CN1416949A - Metal oxide catalyst for synthesizing methyl carbonate by urea process and its prepn - Google Patents
Metal oxide catalyst for synthesizing methyl carbonate by urea process and its prepn Download PDFInfo
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Abstract
The metal oxide catalyst for urea alcoholysis process of synthesizing methyl carbonate consists of 1-3 kinds oxides of Li, Mg, Ni, Zn, Pb, Al, Fe, Mo, Zr and La, and has ZnO as main component accounting for 35-95 wt%. When it consists of three kinds of metal oxide, the other two except ZnO have the same weight percentage. It is prepared through thermal decomposition process, precipitation process, or coprecipitation process. The catalyst is easy to prepare, separate, recover and regenerate, and has high catalytic activity for urea alcoholysis process of synthesizing methyl carbonate, yield up to 49.7%, no corrosion of equipment and no environmental pollution.
Description
Technical field
The invention belongs to methylcarbonate metal oxide catalyst and preparation method thereof, particularly oxide compound of Synthesis of Dimethyl Carbonate from Urea lithium, magnesium, nickel, zinc, lead, aluminium, iron, molybdenum, zirconium, lanthanum and composition thereof and their preparation method.
Technical background
Methylcarbonate is a kind of important Organic Chemicals, can replace phosgene, methyl chloride, the methyl-sulfate of severe toxicity to carry out carbonylation, methylate, methoxylation, be used for synthetic multiple organic chemicals and fine chemicals, also can be used as nontoxic solvent and high performance oil dope.At present, the industrialized preparing process of methylcarbonate has phosgenation, ester-interchange method and oxidative carbonylation of methanol method, but there is drawback in they at aspects such as safety, environmental protection, economy and technologies respectively: as the raw material severe toxicity of phosgenation, and by-product hydrochloric acid not only etching apparatus but also contaminate environment; The ester-interchange method equilibrium conversion is low, and a large amount of by product second (or third) glycol is arranged; The homogeneous catalyst etching apparatus that methanol solution phase oxidation carbonylation method uses, and have the problem of product and catalyst separating and catalyst recycling difficulty; The methanol gas-phase oxidation/carbonylation two-step approach needs two-stage reaction, complex process, the easy blocking pipeline of by product dimethyl oxalate.
Synthesis of Dimethyl Carbonate from Urea technology has the advantage that raw material is cheap and easy to get, technology is simple, operational condition is gentle and avoided other route need separation of methanol-methylcarbonate-water complex system difficulty; But this technology exists that equilibrium conversion is low, homogeneous catalyst is difficult to problems such as Separation and Recovery at present.At present, the catalyzer that is used for Synthesis of Dimethyl Carbonate from Urea mainly is: organo-tin compound and alkali metal compound.For example, WO95-17369 has reported that Dibutyltin oxide, dibutyl dimethoxy tin, dibutyl methoxyl group isocyanate group tin makes catalyzer, with Urethylane or urea and methyl alcohol reaction, though steam simultaneously methylcarbonate continuously. such catalyzer can obtain higher product yield, decomposition reaction that also can the catalytic amino methyl-formiate.US5902894 adopts high boiling point electron donor oxygenatedchemicals to make solvent and co-catalyst, has suppressed the generation of the decomposition of Urethylane and the side reaction that methylates effectively.Its Urethylane transformation efficiency can reach 98.3%, and the selectivity of methylcarbonate reaches 98.2% simultaneously.Though organo-tin compound has good catalytic effect, their toxicity is big, price is high, homogeneous catalyst Separation and Recovery from product is very difficult.
US5534649 reported the employing alkali metal compound (as CsOH, Cs
2CO
3, K
2CO
3, Na
2CO
3, CH
3ONa) and quaternary ammonium compounds make catalyzer, but product yield is very low.Under the alkali metal compound catalyst action, methylcarbonate yield less than 2%.JP10-109960 has adopted a series of basic metal simple substance and compound catalyst, the methylcarbonate yield under the LiH effect wherein, although be up to 36.4%, this reaction needs to carry out in being furnished with the two reactor of distillation column, brings the problem of complex process, operational difficulty to it.
In sum, current exploitation heterogeneous catalyst efficient, non-environmental-pollution is that Synthesis of Dimethyl Carbonate from Urea technology realizes industrialized key.
Summary of the invention
At the problems referred to above, the invention solves that the equilibrium conversion that exists in the prior art is low, homogeneous catalyst is difficult to problems such as Separation and Recovery, thereby provide a series of Synthesis of Dimethyl Carbonate from Urea with metal oxide catalysts and preparation method thereof.
Technical scheme of the present invention:
The Synthesis of Dimethyl Carbonate from Urea metal oxide catalyst, it is made up of the 1-3 kind metal oxide in lithium, magnesium, nickel, zinc, lead, iron, aluminium, molybdenum, zirconium, the lanthanum; The component of mixed metal oxide catalyst wherein must be based on zinc oxide, and its weight percent is 35～95%, and the weight percent sum of other metal oxide is 5～65%.When this catalyzer was three kinds of mixed metal oxide, other the two kinds of metal oxide weight percents beyond the zinc oxide were 1: 1.The optimum weight per-cent of zinc oxide is 60～80% in this catalyzer.
Synthesis of Dimethyl Carbonate from Urea with the preparation method of metal oxide catalyst is: adopt thermal decomposition method to prepare single metal oxide catalyst, be about to the roasting 2～10 hours under 200～700 ℃ of high temperature respectively of metal nitrate, vitriol, (alkali formula) carbonate, acetate, stearate, these decomposable precursor salts compounds of halogenide.Optimum calcination temperature is 200～400 ℃.
Synthesis of Dimethyl Carbonate from Urea also can adopt the precipitator method to prepare single metal oxide catalyst with the preparation method of metal oxide catalyst, and its step is as follows:
(1) takes by weighing a kind of in the metal nitrate, vitriol, acetate, halogenide precursor salts compounds of solubility,, be mixed with the solution of 1.5mol/L with distilled water or alcohol dissolving as catalyst Precursors;
(2) in (1), introduce a kind of in ammoniacal liquor, solubility oxyhydroxide, carbonate, urea or the quaternary ammonium compounds, make the parent metal precipitation fully as precipitation agent.
(3) filter after washing to neutral, replace wherein moisture content with ethanol again;
(4) filter the after drying filter cake to constant weight;
(5) in retort furnace in 200～950 ℃ of following roastings 2～10 hours, take out and promptly to get single metal oxide catalyst.Its optimum calcination temperature is 500～700 ℃.The said drying means of the precipitator method adopts low-temperature vacuum drying, hyperthermia drying or supercritical drying.
The Synthesis of Dimethyl Carbonate from Urea preparation method of metal oxide catalyst, adopt following steps:
(1) get zinc acetate and urea and be dissolved in the middle of the methyl alcohol, wherein, zinc acetate and methyl alcohol mol ratio are 1: 10～100; Urea and methyl alcohol mol ratio are 1: 10～80 or 0; (when promptly adding urea, urea and methyl alcohol mol ratio are 1: 10～80, and urea and this methyl alcohol mol ratio are 0 when not adding urea; )
(2) reacted 1～10 hour down at 100～300 ℃;
(3) cool off, filter, be drying to obtain white powder solid oxidation zinc.
Need to prove that above-mentioned optimal reaction temperature is 180～250 ℃, zinc acetate and methyl alcohol optimum mole ratio are 1: 40～70.
Synthesis of Dimethyl Carbonate from Urea adopts coprecipitation method to prepare mixed metal oxide catalyst with the preparation method of metal oxide catalyst, and its step is as follows:
(1) described according to claim 1, get the metal carrier body saline admixture, with distilled water or alcohol dissolving, be mixed with the solution of 1.5mol/L;
(2) introduce precipitation agent, make the parent metal precipitation fully;
(3) filter and be washed to neutrality;
(4) filtration cakes torrefaction is to constant weight;
(5) in retort furnace in 200～950 ℃ of roastings 2～10 hours, its optimum calcination temperature is 600～750 ℃, gained is mixed metal oxide catalyst.
Wherein, the parent saline admixture described in above-mentioned (1) is in the metal nitrate, vitriol, acetate, halogenide of solubility 2～3 kinds; Precipitation agent described in above-mentioned (2) is ammoniacal liquor, solubility oxyhydroxide, carbonate or urea.
The present invention is beneficial effect compared with prior art:
The invention solves that the equilibrium conversion that exists in the Synthesis of Dimethyl Carbonate from Urea prior art is low, homogeneous catalyst is difficult to key issues such as Separation and Recovery, thereby not only economy but also practical used metal oxide catalyst of a series of Synthesis of Dimethyl Carbonate from Urea and preparation method thereof are provided.Its beneficial effect is summarized as follows:
(1) catalyst activity height.The single metal oxide catalyst of lithium of the present invention, magnesium, nickel, zinc, lead, aluminium, iron, molybdenum, zirconium, lanthanum and all Synthesis of Dimethyl Carbonate from Urea is had advantages of high catalytic activity based on the mixed metal oxide catalyst of zinc oxide makes yield can reach 49.7%.Under the same terms, the yield of methylcarbonate is higher than other heterogeneous catalyst.
(2) preparation method is simple.Catalyst preparation process does not have particular requirement, and a kind of zinc oxide new preparation process of especially being invented can be implemented in methylcarbonate synthesis reactor made acid-stable in situ, and need not utility appliance, helps reducing production costs.
(3) be easy to Separation and Recovery.Catalyzer of the present invention has solved the problem that recycling is separated, is difficult for to homogeneous catalyst and product difficulty, has both reduced process cost, has improved quality product again.
(4) good stability, easily regeneration.Catalyzer of the present invention belongs to metal oxide catalyst, can repeat repeatedly to use; Decaying catalyst only needs simple process can recover active.
(5) catalyst particle size can reach nanometer level.
Embodiment
Embodiment 1:(thermal decomposition method prepares single metal oxide---Zinc oxide catalytic)
Get zinc subcarbonate in retort furnace in 550 ℃ of following roastings 2 hours, make Zinc oxide catalytic.
Only there is ZnO crystalline phase in this catalyst sample through XRD test proof, belongs to hexagonal system.
Catalyst Synthesis of Dimethyl Carbonate from Urea reaction with above-mentioned preparation:
Application experiment 1:
(1) in the 500mL autoclave reactor that is equipped with distillation column, adds the 200mL anhydrous methanol, 14.85g urea, the ZnO catalyst of 2g embodiment 1 preparation;
(2) use the nitrogen purging reactive system;
(3) the 800rpm rotating speed stirs in following 2 hours and is warmed up to 180 ℃, discharges the ammonia that produces the reaction from the distillation column top at any time;
(4) 170 ℃ of reaction coolings after 6 hours down;
(5) take out reaction solution, analyze external standard method counting yield DMC addition with SQ-206 type gas chromatograph after the weighing.Calculation result methylcarbonate yield is 9.42%.
Application experiment 2:
If urea and methyl alcohol mol ratio were increased to 1: 20, other condition of evaluating catalyst is identical with application experiment 1, and the methylcarbonate yield reaches 24.6% as a result.
Embodiment 2-5:(thermal decomposition method prepares Zinc oxide catalytic)
Change catalyst Precursors, promptly use zinc acetate, Zinic stearas, zinc sulfate or zinc chloride to be catalyst Precursors respectively, other is with embodiment 1.
The gained catalyzer is estimated under application experiment 1 condition, and its gained methylcarbonate yield sees Table 1.
The catalytic performance of the ZnO catalyst of the different precursor salts preparations of table 1
The catalyst Precursors maturing temperature, ℃ DMC yield, %
Zinc acetate 200 12.7
Zinic stearas 300 9.55
Zinc sulfate 850 5.36
The embodiment 6:(precipitator method prepare Zinc oxide catalytic)
(1) takes by weighing precursor salts 40gZn (NO
3)
26H
2O uses the 200mL dissolved in distilled water;
(2) preparation precipitation agent: take by weighing 16gNa
2CO
3, use the 200mL dissolved in distilled water;
(3) with (1) and (2) short mix and vigorous stirring;
(4) leave standstill 5 hours after-filtration, replace wherein moisture with ethanol again after being washed to neutrality;
(5) vacuum-drying constant weight;
(6) 450 ℃ of roastings 4 hours in retort furnace make Zinc oxide catalytic.
Catalyst sample is tested through XRD, and phase structure is a hexagonal system; TEM detecting catalyst average diameter of particles is 26.5nm.
Application experiment 3:
Use the zinc oxide of originally executing example 6 preparations, the evaluating catalyst condition is identical with application experiment 1, and the methylcarbonate yield is 6.62%.
The embodiment 7-16:(precipitator method prepare oxide catalyst)
Catalyzer, parent, precipitation agent, maturing temperature and drying mode such as table 2, other is with embodiment 6.
The gained catalyzer is estimated under application experiment 1 condition, and its gained methylcarbonate yield sees Table 2.
The catalytic performance of the different oxide catalysts of table 2
Catalyst Precursors precipitation agent maturing temperature, ℃ drying mode DMC
aYield, %
ZnO zinc nitrate ammoniacal liquor 650 hyperthermia dryings 5.46
ZnO zinc sulfate ammoniacal liquor 650 hyperthermia dryings 4.55
ZnO zinc chloride ammoniacal liquor 650 hyperthermia dryings 6.47
ZnO zinc acetate Tetramethylammonium hydroxide
b200 low-temperature vacuum dryings 5.64
PbO lead nitrate ammoniacal liquor 650 hyperthermia dryings 13.5
PbO lead nitrate yellow soda ash 650 hyperthermia dryings 11.2
PbO lead nitrate urea 650 hyperthermia dryings 8.4
PbO lead nitrate lithium hydroxide
c200 low-temperature vacuum dryings 12.4
La
2O
3Lanthanum nitrate ammoniacal liquor 900 hyperthermia dryings 5.33
La
2O
3Lanthanum nitrate ammoniacal liquor 650 supercritical dryings 9.09
Annotate: a. methylcarbonate
B. in n-propyl alcohol solution, prepare
C. prepare in the ethanol solution
The preparation method of embodiment 17:(catalyst oxidation zinc)
(1) weighing zinc acetate 8g, urea 3g, anhydrous methanol 100mL puts into autoclave, sealing;
Be warming up to 180 ℃ in (2) 2 hours, insulation reaction 1 hour;
(3) cooling, filtration, drying;
The gained catalyzer is estimated by embodiment 1 condition, and the methylcarbonate yield is 14.3% as a result.
Embodiment 18:
Do not add urea in the catalytic preparation process, promptly urea and this methyl alcohol mol ratio are 0; Other is with embodiment 10, and the methylcarbonate yield is 7.49%.
Embodiment 19 (coprecipitation method prepares zinc oxide-plumbous oxide mixed oxide catalyst)
(1) precursor salts takes by weighing 65.5gZn (NO
3)
26H
2O, Pb (NO
3)
28g uses the 300mL dissolved in distilled water;
(2) preparation 10% ammonia soln 150mL makes precipitation agent;
(3) under the vigorous stirring (1) is mixed with (2);
(4) leave standstill 5 hours after-filtration and be washed to neutrality;
(5) filter cake is dried to constant weight for 90 ℃;
(6) 700 ℃ of following roastings 4 hours in retort furnace, gained is the ZnO-PbO catalyzer.
The evaluating catalyst condition is identical with application experiment 1, and under the effect of gained ZnO-PbO mixed oxide catalyst, the methylcarbonate yield is 12.0%.
Embodiment 20-32:(coprecipitation method prepares mixed metal oxide catalyst)
Catalyst component, maturing temperature and time, as table 3, other is with embodiment 19, and catalytic performance sees Table 3.
The catalytic performance of the different mixed metal oxide catalysts of table 3
Weight ratio maturing temperature between catalyst component, ℃ roasting time, h DMC yield, %
ZnO-PbO 90/10 550 4 6.51
ZnO-PbO 80/20 650 4 16.0
ZnO-La
2O
3 80/20 900 4 5.00
ZnO-La
2O
3 80/20 750 4 9.85
ZnO-Li
2O 80/20 400 6 5.88
ZnO-MgO 80/20 400 6 5.80
ZnO-NiO 80/20 400 6 7.61
ZnO-Fe
2O
3 80/20 400 6 4.32
ZnO-ZrO
2 80/20 400 6 8.11
ZnO-Al
2O
3 80/20 400 6 7.33
ZnO-MnO
3 80/20 400 6 7.24
ZnO-PbO-La
2O
3 60/20/20 700 9 6.21
ZnO-PbO-La
2O
3 40/30/30 700 9 4.08
Semi-batch operation Synthesis of dimethyl carbonate application experiment under the different catalysts effect:
(1) weighing 18.5g urea, 300mL methyl alcohol and 5g catalyzer place the autoclave of band distillation column;
(2) use the nitrogen purging system;
(3) the 800rpm rotating speed stirs in following 2 hours and is warming up to 180 ℃, and back pressure valve is regulated column head pressure and maintained 1.8Mpa, feeds 70 ℃ of thermostat(t)ed waters simultaneously in distillation column;
(4) open volume pump, in system, inject methyl alcohol with the flow of 2.5mL/min;
(5) every 1 hour from condenser and sampling valve sampling analysis;
(6) reaction cooling after 8 hours, stopped reaction;
(7) take out reaction solution, use the chromatographic instrument analysis after the weighing, calculate the methylcarbonate yield.
Under the different catalysts effect, the methylcarbonate yield sees Table 4.
Methylcarbonate yield catalyzer ZnO ZnO-PbO ZnO-La under the effect of table 4 different catalysts
2O
3Yield, % 38.5 41.3 49.7
Claims (10)
1. Synthesis of Dimethyl Carbonate from Urea metal oxide catalyst, it is characterized in that: it is made up of the 1-3 kind metal oxide in lithium, magnesium, nickel, zinc, lead, iron, aluminium, molybdenum, zirconium, the lanthanum; Wherein mixed metal oxide catalyst must be based on zinc oxide, its weight percent is 35～95%, the weight percent sum of other metal oxide is 5～65%, when this catalyzer was three kinds of mixed metal oxide, other the two kinds of metal oxide weight percents beyond the zinc oxide were 1: 1.
2. according to the said Synthesis of Dimethyl Carbonate from Urea metal oxide catalyst of claim 1, it is characterized in that: the optimum weight per-cent of zinc oxide is 60～80% in this catalyzer.
3. Synthesis of Dimethyl Carbonate from Urea is with the preparation method of metal oxide catalyst, it is characterized in that: adopt thermal decomposition method to prepare single metal oxide catalyst, be about to the roasting 2～10 hours under 200～700 ℃ of high temperature respectively of metal nitrate, vitriol, (alkali formula) carbonate, acetate, stearate, these decomposable precursor salts compounds of halogenide.
4. according to the preparation method of the said Synthesis of Dimethyl Carbonate from Urea of claim 3 with metal oxide catalyst, it is characterized in that: optimum calcination temperature is 200～400 ℃.
5. Synthesis of Dimethyl Carbonate from Urea is with the preparation method of metal oxide catalyst, and it is characterized in that: adopt the precipitator method to prepare single metal oxide catalyst, its step is as follows:
(1) takes by weighing a kind of in the metal nitrate, vitriol, acetate, halogenide precursor salts compounds of solubility,, be mixed with the solution of 1.5mol/L with distilled water or alcohol dissolving as catalyst Precursors;
(2) in (1), introduce a kind of in ammoniacal liquor, solubility oxyhydroxide, carbonate, urea or the quaternary ammonium compounds, make the parent metal precipitation fully as precipitation agent;
(3) filter after washing to neutral, replace wherein moisture content with ethanol again;
(4) filter the after drying filter cake to constant weight;
(5) in retort furnace in 200～950 ℃ of following roastings 2～10 hours, take out and promptly to get single metal oxide catalyst.
6. according to the preparation method of the said Synthesis of Dimethyl Carbonate from Urea of claim 5 with metal oxide catalyst, it is characterized in that: optimum calcination temperature is 500～700 ℃.
7. Synthesis of Dimethyl Carbonate from Urea is characterized in that adopting following steps with the preparation method of metal oxide catalyst:
(1) get zinc acetate and urea and be dissolved in respectively in the middle of the methyl alcohol, wherein, zinc acetate and methyl alcohol mol ratio are 1: 10～100, and when adding urea, urea and methyl alcohol mol ratio are 1: 10～80, and urea and this methyl alcohol mol ratio are 0 when not adding urea;
(2) reacted 1～10 hour down at 100～300 ℃;
(3) cool off, filter, be drying to obtain white powder solid oxidation zinc.
8. according to the preparation method of the described Synthesis of Dimethyl Carbonate from Urea of claim 7 with metal oxide catalyst, it is characterized in that: optimal reaction temperature is 180～250 ℃, and zinc acetate and methyl alcohol optimum mole ratio are 1: 40～70.
9. Synthesis of Dimethyl Carbonate from Urea is with the preparation method of metal oxide catalyst, and it is characterized in that: adopt coprecipitation method to prepare mixed metal oxide catalyst, its step is as follows:
(1) described according to claim 1, get the metal carrier body saline admixture, with distilled water or alcohol dissolving, be mixed with the solution of 1.5mol/L;
(2) introduce precipitation agent, make the parent metal precipitation fully;
(3) filter and be washed to neutrality;
(4) filtration cakes torrefaction is to constant weight;
(5) in retort furnace in 200～950 ℃ of roastings 2～10 hours, gained is mixed metal oxide catalyst;
Wherein, the parent saline admixture described in above-mentioned (1) is 2～3 kinds in the metal nitrate, vitriol, acetate, halogenide of solubility, and the precipitation agent described in above-mentioned (2) is ammoniacal liquor, solubility oxyhydroxide, carbonate or urea.
10. according to the preparation method of the described Synthesis of Dimethyl Carbonate from Urea of claim 9 with metal oxide catalyst, it is characterized in that: optimum calcination temperature is 600～750 ℃.
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