CN103623802A

CN103623802A - Method for simultaneously producing dimethyl carbonate and dimethyl ether through urea alcoholysis process, catalyst used thereby, and preparation method of catalyst

Info

Publication number: CN103623802A
Application number: CN201210308835.4A
Authority: CN
Inventors: 吴鹏; 李志坚; 冯叶飞; 吴庆敏; 高滋
Original assignee: Accelergy Shanghai R & D Center Co Ltd
Current assignee: Accelergy Shanghai R & D Center Co Ltd
Priority date: 2012-08-27
Filing date: 2012-08-27
Publication date: 2014-03-12

Abstract

The invention provides a method for simultaneously producing dimethyl carbonate and dimethyl ether through a urea alcoholysis process, a catalyst used thereby, and a preparation method of the catalyst. The method for simultaneously producing dimethyl carbonate and dimethyl ether through a urea alcoholysis process adopts a two-stage slurry bed reactor or fixed bed reactor technology, and in the preparation process, when dimethyl carbonate and dimethyl ether are prepared from methyl carbamate and methanol in a second-stage fixed bed reactor, a multi-component composite oxide catalyst using one or more of transition metal oxides, rare earth oxides, alkali metal oxides, alkaline earth oxides, IVA group metal oxides, VA group non-metal oxides or IIIA group non-metal oxides and Al2O3 as active components is filled into the fixed bed reactor, so the methyl carbamate conversion rate is improved, and the dimethyl carbonate and dimethyl ether selectivity is substantially improved.

Description

The catalyst that the method for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether and the method adopt and the preparation method of this catalyst

Technical field

The present invention relates to a kind of method of alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether and catalyst that the method adopts and the preparation method of this catalyst.

Background technology

Dimethyl carbonate (Dimethyl Carbonate, be called for short DMC, chemical formula:

in its molecule, contain CH ₃-, CH ₃o-, CH ₃o-CO-,-CO-Duo Zhong functional group, have good reactivity, can methylate with classes of compounds such as alcohol, phenol, amine, hydrazine, esters, carbonylation, esterification and ester exchange reaction.Thereby DMC can replace the poisonous reagents such as methylating reagent and carbonylation agent (such as phosgene), be widely used in as organic synthesis industry such as Merlon preparations.Under normal temperature, DMC is a kind of water white transparency, summary scent of, micro-sweet liquid, be insoluble in water, but immiscible organic solvent that can be nearly all with alcohol, ether, ketone etc., thereby it also can be used as solvent and replaces the preparation that in the past conventional toxic solvent and cleaning agent (for daily necessities, furniture, interior decoration, toy etc.) are widely used in paint and coating.In addition in view of the abundant oxygen content of DMC (up to 53%), suitable vapour pressure, water-resistance and mixed allocation coefficient, thereby also can be used as diesel oil and mix the soot emissions that fuel burning reduces diesel combustion.

DMC meets the requirements of the times of cleaner production and green chemical industry and has broad application prospects, and is described as " the new foundation stone " of 21 century organic synthesis, be to be quite subject in recent years the novel green chemicals of attention both at home and abroad, and its preparation technology receives much concern naturally.

Wherein, as far back as 1919, H.P.Hood and H.R.Murdock be at J.Phys.Chem., proposed to produce with methylchloroformate and methanol azeotropic the method (developing into afterwards phosgenation) of dimethyl carbonate in 1919,23,498.This technique produces that DMC productive rate is high, product purity is also very high, thereby within a suitable period, phosgenation has obtained generally application.But, due to hypertoxicity, the corrosivity of phosgene and the three wastes problem producing in technique (comprising phosgene itself), make phosgenation be subject to the restriction of environmental regulation, in decades, be progressively eliminated recently.

Afterwards, since the eighties, the non-phosgene routes such as methanol oxidation oxo synthesis and ester exchange process have been developed successively abroad.First set non-phosgene-liquid-phase oxidative carbonylation synthesis technique of its exploitation is disclosed in the United States Patent (USP) that Italy A Nike company (Anic S.p.A) is first US4318862 in the patent No..Soon company of Ube Industries Ltd. discloses the synthetic DMC technique of vapor phase method methanol oxidation carbonylation in European patent EP 0425197.The synthetic DMC technique of vapor phase method is usingd carbon monoxide, methyl alcohol, methyl nitrite and oxygen as raw material, to adsorb PdCl ₂/ CuCl ₂activated carbon is as catalyst, and its principles of chemistry and liquid phase method are basic identical.But in the synthetic DMC technique of methanol oxidation carbonyl, no matter be liquid phase method or vapor phase method, it is principal component that catalyst be take stannous chloride or copper chloride, in use procedure, stannous chloride or copper chloride inactivation are more serious, and its water generating in reaction is combined, and the hydrochloric acid of formation is larger to equipment corrosion, causes production equipment gross investment higher; Meanwhile, the chlorion in product is difficult to remove, and affects the quality of product; And this technique is carried out under elevated pressures, operating condition is harsh, thereby the economic benefit of product is poor.

U.S. Texaco (Texaco) all discloses the synthetic DMC technique of ester exchange of its research and development in the patent No. is the United States Patent (USP) of US461609 and US4691041.Take oxirane or expoxy propane, methyl alcohol and carbon dioxide as raw material, first make oxirane or expoxy propane and carbon dioxide reaction Formed vinyl acetate or propene carbonate, and then react generation final products DMC with methyl alcohol, and by-product ethylene glycol or 1,2-PD.Therefore and be unsuitable for extensive development but in this technique, the raw material sources required due to ester-interchange method depend on petroleum path, and its production cost is also higher.

At the beginning of the eighties in last century, the Peter Ball of Germany, the people such as Heinz Fullmann are at Carbonates and polycarbonates from urea and alcohol.Angew.Chem.Int.Ed., 1980,19,718 and Synthesis of carbonates and polycarbonates by reaction of urea with hydroxyl compounds.C1 Mol.Chem.1984, in 1,95 Preliminary report by the possibility of urea and the direct synthesis of dialkyl carbonates of long-chain alcohol.And afterwards, the people such as the Ryu of the U.S. have just disclosed in destilling tower the technique with methyl alcohol and urea Direct Synthesis of Dimethyl Carbonate in the patent No. is the United States Patent (USP) of US5902894 and US6392078.

Although above-mentioned alcoholysis of urea is prepared the defects such as poor selectivity that have the low and DMC of feed stock conversion in dimethyl carbonate technique, at that time, this technology does not obtain large-scale promotion, but because of its raw materials used urea and methyl alcohol cheap and easy to get, and the major product dimethyl carbonate product quality of producing is high, impurity content is few, the also advantage such as lower of separating-purifying cost, and after DMC preparation technology in be constantly improved, and become gradually Research Emphasis prepared by DMC.

As, Chinese patent application CN1431190A " a kind of method with urea and methyl alcohol Synthesis of dimethyl carbonate ", Chinese patent application CN1428329A " urea and methyl alcohol adopt the method for heterogeneous catalysis Synthesis of dimethyl carbonate ", Chinese patent application CN1421430A " a kind of method of alcoholysis of urea Synthesis of dimethyl carbonate " disclose with catalytic distillation technology and have adopted alcoholysis of urea to prepare the technique of dimethyl carbonate.Yet in above-mentioned technique, the reactor structure complexity that catalytic distillation technology is required, operating condition is harsh, thereby is still difficult to realize large-scale production.And for example Chinese patent application CN1569809A provides in high-pressure reactor, with amine salt type ionic-liquid catalyst, by the method for methyl alcohol and Synthesis of Dimethyl Carbonate from Urea.Thereby simplification reactor structure, but the cost of this technique is higher, and catalyst life is shorter, is also not suitable for the large-scale production that has high input.

For this reason as Chinese patent application CN1062009A provides a kind of " method of alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether ".It first generates methyl carbamate (MC) by urea and methyl alcohol reaction, afterwards again by methyl carbamate and methyl alcohol reaction Formed dimethyl phthalate and dimethyl ether (DME).The dimethyl carbonate product quality obtained by this technique is high, impurity is few and separation costs is also lower, can increase substantially the competition of market economy power of dimethyl carbonate.And, in this technique, when obtaining dimethyl carbonate, also can extract the highly purified dimethyl ether forming that decomposed by dimethyl carbonate.

Dimethyl ether (DME) is a kind of colourless flammable, and it is the gas of compressible liquefaction not only, and it has been widely used at chemical industry tools such as synthetic, pharmacy, fuel, agricultural chemicals; And the substitute of dimethyl ether or town gas and liquefied gas, also can make the substitute fuel of future automobile; In addition, dimethyl ether its during as environmental protection refrigerant, there is inertia, non-carcinogenesis, the characteristic such as almost non-toxic, and do not there is ozone layer destroying effect and can not cause greenhouse effects, thereby dimethyl ether is the clean energy products of 21st century, the same utmost point has application prospect.

As mentioned above, existing alcoholysis of urea is prepared in dimethyl carbonate technique, in the conversion ratio of raw material and the Selective Control of dimethyl carbonate, and on reactor structure and operating procedure, also has defect.Thereby, how to simplify reactor structure and operating condition, when how to obtain high-quality dimethyl carbonate, the conversion ratio and the dimethyl carbonate that further improve raw material are selectively the key points of further optimizing alcoholysis of urea.

Summary of the invention

For existing alcoholysis of urea, prepare in dimethyl carbonate technique, feed stock conversion and dimethyl carbonate obtain that rate is low, the defect of structure of reactor and operating condition complexity etc., the invention provides a kind of method of alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether and catalyst that the method adopts and the preparation method of this catalyst.

A kind of catalyst for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether provided by the invention, wherein,

The active component of catalyst comprises: in transition metal oxide, rare-earth oxide, alkali metal oxide, alkaline earth oxide, IV family metal oxide ,VA family's nonmetal oxide or IIIA family nonmetal oxide or one or more and Al ₂o ₃.

Alternatively, described transition metal oxide is TiO ₂, ZrO ₂, Co ₂o ₃, ZnO, CuO, MoO ₃, Fe ₂o ₃, NiO and Cr ₂o ₃in one or more;

Described rare-earth oxide is La ₂o ₃and/or Ce ₂o ₃;

Described alkali metal oxide is Li ₂o, Na ₂o and K ₂one or more in O;

Described alkaline earth oxide is one or more in MgO, CaO, SrO and BaO;

Described IVA family metal oxide is SnO and/or PbO;

Described VA family nonmetal oxide is P ₂o ₅;

Described IIIA family nonmetal oxide is B ₂o ₃.

Alternatively, in the mass percent of the active component of described catalyst forms, described Al ₂o ₃content is 20 ~ 85wt%;

Described transition metal oxide content is 0 ~ 75wt%;

Wherein, TiO ₂, ZrO ₂, Co ₂o ₃, MoO ₃, Fe ₂o ₃and Cr ₂o ₃total content is 0 ~ 8wt%; CuO and NiO total content are 0 ~ 40wt%; ZnO content is 0 ~ 75wt%;

Described rare-earth oxide, alkali metal oxide, IVA family metal oxide ,VA family nonmetal oxide, IIIA family nonmetal oxide and except MgO the total content of all the other alkaline earth oxides be 0 ~ 10wt%; MgO content is 0 ~ 45wt%.

Alternatively, one or more and the Al of the active component of described catalyst in transition metal oxide, alkali metal oxide, alkaline earth oxide and rare-earth oxide, IVA family metal oxide ,VA family's nonmetal oxide or IIIA family nonmetal oxide ₂o ₃form; Wherein, the mass percent component of the active component of described catalyst is:

Al ₂o ₃content is 50 ~ 85wt%; Transition metal oxide content is 15 ~ 48wt%;

The content of rest activity component is 0 ~ 2wt%.

Alternatively, the mass percent component of the active component of described catalyst is:

Al ₂o ₃content is 53 ~ 70wt%; Transition metal oxide content is 30 ~ 45wt%;

The total content of rest activity component is 0 ~ 2wt%.

Al ₂o ₃content is 55 ~ 65wt%; Described one or more transition metal oxide total contents are 35 ~ 45wt%; Rest activity constituent content is 0～1%.

Alternatively, described transition metal oxide is ZnO or CuO.

The present invention also provides a kind of preparation method of the above-mentioned catalyst for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, and its process comprises:

By in the active component of described catalyst, except Al ₂o ₃the outer corresponding salting liquid of rest activity component disposable or repeatedly in batches with Al ₂o ₃mix, and Al described in submergence ₂o ₃; And roasting 1 ~ 16 hour at 500 ~ 900 ℃, make multicomponent composite oxide catalysts after cooling.

The present invention also provides the preparation method of the another kind of above-mentioned catalyst for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, and its process comprises:

By Al in described catalyst and the corresponding mixing salt solution of all the other one or more active components and alkaline solution generation coprecipitation reaction; And by the sediment making through washing, dry after roasting 1 ~ 16 hour at 500 ~ 900 ℃, make multicomponent composite oxide catalysts after cooling.

Alternatively, described alkaline solution comprises the aqueous solution of ammonium carbonate, carbonic hydroammonium, urea, NaOH or sodium carbonate.

The present invention also provides a kind of method of alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, comprising:

In paste state bed reactor or the first fixed bed reactors, pass into urea and methyl alcohol reaction generation methyl carbamate and ammonia;

Product is passed in the second fixed bed reactors, Formed dimethyl phthalate and ammonia, wherein part dimethyl carbonate is decomposed into dimethyl ether and carbon dioxide; And product is purified, obtain dimethyl carbonate and dimethyl ether.

Wherein, described the second fixed bed reactors are equipped with multicomponent composite oxide catalysts, thereby control the selective of dimethyl carbonate and dimethyl ether, and the conversion ratio of methyl carbamate;

The active component of described multicomponent composite oxide catalysts comprises: one or more in transition metal oxide, rare-earth oxide, alkali metal oxide, alkaline earth oxide, IVA family metal oxide ,VA family's nonmetal oxide and IIIA family nonmetal oxide and Al ₂o ₃.

Described rare-earth oxide is La ₂o ₃and/or Ce ₂o ₃;

Described alkali metal oxide is Li ₂o, Na ₂o and K ₂one or more in O;

Described alkaline earth oxide is one or more in MgO, CaO, SrO and BaO;

Described IVA family metal oxide is SnO and/or PbO;

Described VA family nonmetal oxide is P ₂o ₅;

Described IIIA family nonmetal oxide is B ₂o ₃.

Described transition metal oxide content is 0 ~ 75wt%;

Wherein, TiO ₂, ZrO ₂, Co ₂o ₃, MoO ₃, Fe ₂o ₃and Cr ₂o ₃total content is 0 ~ 8wt%; CuO and/or NiO total content are 0 ~ 40wt%; ZnO content is 0 ~ 75wt%;

Al ₂o ₃content is 50 ~ 85wt%; Transition metal oxide content is 15 ~ 48wt%;

The content of rest activity component is 0 ~ 2wt%;

Al ₂o ₃content is 53 ~ 70wt%; Transition metal oxide content is 30 ~ 45wt%;

The total content of rest activity component is 0 ~ 2wt%;

Alternatively, described transition metal oxide is ZnO or CuO.

Alternatively, utilize above-mentioned two kinds of described catalyst of preparing for the preparation method of the catalyst of alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, thereby control the selective of dimethyl carbonate and dimethyl ether in the method for above-mentioned alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, and the conversion ratio of methyl carbamate.

Alternatively, in the method for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, the catalyst regulate adopting is in above-mentioned two kinds of sintering temperature and/or times for preparation method's process of the catalyst of alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, to control the conversion ratio of MC, the selective and DME of DMC selective.

Compared with prior art, the present invention has the following advantages:

The method of alcoholysis of urea co-producing dimethyl carbonate of the present invention and dimethyl ether is with two section type paste state bed reactor or fixed bed reactors technique, adopt alcoholysis of urea to prepare dimethyl carbonate and dimethyl ether, while preparing dimethyl carbonate and dimethyl ether technique so that methyl carbamate and methyl alcohol are synthetic during this time in second segment fixed bed reactors, in fixed bed reactors, insert with Al ₂o ₃and in transition metal oxide, rare-earth oxide, alkali metal oxide, alkaline earth oxide, IVA family metal oxide ,VA family's nonmetal oxide or IIIA family nonmetal oxide or one or more multicomponent composite oxide catalysts that are active component;

In the present invention, adopt two section type paste state bed reactor or fixed bed reactors technique to compare to adopt rectifying evaporation technology to realize urea alcoholysis with tradition and prepare dimethyl carbonate technique, its reaction unit is simple in structure, and operating condition is easy to control, and meets large-scale industrialization Production requirement;

And in above-mentioned technique, the catalyst activity adopting is strong, improving methyl carbamate conversion ratio simultaneously, greatly improved the selective of dimethyl carbonate and dimethyl ether; But also can greatly save in the energy consumption of alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether reaction process and the purification energy consumption of follow-up dimethyl carbonate and dimethyl ether;

In addition described catalyst raw material is easy to get, and can adopt coprecipitation, infusion process or two kinds of methods to be mixed with, and its preparation process is simple, and condition is easy to control, and is applicable to large-scale industrial production.

The specific embodiment

Described in background information, at existing urea alcoholysis method, prepare in dimethyl carbonate technique, have that feed stock conversion is low, the poor selectivity of dimethyl carbonate and dimethyl carbonate production equipment complex structure, operating condition are harsh, be difficult to control, be not suitable for the defects such as large-scale industrialization production, and then affected alcoholysis of urea further develop with and the market competitiveness.In order to overcome above-mentioned defect, the invention provides a kind of Catalysts and its preparation method for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether and application.

The invention provides the catalyst for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, described catalyst is multicomponent composite oxide catalysts, and its active component comprises: in transition metal oxide, rare-earth oxide, alkali metal oxide, alkaline earth oxide, IVA family metal oxide ,VA family's nonmetal oxide or IIIA family nonmetal oxide or one or more and Al ₂o ₃.

Described transition metal oxide is TiO ₂, ZrO ₂, Co ₂o ₃, ZnO, CuO, MoO ₃, Fe ₂o ₃, NiO and Cr ₂o ₃in one or more, be particularly preferably ZnO or CuO.Described rare-earth oxide is La ₂o ₃and/or Ce ₂o ₃; Described alkali metal oxide is Li ₂o, Na ₂o or K ₂one or more in O; Described alkaline earth oxide is one or more in MgO, CaO, SrO and BaO; Described IVA family metal oxide is SnO and/or PbO; Described VA family nonmetal oxide is P ₂o ₅; Described IIIA family nonmetal oxide is B ₂o ₃.

Described multicomponent composite oxide catalysts can adopt infusion process preparation, and its process comprises:

By described catalyst, be in multicomponent composite oxide catalysts, except Al ₂o ₃the outer corresponding salting liquid of all the other one or more active components disposable or repeatedly in batches with Al ₂o ₃mix, and Al described in submergence ₂o ₃, at 500 ~ 900 ℃, roasting is 1 ~ 16 hour, makes multicomponent composite oxide catalysts after cooling.

Described catalyst also can adopt coprecipitation preparation, and its process comprises:

By Al in described catalyst and the corresponding mixing salt solution of all the other one or more active components and one or more alkaline solution generation coprecipitation reactions; And by the sediment making through washing, dry after roasting 1 ~ 16 hour at 500 ~ 900 ℃, make multicomponent composite oxide catalysts after cooling.Wherein, the salting liquid of Al can be arbitrary soluble-salt solution, and wherein, preferably as acetate, nitrate etc. are in roasting process, and except Al element, remaining is as " C ₂h ₃o ₂ ^-" " NO ₃ ^-" the most salting liquid decomposing of going, thereby the catalyst quality that assurance makes.

Described alkaline solution is chosen as the aqueous solution of ammonium carbonate, carbonic hydroammonium, urea, NaOH or sodium carbonate.

Again or adopt the method that is mixed with of infusion process and coprecipitation to obtain described catalyst.

The method of alcoholysis of urea co-producing dimethyl carbonate of the present invention and dimethyl ether adopts two section type paste state bed reactor or fixed bed reactors technique, adopt alcoholysis of urea coproduction to prepare dimethyl carbonate and dimethyl ether, first adopt in paste state bed reactor or the first fixed bed reactors, to pass into urea and methyl alcohol reacting gas generates methyl carbamate and ammonia; Afterwards product is passed in the second fixed bed reactors, with methyl carbamate and methyl alcohol, further react Synthesis of dimethyl carbonate; Part dimethyl carbonate is further decomposed into dimethyl ether and carbon dioxide during this time.The present invention is characterised in that, in described the second fixed bed reactors, inserts multicomponent composite oxide catalysts, thereby is improving methyl carbamate conversion ratio simultaneously, can effectively control the selective of dimethyl carbonate and dimethyl ether.

When described multicomponent composite oxide catalysts is applied in alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether technique, it can effectively improve the conversion ratio of raw material, and controls the selective of DMC and DME.Described multicomponent composite oxide catalysts is applied to alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether technique, and its detailed process comprises:

S1: first pass into urea and methyl alcohol reacting gas generation methyl carbamate and ammonia in paste state bed reactor or the first fixed bed reactors; Wherein, described paste state bed reactor or the first fixed bed reactors reaction condition are controlled is made as 110 ~ 160 ℃, 0.2 ~ 2.0MPa.

S2: in the second fixed bed reactors that afterwards product passed into, Formed dimethyl phthalate and ammonia, wherein part dimethyl carbonate is decomposed into dimethyl ether and carbon dioxide, and product is purified, and obtains dimethyl carbonate and dimethyl ether.Wherein, the reaction condition that can control particularly described the second fixed bed reactors is 150 ~ 200 ℃, 0.1 ~ 1.0MPa.

During this time: described the second fixed bed reactors are equipped with described multicomponent composite oxide catalysts, thus control the conversion ratio of the selective and methyl carbamate of dimethyl carbonate and dimethyl ether.

Wherein, in the mass percent of the active component of adopted catalyst forms, described Al ₂o ₃content is 20 ~ 85wt%; Described transition metal oxide content is 0 ~ 75wt%, wherein, and described TiO ₂, ZrO ₂, Co ₂o ₃, MoO ₃, Fe ₂o ₃and Cr ₂o ₃total content is 0 ~ 8wt% of catalyst activity component total amount; CuO and/or NiO total content are 0 ~ 40wt% of catalyst activity component total amount; ZnO content is 0 ~ 75wt% of catalyst activity component total amount.Described rare-earth oxide, alkali metal oxide, IVA family metal oxide ,VA family nonmetal oxide, boron oxide and except MgO the total content of all the other alkaline earth oxides be 0 ~ 10wt% of catalyst activity component total amount; If described catalyst activity component comprises MgO, the content of MgO is 0 ~ 45wt% of catalyst activity component total amount.

In preferred version, one or more and the Al of the active component of described catalyst in transition metal oxide, alkali metal oxide, alkaline earth oxide and rare-earth oxide, IVA family metal oxide ,VA family's nonmetal oxide or IIIA family nonmetal oxide ₂o ₃form; Wherein, the mass percent component of the active component of described catalyst is:

Al ₂o ₃content is 50 ~ 85wt%; Transition metal oxide content is 15 ~ 48wt%;

The content of rest activity component (alkali metal oxide, alkaline earth oxide and rare-earth oxide, IVA family metal oxide ,VA family's nonmetal oxide or IIIA family nonmetal oxide) is 0 ~ 2wt%.

Further preferably, the mass percent component of the active component of described catalyst is:

Al ₂o ₃content is 53 ~ 70wt%; Transition metal oxide content is 30 ~ 45wt%;

The total content of rest activity component is 0 ~ 2wt%.

Again further preferably, the mass percent component of the active component of described catalyst is:

In the method for alcoholysis of urea co-producing dimethyl carbonate of the present invention and dimethyl ether, by catalyst, use the conversion ratio that can greatly improve MC, improve the selective of DMC and DME simultaneously.Thereby than conventional alcoholysis of urea preparing dimethyl carbonate technique, by further adherence pressure and corresponding temperature, further improve the conversion operation of MC, the present invention has saved the consumption of the energy greatly, and reduced the harsh requirement for equipment, thereby produce good economic benefit.

Wherein, by adjusting the catalyst adopt sintering temperature and/or the time in above-mentioned two kinds of preparation process, the also selective and DME of the conversion ratio of MC, DMC selective in step S2 described in capable of regulating.Wherein, in the roasting process of preparing at catalyst, preferably roasting 2 ~ 12 hours at 700 ~ 900 ℃, more further preferably roasting 4～10 hours at 750 ~ 850 ℃.

Below, we set forth in conjunction with specific embodiments and adopt above-mentioned two kinds of methods under different conditions, to prepare the described multicomponent composite oxide catalysts that component is different, and the described multicomponent composite oxide catalysts obtaining regulating and controlling the conversion ratio of MC, the optionally effectiveness of the selective and DME of DMC for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether technique, thereby further discuss technical scheme of the present invention and advantage:

(1). the preparation of multicomponent composite oxide catalysts:

Embodiment mono-:

Raw material: Mg (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 13.3gMg (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 30ml water, gets the dried Al of 7.9g ₂o ₃sample, evenly mixes both latter standing 60 minutes.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 20wt% of MgO, Al ₂o ₃about 80wt%.

Example two:

Raw material: Ni (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 25.3g Ni (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 38ml water, gets the dried Al of 11.5g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 800 ℃ of air atmospheres, calcine 6 hours.

Product: gained catalyst sample is containing the about 36wt% of NiO, Al ₂o ₃about 64wt%.

Example three:

Raw material: LiNO ₃, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 12.5g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 20ml water, gets the dried Al of 5.6g ₂o ₃sample, evenly mixes both latter standing 60 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine and within 12 hours, obtain sample A.By 0.8g LiNO ₃be dissolved in wiring solution-forming in 19ml water, and evenly mix with sample A, under infrared lamp, dry, be placed in afterwards 120 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing Li ₂the about 4wt% of O, the about 37wt% of ZnO, Al ₂o ₃about 59wt%.

Example four:

Raw material: Mg (NO ₃) ₂6H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: first the way with reference to example three obtains sample A.By 1.2g Mg (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 19ml water, and evenly mixes with sample A, under infrared lamp, dries, and is placed in afterwards 120 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 2wt% of MgO, the about 38wt% of ZnO, Al ₂o ₃about 60wt%.

Example five:

Raw material: Ca (NO ₃) ₂4H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: first the way with reference to example three obtains sample A.By 0.8g Ca (NO ₃) ₂4H ₂o is dissolved in wiring solution-forming in 19ml water, and evenly mixes with sample A, under infrared lamp, dries, and is placed in afterwards 120 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 2wt% of CaO, the about 38wt% of ZnO, Al ₂o ₃about 60wt%.

Example six:

Raw material: Ni (NO ₃) ₂6H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: first the way with reference to example three obtains sample A.By 0.8g Ni (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 19ml water, and evenly mixes with sample A, under infrared lamp, dries, and is placed in afterwards 120 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 2wt% of NiO, the about 38wt% of ZnO, Al ₂o ₃about 60wt%.

Example seven:

Raw material: Co (NO ₃) ₂6H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 12.5g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 20ml water, gets the dried Al of 5.6g ₂o ₃sample, evenly mixes both latter standing 60 minutes.Under infrared lamp, stir and dry, be placed in afterwards 120 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine and within 12 hours, obtain sample B.By 0.3g Co (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 15ml water, and evenly mixes with sample B, under infrared lamp, dries, and is placed in afterwards 120 ℃ of baking ovens.Finally in 600 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing Co ₂o ₃about 1wt%, the about 38wt% of ZnO, Al ₂o ₃about 61wt%.

Example eight:

Raw material: Ba (NO ₃) ₂, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: the way with reference to example seven obtains sample B.By 0.2g Ba (NO ₃) ₂be dissolved in wiring solution-forming in 15ml water, and evenly mix with sample B, under infrared lamp, dry, be placed in afterwards 120 ℃ of baking ovens.Finally in 800 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 1wt% of BaO, the about 38wt% of ZnO, Al ₂o ₃about 61wt%.

Example nine:

Raw material: Cu (NO ₃) ₂3H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: the way with reference to example seven obtains sample B.By 0.3g Cu (NO ₃) ₂3H ₂o is dissolved in wiring solution-forming in 16ml water, and evenly mixes with sample B, under infrared lamp, dries, and is placed in afterwards 120 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 1wt% of CuO, the about 38wt% of ZnO, Al ₂o ₃about 61wt%.

Example ten:

Raw material: Cr (NO ₃) ₃9H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: the way with reference to example seven obtains sample B.By 0.5g Cr (NO ₃) ₃9H ₂o is dissolved in wiring solution-forming in 16ml water, and evenly mixes with sample B, under infrared lamp, dries, and is placed in afterwards 120 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing Cr ₂o ₃about 1wt%, the about 38wt% of ZnO, Al ₂o ₃about 61wt%.

Example 11:

Preparation process: by 4.5g Cu (NO ₃) ₂3H ₂o and 22.3g Zn (NO ₃) ₂6H ₂o is dissolved in 16ml water and is made into mixed solution, gets the dried Al of 12.4g ₂o ₃sample, evenly mixes both latter standing 45 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 800 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 8wt% of CuO, containing the about 30wt% of ZnO, containing Al ₂o ₃about 62wt%.

Example 12:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

By 130.2g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 70ml water, gets the dried Al of 23.2g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 800 ℃ of air atmospheres, calcine 16 hours.

Product: gained catalyst sample is containing the about 60wt% of ZnO, Al ₂o ₃about 40wt%.

Example 13:

Raw material: Cu (NO ₃) ₂3H ₂o, Fe (NO ₃) ₃9H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 1.1gCu (NO ₃) ₂3H ₂o, 1.9g Fe (NO ₃) ₃9H ₂o and 12.4gZn (NO ₃) ₂6H ₂o is dissolved in 7ml water and is made into mixed solution, gets the dried Al of 5.9g ₂o ₃sample, evenly mixes both latter standing 45 minutes.Under infrared lamp, stir and dry, be placed in afterwards 120 ℃ of oven dryings.In 900 ℃ of air atmospheres, calcine 16 hours.

Product: gained catalyst sample is containing the about 4wt% of CuO, Fe ₂o ₃about 4wt%, the about 33wt% of ZnO, Al ₂o ₃about 59wt%.

Example 14:

Raw material: Ni (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 36.6g Ni (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 31ml water, gets the dried Al of 10.4g ₂o ₃sample, evenly mixes both latter standing 45 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 800 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 40wt% of NiO, Al ₂o ₃about 60wt%.

Example 15:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 79.8g Zn (NO ₃) ₂6H ₂o is dissolved in 140ml water and is made into mixed solution, gets the dried Al of 38.3g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 120 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 36wt% of ZnO, containing Al ₂o ₃about 64wt%.

Example 16:

Raw material: Mg (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 28.2g Mg (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 15ml water, gets the dried Al of 5.6g ₂o ₃sample, evenly mixes both latter standing 60 minutes.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.In 800 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 44wt% of MgO, Al ₂o ₃about 56wt%.

Example 17:

Raw material: Mg (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 18.1g Mg (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 28ml water, gets the dried Al of 7.2g ₂o ₃sample, evenly mixes both latter standing 60 minutes.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.In 800 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 28wt% of MgO, Al ₂o ₃about 72wt%.

Example 18:

Raw material: KNO ₃, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

By 69.6g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 110ml water, gets the dried Al of 31.0g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings and obtain presoma.By 0.3g KNO ₃be dissolved in 13ml water, with 14.0g presoma, mix latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.Finally in 800 ℃ of air atmospheres, calcine 16 hours.

Product: gained catalyst sample is containing K ₂the about 3wt% of O, the about 36wt% of ZnO, Al ₂o ₃about 61wt%.

Example 19:

Raw material: KNO ₃, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

By 76.3g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 130ml water, gets the dried Al of 39.2g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings and obtain presoma.By 0.6g KNO ₃be dissolved in 22ml water, with 14.0g presoma, mix latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.Finally in 800 ℃ of air atmospheres, calcine 16 hours.

Product: gained catalyst sample is containing K ₂the about 5wt% of O, the about 33wt% of ZnO, Al ₂o ₃about 62wt%.

Example 20:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

By 167.6g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 70ml water, gets the dried Al of 14.4g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 500 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 76wt% of ZnO, Al ₂o ₃about 24wt%.

Example 21:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

By 135.2g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 70ml water, gets the dried Al of 23.2g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 500 ℃ of air atmospheres, calcine 8 hours.

Example 22:

Raw material: La (NO ₃) ₃6H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

By 97.5g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 110ml water, gets the dried Al of 33.5g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings and obtain presoma.By 0.8g La (NO ₃) ₃6H ₂o is dissolved in 16ml water, with 15.0g presoma, mixes latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.Finally in 800 ℃ of air atmospheres, calcine 16 hours.

Product: gained catalyst sample is containing La ₂o ₃about 2wt%, the about 42wt% of ZnO, Al ₂o ₃about 56wt%.

Example 23:

Raw material: C ₄h ₆o ₄zn2H ₂o, Al ₂o ₃, deionized water.

By 10.3g C ₄h ₆o ₄zn2H ₂o is dissolved in wiring solution-forming in 30ml water, gets the dried Al of 6.2g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 120 ℃ of oven dryings.In 700 ℃ of air atmospheres, calcine 16 hours.

Product: gained catalyst sample is containing the about 38wt% of ZnO, Al ₂o ₃about 62wt%.

Example 24:

Raw material: H ₃bO ₄, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 63.1g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 100ml water, gets the dried Al of 28.3g ₂o ₃sample, evenly mixes both latter standing 60 minutes.Under infrared lamp, stir and dry, be placed in afterwards 120 ℃ of oven dryings.In 900 ℃ of air atmospheres, calcine and within 12 hours, obtain sample C.By 0.1gH ₃bO ₄be dissolved in wiring solution-forming in 15ml water, and evenly mix with 8g sample C, under infrared lamp, dry, be placed in afterwards 120 ℃ of baking ovens.Finally in 600 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing B ₂o ₃about 1wt%, the about 38wt% of ZnO, Al ₂o ₃about 61wt%.

Example 25:

Raw material: Sn (OCH (CH ₃) ₂) ₄, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, methyl alcohol, isobutanol.

Preparation process: by 0.2g Sn (OCH (CH ₃) ₂) ₄be dissolved in the mixed solution of 20ml methyl alcohol and isobutanol (both volume ratios are 1:1), and evenly mix with the sample C described in 8.0g example 24, under infrared lamp, dry, be placed in afterwards 100 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 1wt% of SnO, the about 38wt% of ZnO, Al ₂o ₃about 61wt%.

Example 26:

Raw material: (NH4) ₃pO ₄.3H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 0.2g (NH4) ₃pO ₄.3H ₂o is dissolved in the mixed solution of 20ml methyl alcohol and isobutanol (both volume ratios are 1:1), and evenly mixes with the sample C described in 8.0g example 24, under infrared lamp, dries, and is placed in afterwards 100 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing P ₂o ₅about 1wt%, the about 38wt% of ZnO, Al ₂o ₃about 61wt%.

Example 27:

Raw material: Ti (OC ₄h ₉) ₄, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, isopropyl alcohol.

Preparation process: by 0.4g Ti (OC ₄h ₉) ₄be dissolved in 10ml isopropyl alcohol, and evenly mix with the sample C described in 8.0g example 24, under infrared lamp, dry, be placed in afterwards 100 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing TiO ₂about 1wt%, the about 38wt% of ZnO, Al ₂o ₃about 61wt%.

Example 28:

Raw material: (NH ₄) ₆mo ₇o ₂₄4H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 0.7g (NH ₄) ₆mo ₇o ₂₄.4H ₂o is dissolved in wiring solution-forming in 16ml water, and evenly mixes with the sample C described in 8.0g example 24, under infrared lamp, dries, and is placed in afterwards 110 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing MoO ₃about 1wt%, the about 38wt% of ZnO, Al ₂o ₃about 61wt%.

Example 29

Preparation process: by 30.1g Zn (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 100ml water, gets the dried Al of 15.8g ₂o ₃sample, evenly mixes both latter standing 40 minutes.Under infrared lamp, stir and dry, be placed in afterwards 120 ℃ of oven dryings.In 900 ℃ of air atmospheres, calcine and within 12 hours, obtain sample D.By 2.7g Cu (NO ₃) ₂3H ₂o is dissolved in wiring solution-forming in 15ml water, and evenly mixes with 9.0g sample A, under infrared lamp, dries, and is placed in afterwards 120 ℃ of baking ovens.Finally in 600 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 9wt% of CuO, the about 30wt% of ZnO, Al ₂o ₃about 61wt%.

Example 30:

Preparation process: by 5.5g Cu (NO ₃) ₂3H ₂o is dissolved in wiring solution-forming in 15ml water, and evenly mixes with the sample D described in 9.0g example 29, under infrared lamp, dries, and is placed in afterwards 120 ℃ of baking ovens.Finally in 600 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 17wt% of CuO, the about 28wt% of ZnO, Al ₂o ₃about 55wt%.

Example 31:

Raw material: Fe (NO ₃) ₃9H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 1.4g Fe (NO ₃) ₃9H ₂o is dissolved in wiring solution-forming in 15ml water, and evenly mixes with the sample D described in 9.0g example 29, under infrared lamp, dries, and is placed in afterwards 110 ℃ of baking ovens.Finally in 500 ℃ of air atmospheres, calcine 5 hours.

Product: gained catalyst sample is containing Fe ₂o ₃about 3wt%, the about 33wt% of ZnO, Al ₂o ₃about 64wt%.

Example 32:

Raw material: Sr (NO ₃) ₂, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 0.2g Sr (NO ₃) ₂be dissolved in wiring solution-forming in 16ml water, and evenly mix with the sample D described in 9.0g example 29, under infrared lamp, dry, be placed in afterwards 110 ℃ of baking ovens.Finally in 550 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 1wt% of SrO, the about 34wt% of ZnO, Al ₂o ₃about 65wt%.

Example 33:

Raw material: Ce (NO ₃) ₃6H ₂o, Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 0.2g Ce (NO ₃) ₃.6H ₂o is dissolved in wiring solution-forming in 16ml water, and evenly mixes with the sample D described in 9.0g example 29, under infrared lamp, dries, and is placed in afterwards 110 ℃ of baking ovens.Finally in 550 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing Ce ₂o ₃about 1wt%, the about 34wt% of ZnO, Al ₂o ₃about 65wt%.

Example 34:

Preparation process: by 1.9g Fe (NO ₃) ₃9H ₂o and 13.80g Zn (NO ₃) ₂6H ₂o is dissolved in 6ml water and is made into mixed solution, gets the dried Al of 5.9g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 120 ℃ of oven dryings.In 900 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing Fe ₂o ₃about 4wt%, the about 34wt% of ZnO, Al ₂o ₃about 61wt%.

Example 35:

Preparation process: by 11.3g Cu (NO ₃) ₂3H ₂o and 13.9g Zn (NO ₃) ₂6H ₂o is dissolved in 17ml water and is made into mixed solution, gets the dried Al of 12.4g ₂o ₃sample, evenly mixes both latter standing 45 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 900 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 19wt% of CuO, containing the about 19wt% of ZnO, containing Al ₂o ₃about 62wt%.

Example 36:

Preparation process: by 5.7g Cu (NO ₃) ₂3H ₂o and 20.91g Zn (NO ₃) ₂6H ₂o is dissolved in 20ml water and is made into mixed solution, gets the dried Al of 12.4g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 9wt% of CuO, containing the about 29wt% of ZnO, containing Al ₂o ₃about 62wt%.

Example 37:

Preparation process: by 3.8g Cu (NO ₃) ₂3H ₂o and 23.2g Zn (NO ₃) ₂6H ₂o is dissolved in 17ml water and is made into mixed solution, gets the dried Al of 12.4g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 6wt% of CuO, containing the about 32wt% of ZnO, containing Al ₂o ₃about 62wt%.

Example 38:

Preparation process: by 4.5g Cu (NO ₃) ₂3H ₂o and 22.3g Zn (NO ₃) ₂6H ₂o is dissolved in 42ml water and is made into mixed solution, gets the dried Al of 12.4g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine 8 hours.

Example 39:

Raw material: Cu (NO ₃) ₂3H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 22.7g Cu (NO ₃) ₂3H ₂o is dissolved in 20ml water, gets the dried Al of 12.5g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 900 ℃ of air atmospheres, calcine 16 hours.

Product: gained catalyst sample is containing the about 38wt% of CuO, Al ₂o ₃about 62wt%.

Example 40:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 78.1gZn (NO ₃) ₂6H ₂o is dissolved in 150ml water, gets the dried Al of 40.1g ₂o ₃sample, evenly mixes both latter standing 60 minutes.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.In 800 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 35wt% of ZnO, containing Al ₂o ₃about 65wt%.

Example 41:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 10.4g Zn (NO ₃) ₂6H ₂o is dissolved in 5ml water, gets the dried Al of 7.2g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 28wt% of ZnO, containing Al ₂o ₃about 72wt%.

Example 42:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 7.7g Zn (NO ₃) ₂6H ₂o is dissolved in 5ml water, gets the dried Al of 7.9g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 21wt% of ZnO, containing Al ₂o ₃about 79wt%.

Example 43:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 6.1gZn (NO ₃) ₂6H ₂o is dissolved in 5ml water, gets the dried Al of 8.3g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.In 850 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 16wt% of ZnO, containing Al ₂o ₃about 84wt%.

Example 44:

Preparation process: by 4.5g Cu (NO ₃) ₂3H ₂o and 22.3g Zn (NO ₃) ₂6H ₂o is dissolved in 16ml water and is made into mixed solution, gets the dried Al of 12.4g ₂o ₃sample, evenly mixes both latter standing 45 minutes.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.In 900 ℃ of air atmospheres, calcine 8 hours.

Example 45:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: by 76.3g Zn (NO ₃) ₂6H ₂o is dissolved in 130ml water, gets the dried Al of 39.2g ₂o ₃sample, evenly mixes both latter standing 30 minutes.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings, finally in 500 ℃ of air atmospheres, calcine 8 hours.

Example 46:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: preparation process, described in example 45, is calcined the sample of oven dry 8 hours in 700 ℃ of air atmospheres.Product: gained catalyst sample is containing the about 35wt% of ZnO, containing Al ₂o ₃about 65wt%.

Example 47:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: preparation process, described in example 45, is calcined the sample of oven dry 8 hours in 600 ℃ of air atmospheres.

Example 48:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: preparation process, described in example 45, is calcined the sample of oven dry 8 hours in 900 ℃ of air atmospheres.

Example 49:

Raw material: Zn (NO ₃) ₂6H ₂o, Al ₂o ₃, deionized water.

Preparation process: preparation process, described in example 45, is calcined the sample of oven dry 16 hours in 900 ℃ of air atmospheres.

Example 50:

Raw material: Cu (NO ₃) ₂3H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, (NH ₄) ₂cO ₃, deionized water.

Preparation process: by 1.2g Cu (NO ₃) ₂3H ₂o, 13.5g Zn (NO ₃) ₂6H ₂o and 43.5gAl (NO ₃) ₃9H ₂o is dissolved in 140ml water and is made into mixing salt solution.Separately by 22.3g (NH ₄) ₂cO ₃be dissolved in proportionaling alkali-forming solution in 150ml water.Under agitation, mixing salt solution is slowly added drop-wise in aqueous slkali, dropwises rear continuation and stir standing sedimentation after 8 hours.Gained precipitation after centrifuge washing, 60 ℃ of oven dry, finally 850 ℃ of calcinings 4 hours in air atmosphere.

Product: gained catalyst sample is containing the about 4wt% of CuO, the about 36wt% of ZnO, Al ₂o ₃be about 60wt%.

Example 51:

Raw material: Cu (NO ₃) ₂3H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 11.9g Cu (NO ₃) ₂3H ₂o and 44.5g Al (NO ₃) ₃9H ₂o is dissolved in 140ml water and is made into mixing salt solution.Separately by 53.9g NH ₄hCO ₃be dissolved in proportionaling alkali-forming solution in 450ml water.Under agitation, mixing salt solution is slowly added drop-wise in aqueous slkali, dropwises rear continuation and stir standing sedimentation after 4 hours.Gained precipitation after centrifuge washing, 90 ℃ of oven dry, finally 850 ℃ of calcinings 8 hours in air atmosphere.

Product: gained catalyst sample is containing the about 40wt% of CuO, containing Al ₂o ₃about 60wt%.

Example 52:

Raw material: Cu (NO ₃) ₂3H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 6.0g Cu (NO ₃) ₂3H ₂o, 7.3g Zn (NO ₃) ₂6H ₂o and 44.4gAl (NO ₃) ₃9H ₂o is dissolved in 140ml water and is made into mixing salt solution.Separately by 53.7g NH ₄hCO ₃be dissolved in proportionaling alkali-forming solution in 450ml water.Under agitation, mixing salt solution is slowly added drop-wise in aqueous slkali, dropwises rear continuation and stir standing sedimentation after 1.5 hours.Gained precipitation after centrifuge washing, 70 ℃ of oven dry, finally 900 ℃ of calcinings 16 hours in air atmosphere.

Product: gained catalyst sample is containing the about 20wt% of CuO, the about 20wt% of ZnO, Al ₂o ₃about 60wt%.

Example 53:

Raw material: Fe (NO ₃) ₃9H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, (NH ₄) ₂cO ₃, deionized water.

Preparation process: by 2.0g Fe (NO ₃) ₃9H ₂o, 14.8g Zn (NO ₃) ₂6H ₂o and 41.0gAl (NO ₃) ₃9H ₂o is dissolved in 137ml deionized water and is made into mixing salt solution.Separately by 22.0g (NH ₄) ₂cO ₃be dissolved in proportionaling alkali-forming solution in 150ml water.Under agitation, mixing salt solution is slowly added drop-wise in aqueous slkali, dropwises rear continuation and stir standing sedimentation after 8 hours.Gained precipitation after centrifuge washing, 60 ℃ of oven dry, finally 850 ℃ of calcinings 4 hours in air atmosphere.

Product: gained catalyst sample is containing Fe ₂o ₃about 4wt%, the about 40wt% of ZnO, Al ₂o ₃be about 56wt%.

Example 54:

Raw material: Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NaOH, Na ₂cO ₃, deionized water.

Preparation process: by 53.6g Zn (NO ₃) ₂6H ₂o and 22.5g Al (NO ₃) ₃9H ₂o is dissolved in 200ml deionized water and is made into mixing salt solution.Separately by 15.4gNaOH and 12.7g Na ₂cO ₃be dissolved in proportionaling alkali-forming solution in 200ml water.Under agitation, mixing salt solution is slowly added drop-wise in aqueous slkali, dropwises rear 90 ℃ of ageings 4 hours.Gained precipitation after centrifuge washing, 60 ℃ of oven dry, finally 800 ℃ of calcinings 3 hours in air atmosphere.

Product: gained catalyst sample is containing Na ₂o approximately 0.1%, the about 69.9wt% of ZnO, Al ₂o ₃be about 30wt%.

Example 55:

Preparation process: get 10.0g example 54 products obtained therefroms, be placed in 25ml 10M NaOH solution, 60 ℃ are stirred 48h.Afterwards gained sample filtering is dried.

Product: gained catalyst sample is containing Na ₂o is about 0.1%, ZnO and is about 40wt%, Al ₂o ₃be about 59.9wt%.

Example 56:

Raw material: Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, (NH ₄) ₂cO ₃, deionized water.

Preparation process: by 55.7g Zn (NO ₃) ₂6H ₂o and 182.6g Al (NO ₃) ₃9H ₂o is dissolved in 560ml water and is made into mixing salt solution.Separately by 93.6g (NH ₄) ₂cO ₃be dissolved in proportionaling alkali-forming solution in 560ml water.Under agitation, mixing salt solution and aqueous slkali are slowly added drop-wise in 360ml water, dropwise rear continuation and stir standing sedimentation after 16 hours.Gained precipitation after centrifuge washing, 85 ℃ of oven dry, finally 700 ℃ of calcinings 12 hours in air atmosphere.

Example 57:

Preparation process: by 90.0g Zn (NO ₃) ₂6H ₂o and 260.9g Al (NO ₃) ₃9H ₂o is dissolved in 830ml water and is made into mixing salt solution.Separately by 134.0g (NH ₄) ₂cO ₃be dissolved in proportionaling alkali-forming solution in 830ml water.Under agitation, mixing salt solution and aqueous slkali are slowly added drop-wise in 530ml water, after dropwising immediately by gained precipitation after centrifuge washing, 85 ℃ of oven dry, finally 750 ℃ of calcinings 6 hours in air atmosphere.

Product: gained catalyst sample is containing the about 39wt% of ZnO, Al ₂o ₃about 61wt%.

Example 58:

Preparation process: by 45.0g Zn (NO ₃) ₂6H ₂o and 130.5g Al (NO ₃) ₃9H ₂o is dissolved in 400ml water and is made into mixing salt solution.Separately by 80.0g (NH ₄) ₂cO ₃be dissolved in proportionaling alkali-forming solution in 400ml water.Under agitation, mixing salt solution and aqueous slkali are slowly added drop-wise in 260ml water, dropwise rear continuation and stir after 4 hours and staticly settle, by gained precipitation after centrifuge washing, 85 ℃ of oven dry, finally 750 ℃ of calcinings 8 hours in air atmosphere.

Example 59:

Preparation process: by 1.2g Cu (NO ₃) ₂3H ₂o, 13.2g Zn (NO ₃) ₂6H ₂o and 44.3gAl (NO ₃) ₃9H ₂o is dissolved in 140ml water and is made into mixing salt solution.Separately by 53.6g NH ₄hCO ₃be dissolved in proportionaling alkali-forming solution in 450ml water.Under agitation, mixing salt solution is slowly added drop-wise in aqueous slkali, dropwises rear continuation and stir standing sedimentation after 1.5 hours.Gained precipitation after centrifuge washing, 80 ℃ of oven dry, finally 900 ℃ of calcinings 16 hours in air atmosphere.

Product: gained catalyst sample is containing the about 4wt% of CuO, the about 36wt% of ZnO, Al ₂o ₃about 60wt%.

Example 60:

Preparation process: by 22.5g Zn (NO ₃) ₂6H ₂o and 65.2g Al (NO ₃) ₃9H ₂o is dissolved in 100ml water and is made into mixing salt solution.Separately by 33.4g (NH ₄) ₂cO ₃be dissolved in proportionaling alkali-forming solution in 100ml water.Under agitation, mixing salt solution and aqueous slkali are slowly added drop-wise in 70ml water, dropwise rear continuation and stir after 1 hour and staticly settle, by gained precipitation after centrifuge washing, 60 ℃ of oven dry, finally 700 ℃ of calcinings 16 hours in air atmosphere.

Product: gained catalyst sample is containing the about 40wt% of ZnO, Al ₂o ₃about 60wt%.

Example 61:

Preparation process: by 23.8g Zn (NO ₃) ₂6H ₂o and 60.0g Al (NO ₃) ₃9H ₂o is dissolved in 200ml water and is made into mixing salt solution.Separately by 53.8g (NH ₄) ₂cO ₃be dissolved in proportionaling alkali-forming solution in 200ml water.In flask, put into 160ml water, under stirring condition, mixing salt solution and aqueous slkali are slowly added drop-wise in system, dropwise latter 90 ℃ still aging 16 hours, by gained precipitation after centrifuge washing, 60 ℃ of oven dry, finally in air atmosphere 500 ℃ calcining 8 hours.

Product: gained catalyst sample is containing the about 43wt% of ZnO, Al ₂o ₃about 57wt%.

Example 62:

Preparation process: by 80.0g Zn (NO ₃) ₂6H ₂o and 217.5g Al (NO ₃) ₃9H ₂o is dissolved in 700ml water and is made into mixing salt solution.Separately by 112.0g (NH ₄) ₂cO ₃be dissolved in proportionaling alkali-forming solution in 700ml water.Under agitation, mixing salt solution and aqueous slkali are slowly added drop-wise in 300ml water, dropwise rear continuation stirring and staticly settle after 16 hours.By gained precipitation after centrifuge washing, 85 ℃ of oven dry, finally 700 ℃ of calcinings 4 hours in air atmosphere.

Example 63:

Raw material: Cu (NO ₃) ₂3H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, urea, deionized water.

Preparation process: by 1.0gCu (NO ₃) ₂3H ₂o, 13.3g Zn (NO ₃) ₂6H ₂o, 46.9gAl (NO ₃) ₃9H ₂o and 41.8g urea are dissolved in 400ml water and are made into mixed solution.At 90 ℃, stir 5 hours, afterwards standing sedimentation.Gained precipitation after centrifuge washing, 90 ℃ of oven dry, finally 700 ℃ of calcinings 12 hours in air atmosphere.

Product: gained catalyst sample is containing the about 2wt% of CuO, the about 20wt% of ZnO, Al ₂o ₃about 78wt%.

Example 64:

Raw material: Cu (NO ₃) ₂3H ₂o, Fe (NO ₃) ₃9H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, urea, deionized water.

Preparation process: by 1.0g Cu (NO ₃) ₂3H ₂o, 0.3g Fe (NO ₃) ₃9H ₂o, 12.2gZn (NO ₃) ₂6H ₂o, 49.2g Al (NO ₃) ₃9H ₂o and 42.15g urea are dissolved in 407ml water and are made into mixed solution.At 90 ℃, stir 5 hours, afterwards standing sedimentation.Gained precipitation after centrifuge washing, 90 ℃ of oven dry, finally 700 ℃ of calcinings 12 hours in air atmosphere.

Product: gained catalyst sample is containing the about 2wt% of CuO, Fe ₂o ₃about 0.5wt%, the about 17.5wt% of ZnO, Al ₂o ₃about 80wt%.

Example 65:

Raw material: Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, urea, deionized water.

Preparation process: by 14.6g Zn (NO ₃) ₂6H ₂o, 44.3g Al (NO ₃) ₃9H ₂o and 40.7g urea are dissolved in 400ml water and are made into mixed solution.At 90 ℃, stir 6 hours, afterwards standing sedimentation.Gained precipitation after centrifuge washing, 90 ℃ of oven dry, finally 700 ℃ of calcinings 8 hours in air atmosphere.

Product: gained catalyst sample is containing the about 41wt% of ZnO, Al ₂o ₃about 59wt%.

Example 66:

Preparation process: by 23.3g Zn (NO ₃) ₂6H ₂o, 56.3g Al (NO ₃) ₃9H ₂o and 54.0g urea are dissolved in 560ml water and are made into mixed solution.At 90 ℃, stir 5 hours, afterwards standing sedimentation.Gained precipitates after centrifuge washing, 90 ℃ of oven dry.Finally in air atmosphere 700 ℃ calcining 8 hours.

Product: gained catalyst sample is containing the about 45wt% of ZnO, Al ₂o ₃about 55wt%.

Example 67:

Raw material: (NH ₄) ₃pO ₄.3H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 482.6g Zn (NO ₃) ₂6H ₂o and 1460.2g Al (NO ₃) ₃9H ₂o is dissolved in 4600ml water and is made into mixing salt solution.Separately by 1768.8g NH ₄hCO ₃be dissolved in proportionaling alkali-forming solution in 14920ml water.Under agitation, mixing salt solution is slowly added drop-wise in aqueous slkali, dropwises rear continuation and stir standing sedimentation after 4 hours.Gained precipitation, after centrifuge washing, in 70 ℃ of oven dry, obtains presoma E.Separately by 1.2g (NH ₄) ₃pO ₄.3H ₂o is dissolved in wiring solution-forming in 8ml water, evenly mixes latter standing 60 minutes with 13.5g presoma E.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.Finally in 750 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 5wt% of P2O5, the about 38wt% of ZnO, Al ₂o ₃about 57wt%.

Example 68:

Raw material: Pb (NO ₃) ₂, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 0.1g Pb (NO ₃) ₂be dissolved in wiring solution-forming in 8ml water, evenly mix latter standing 45 minutes with the presoma E in 13.5g example 67.Under infrared lamp, stir and dry, be placed in afterwards 120 ℃ of oven dryings.Finally in 750 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is about 1wt%, the about 40wt% of ZnO, Al containing PbO ₂o ₃be about 59wt%.

Example 69:

Raw material: Zr (NO ₃) ₄5H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 0.3g Zr (NO ₃) ₄5H ₂o is dissolved in wiring solution-forming in 8ml water, evenly mixes latter standing 45 minutes with the presoma E in 13.5g example 67.Under infrared lamp, stir and dry, be placed in afterwards 120 ℃ of oven dryings.Finally in 850 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing ZrO ₂about 1wt%, the about 40wt% of ZnO, Al ₂o ₃about 59wt%.

Example 70:

Raw material: Fe (NO ₃) ₃9H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 0.4g Fe (NO ₃) ₃9H ₂o is dissolved in wiring solution-forming in 8ml water, evenly mixes latter standing 60 minutes with the presoma E in 13.5g example 67.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.Finally in 900 ℃ of air atmospheres, calcine 10 hours.

Product: gained catalyst sample is containing Fe ₂o ₃about 1wt%, the about 40wt% of ZnO, Al ₂o ₃about 59wt%.

Example 71:

Preparation process: by 0.2g Cu (NO ₃) ₂3H ₂o is dissolved in wiring solution-forming in 8ml water, evenly mixes latter standing 40 minutes with the presoma E in 13.5g example 67.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.Finally in 800 ℃ of air atmospheres, calcine 8 hours.

Product: gained catalyst sample is containing the about 1wt% of CuO, the about 40wt% of ZnO, Al ₂o ₃about 59wt%.

Example 72:

Raw material: Co (NO ₃) ₂6H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 0.3g Co (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 8ml water, evenly mixes latter standing 40 minutes with the presoma E in 13.5g example 67.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.Finally in 900 ℃ of air atmospheres, calcine 10 hours.

Product: gained catalyst sample is containing Co ₂o ₃about 1wt%, the about 40wt% of ZnO, Al ₂o ₃about 59wt%.

Example 73:

Raw material: SnCl ₂, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 0.1gSnCl ₂be dissolved in 10ml water, evenly mix latter standing 40 minutes with the presoma E in 13.5g example 67.Under infrared lamp, stir and dry, be placed in afterwards 100 ℃ of oven dryings.Finally in 750 ℃ of air atmospheres, calcine 10 hours.

Product: gained catalyst sample is containing the about 1wt% of SnO, the about 40wt% of ZnO, Al ₂o ₃about 59wt%.

Example 74:

Raw material: LiNO ₃, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 1.9g LiNO ₃be dissolved in wiring solution-forming in 14ml water, evenly mix latter standing 60 minutes with the presoma E described in 13.5g example 67.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.Finally in 750 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing Li ₂the about 5wt% of O, the about 38wt% of ZnO, Al ₂o ₃about 57wt%.

Example 75:

Raw material: Ni (NO ₃) ₂6H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, deionized water.

Preparation process: by 1.6g Ni (NO ₃) ₂6H ₂o is dissolved in wiring solution-forming in 14ml water, evenly mixes latter standing 60 minutes with the presoma E described in 13.5g example 67.Under infrared lamp, stir and dry, be placed in afterwards 110 ℃ of oven dryings.Finally in 750 ℃ of air atmospheres, calcine 3 hours.

Product: gained catalyst sample is containing the about 5wt% of NiO, the about 38wt% of ZnO, Al ₂o ₃about 57wt%.

Example 76:

Raw material: La (NO ₃) ₃.6H ₂o, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, urea, deionized water.

Preparation process: by 50.2g Zn (NO ₃) ₂6H ₂o, 126.6g Al (NO ₃) ₃9H ₂o and 121.5g urea are dissolved in 1200ml water and are made into mixed solution.At 90 ℃, stir 5 hours, afterwards standing sedimentation.Gained precipitation is after centrifuge washing, and 90 ℃ of oven dry obtain presoma E.By 0.8g La (NO ₃) ₃6H ₂o is dissolved in 5ml water, with 15.0g presoma, evenly mixes latter standing 30 minutes, under infrared lamp, dries, and is placed in afterwards 100 ℃ of baking ovens.Finally in air atmosphere 750 ℃ calcining 8 hours.

Example 77:

Raw material: KNO ₃, Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, urea, deionized water.

Preparation process: by 0.6g KNO ₃be dissolved in 5ml water, with the presoma E described in 15.0g example 76, evenly mix latter standing 30 minutes, under infrared lamp, dry, be placed in afterwards 100 ℃ of baking ovens.Finally in air atmosphere 750 ℃ calcining 8 hours.

Product: gained catalyst sample is containing K ₂the about 2wt% of O, the about 42wt% of ZnO, Al ₂o ₃about 56wt%.

Example 78:

Raw material: Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, C ₂h ₂o ₄, deionized water.

Preparation process: by 14.6g Zn (NO ₃) ₂6H ₂o and 44.3g Al (NO ₃) ₃9H ₂o is dissolved in 140ml water and is made into mixing salt solution.Separately by 53.6g NH ₄hCO ₃be dissolved in proportionaling alkali-forming solution in 450ml water.Under agitation, mixing salt solution is slowly added drop-wise in aqueous slkali, dropwises rear continuation and stir standing sedimentation after 4 hours.Gained precipitation, after centrifuge washing, in 70 ℃ of oven dry, then is calcined 3 hours in 750 ℃ of air atmospheres.Use again 20ml C ₂h ₂o ₄at 70 ℃ of solution (0.2M), soak filtration washing after 4 hours, 120 ℃ of oven dry.

Product: gained catalyst sample is containing the about 44wt% of ZnO, Al ₂o ₃about 56wt%.

Example 79:

Raw material: Zn (NO ₃) ₂6H ₂o, Al (NO ₃) ₃9H ₂o, NH ₄hCO ₃, NaOH, deionized water.

Preparation process: by 14.6g Zn (NO ₃) ₂6H ₂o and 44.3g Al (NO ₃) ₃9H ₂o is dissolved in 140ml water and is made into mixing salt solution.Separately by 53.6g NH ₄hCO ₃be dissolved in proportionaling alkali-forming solution in 450ml water.Under agitation, mixing salt solution is slowly added drop-wise in aqueous slkali, dropwises rear continuation and stir standing sedimentation after 4 hours.Gained precipitation, after centrifuge washing, in 70 ℃ of oven dry, then is calcined 3 hours in 750 ℃ of air atmospheres.Use again at 70 ℃ of 20ml NaOH solution (0.2M) and soak filtration washing after 4 hours, 120 ℃ of oven dry.

Product: gained catalyst sample is containing Na ₂o approximately 0.2%, the about 42.9wt% of ZnO, Al ₂o ₃about 56.9wt%.

Example 80:

Preparation process: described in the similar example 78 of experimental technique, the sample after roasting is adopted to 20mlC ₂h ₂o ₄under solution (0.2M) room temperature, soak filtration washing after 4 hours, 120 ℃ of oven dry.

Product: gained catalyst is containing the about 41wt% of ZnO, Al ₂o ₃about 59wt%.

Example 81:

Preparation process: described in the similar example 79 of experimental technique, sample after roasting is adopted and soaks filtration washing after 4 hours, 120 ℃ of oven dry under 20mlNaOH solution (0.2M) room temperature.

Product: gained catalyst sample is containing Na ₂o approximately 0.2%, the about 39.9wt% of ZnO, Al ₂o ₃about 59.9wt%.

Note: wherein, in product, contain a large amount of CO preparing before roasting ₃ ^2-, NH ₄ ⁺, and NO ₃ ^-, it decomposes removal in roasting process, and this common practise that is those skilled in the art, does not repeat them here.

(2). application and measure of merit:

Test process: for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, wherein, alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether process comprise by the above-mentioned catalyst making:

First in paste state bed reactor or the first fixed bed reactors, pass into urea and methyl alcohol, to react, generate methyl carbamate and ammonia; Wherein, it is 110 ~ 160 ℃ that described paste state bed reactor or the first fixed bed reactors reaction condition are controlled, 0.2 ~ 2.0MPa;

Afterwards by product with liquid hourly space velocity (LHSV) LHSV=0.25h ^-1pass in the second fixed bed reactors that the multicomponent composite oxide catalysts that the various embodiments described above produce is housed, controlling reaction condition is 185 ℃, 0.7MPa, Formed dimethyl phthalate, dimethyl ether, ammonia and carbon dioxide, gather the product being generated by the second fixed bed reactors and do chromatography and detect.Concrete testing result is as shown in table 1:

Table 1 alcoholysis of urea Raw conversion ratio and each selectivity of product test result list

Above-mentioned table 1 for only with under above-mentioned specified conditions, above-mentioned 81 embodiment in the method for alcoholysis of urea co-producing dimethyl carbonate of the present invention and dimethyl ether, for the conversion ratio of MC, the example of the selective regulation effect of the selective and DME of DMC.So in the method for alcoholysis of urea co-producing dimethyl carbonate of the present invention and dimethyl ether, above-mentioned 81 embodiment its all can according to different component and content in each embodiment, different preparation method and and preparation process in different roasting conditions realize its in the method for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether for the conversion ratio of MC, the optionally adjustment of the selective and DME of DMC.At this, enumerate no longer one by one.

In sum, multicomponent composite oxide catalysts of the present invention is applied in alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether technique, can effectively improve the conversion ratio of raw material, the selective and dimethyl ether of dimethyl carbonate selective.And be conducive to follow-up in DMC, DME, MC, ammonia and methyl alcohol separation and Extraction DMC, DME and reduce energy consumption.In addition, this process device structure is simple, and process conditions are easy to control, and are applicable to industrial mass production.

Although the present invention discloses as above with preferred embodiment, the present invention is not defined in this.Any those skilled in the art, various changes and the modification done without departing from the spirit and scope of the present invention, all within protection scope of the present invention.Therefore protection scope of the present invention should be as the criterion with claim limited range.

Claims

1. for a catalyst for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether, it is characterized in that,

The active component of catalyst comprises: in transition metal oxide, rare-earth oxide, alkali metal oxide, alkaline earth oxide, IVA family metal oxide ,VA family's nonmetal oxide or IIIA family nonmetal oxide or one or more and Al ₂o ₃.

2. catalyst as claimed in claim 1, is characterized in that, described transition metal oxide is TiO ₂, ZrO ₂, Co ₂o ₃, ZnO, CuO, MoO ₃, Fe ₂o ₃, NiO and Cr ₂o ₃in one or more;

Described rare-earth oxide is La ₂o ₃and/or Ce ₂o ₃;

Described alkali metal oxide is Li ₂o, Na ₂o and K ₂one or more in O;

Described alkaline earth oxide is one or more in MgO, CaO, SrO and BaO;

Described IVA family metal oxide is SnO and/or PbO;

Described VA family nonmetal oxide is P ₂o ₅;

Described IIIA family nonmetal oxide is B ₂o ₃.

3. catalyst as claimed in claim 2, is characterized in that, in the mass percent of the active component of described catalyst forms, and described Al ₂o ₃content is 20 ~ 85wt%;

Described transition metal oxide content is 0 ~ 75wt%;

4. catalyst as claimed in claim 3, it is characterized in that one or more and the Al of the active component of described catalyst in transition metal oxide, alkali metal oxide, alkaline earth oxide and rare-earth oxide, IVA family metal oxide ,VA family's nonmetal oxide or IIIA family nonmetal oxide ₂o ₃form; Wherein, the mass percent component of the active component of described catalyst is:

Al ₂o ₃content is 50 ~ 85wt%; Transition metal oxide content is 15 ~ 48wt%;

The content of rest activity component is 0 ~ 2wt%.

5. catalyst as claimed in claim 4, is characterized in that, the mass percent component of the active component of described catalyst is:

Al ₂o ₃content is 53 ~ 70wt%; Transition metal oxide content is 30 ~ 45wt%;

The total content of rest activity component is 0 ~ 2wt%.

6. catalyst as claimed in claim 5, is characterized in that, the mass percent component of the active component of described catalyst is:

7. the catalyst as described in claim 1 ~ 6 any one, is characterized in that, described transition metal oxide is ZnO or CuO.

8. a preparation method for the catalyst for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether as described in claim 1 ~ 7 any one, is characterized in that, its process comprises:

9. a preparation method for the catalyst for alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether as described in claim 1 ~ 7 any one, is characterized in that, its process comprises:

10. method for preparing catalyst as claimed in claim 9, is characterized in that, described alkaline solution comprises the aqueous solution of ammonium carbonate, carbonic hydroammonium, urea, NaOH or sodium carbonate.

The method of 11. 1 kinds of alcoholysis of urea co-producing dimethyl carbonates and dimethyl ether, is characterized in that, to passing into urea in paste state bed reactor or the first fixed bed reactors and methyl alcohol reaction generates methyl carbamate and ammonia;

Product is passed in the second fixed bed reactors, Formed dimethyl phthalate and ammonia, wherein part dimethyl carbonate is decomposed into dimethyl ether and carbon dioxide;

12. methods of alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether as claimed in claim 11, is characterized in that, described transition metal oxide is TiO ₂, ZrO ₂, Co ₂o ₃, ZnO, CuO, MoO ₃, Fe ₂o ₃, NiO and Cr ₂o ₃in one or more;

Described rare-earth oxide is La ₂o ₃and/or Ce ₂o ₃;

Described alkali metal oxide is Li ₂o, Na ₂o and K ₂one or more in O;

Described alkaline earth oxide is one or more in MgO, CaO, SrO and BaO;

Described IVA family metal oxide is SnO and/or PbO;

Described VA family nonmetal oxide is P ₂o ₅;

Described IIIA family nonmetal oxide is B ₂o ₃.

13. methods of alcoholysis of urea co-producing dimethyl carbonate and dimethyl ether as claimed in claim 12, is characterized in that, in the mass percent of the active component of described catalyst forms, and described Al ₂o ₃content is 20 ~ 85wt%;

Described transition metal oxide content is 0 ~ 75wt%;

The method of 14. alcoholysis of urea co-producing dimethyl carbonates as claimed in claim 13 and dimethyl ether, it is characterized in that one or more and the Al of the active component of described catalyst in transition metal oxide, alkali metal oxide, alkaline earth oxide and rare-earth oxide, IVA family metal oxide ,VA family's nonmetal oxide or IIIA family nonmetal oxide ₂o ₃form; Wherein, the mass percent component of the active component of described catalyst is:

Al ₂o ₃content is 50 ~ 85wt%; Transition metal oxide content is 15 ~ 48wt%;

The content of rest activity component is 0 ~ 2wt%;

The method of 15. alcoholysis of urea co-producing dimethyl carbonates as claimed in claim 14 and dimethyl ether, is characterized in that, the mass percent component of the active component of described catalyst is:

Al ₂o ₃content is 53 ~ 70wt%; Transition metal oxide content is 30 ~ 45wt%;

The total content of rest activity component is 0 ~ 2wt%;

The method of 16. alcoholysis of urea co-producing dimethyl carbonates as claimed in claim 15 and dimethyl ether, is characterized in that, the mass percent component of the active component of described catalyst is: Al ₂o ₃content is 55 ~ 65wt%; Described one or more transition metal oxide total contents are 35 ~ 45wt%; Rest activity constituent content is 0 ~ 1%.

17. alcoholysis of urea co-producing dimethyl carbonates as described in claim 11 ~ 16 any one and the method for dimethyl ether, is characterized in that, described transition metal oxide is ZnO or CuO.

The method of 18. alcoholysis of urea co-producing dimethyl carbonates as claimed in claim 11 and dimethyl ether, is characterized in that, utilizes the method described in claim 8 ~ 10 any one to prepare described catalyst.

The method of 19. alcoholysis of urea co-producing dimethyl carbonates as claimed in claim 18 and dimethyl ether, it is characterized in that, sintering temperature and/or the time of the catalyst regulate adopting in preparation process, to control the conversion ratio of MC, the selective and DME of DMC selective.