and preparation method and application of platinum catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030166972A1 (en) * 2002-02-20 2003-09-04 Regents Of The University Of California Office Of Technology Licensing Process for production of formaldehyde from dimethyl ether
CN1634655A (en) * 2004-11-26 2005-07-06 南京大学 Catalyst for producing methylal by selective oxidation of methanol and preparation method and use thereof
US20060266673A1 (en) * 2005-05-25 2006-11-30 Rende Dean E Layered composition and processes for preparing and using the composition
CN101224431A (en) * 2008-01-30 2008-07-23 中国科学院山西煤炭化学研究所 Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof
CN102284283A (en) * 2010-06-18 2011-12-21 上海牛翼新能源科技有限公司 Flue gas denitrification titanium oxide load-type vanadium-tungsten composite oxide integral-type catalyst
CN102824906A (en) * 2012-09-07 2012-12-19 天津大学 Loaded type molybdenum oxide catalyst for selectively oxidizing methanol to synthesize dimethoxymethane (DMM) and application
CN104148060A (en) * 2014-07-14 2014-11-19 天津大学 Platinum catalyst supported on double-oxide composite carrier and preparation method and application of platinum catalyst

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
任攀杰等: "V2O5/Al2O3-TiO2催化剂上乙醇催化氧化性能研究", 《分子催化》 *
任攀杰等: "V2O5/Al2O3-TiO2催化剂上乙醇催化氧化性能研究", 《分子催化》, vol. 21, 31 August 2007 (2007-08-31), pages 1 - 2 *
邓存等: "TiO2调变对MoO3/γ-Al2O3和CoO-MoO3/γ-Al2O3催化性能的影响", 《分子催化》 *
邓存等: "TiO2调变对MoO3/γ-Al2O3和CoO-MoO3/γ-Al2O3催化性能的影响", 《分子催化》, vol. 12, no. 2, 30 April 1998 (1998-04-30), pages 107 - 112 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113649079A (en) * 2020-05-12 2021-11-16 中国石油化工股份有限公司 Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof
CN113649079B (en) * 2020-05-12 2023-10-10 中国石油化工股份有限公司 Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof

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