CN100551531C - The Catalysts and its preparation method that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation - Google Patents
The Catalysts and its preparation method that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation Download PDFInfo
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- CN100551531C CN100551531C CNB2007100603564A CN200710060356A CN100551531C CN 100551531 C CN100551531 C CN 100551531C CN B2007100603564 A CNB2007100603564 A CN B2007100603564A CN 200710060356 A CN200710060356 A CN 200710060356A CN 100551531 C CN100551531 C CN 100551531C
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- diethyl carbonate
- carbonylsynthesizingdiethyl
- byethanol
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Abstract
The invention discloses a kind of Catalysts and its preparation method that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation.The activity of such catalysts component is CuCl, CuCl
2, Cu (NO
3)
2Or Cu (Ac)
2, carrier is H β, HZSM-5 or HY molecular sieve, the preparation method is: mantoquita is joined in the HCl solution, and molecular sieve carrier be impregnated in the above-mentioned solution, dropwise drip NH
3H
2O makes its precipitation.The gained solid catalyst is at N
2Protection heats up down, and heated at constant temperature naturally cools to room temperature, makes catalyst.The invention has the advantages that catalyst preparation process is simple, advantages such as prepared catalyst is used for the reaction of carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation, and the selectivity with purpose product diethyl carbonate is higher, catalyst cheaply is easy to get, catalytic activity is stable.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation, belong to the gas phase synthesis catalytic technology of diethyl carbonate.
Background technology
Diethyl carbonate (DEC) is described as " green chemical " because environmental friendliness is of many uses.As important organic synthesis intermediate, DEC has very high industrial value in the energy, electronics, medicine and other fields, and DEC still is one of the most competitive substitute of gasoline additive methyl tertiary butyl ether simultaneously, and application prospect is very extensive.Therefore, the synthesis technique of DEC had caused extensive attention in recent years.Its important process comprises phosgenation, ester-interchange method, ethanol carbon dioxide direct synthesis technique and oxidation of ethanol oxo synthesis etc.
Phosgenation
[1]Owing to use hypertoxic phosgene as raw material, serious environment pollution; The while by-product hydrogen chloride, corrosion pipeline equipment.Though done many improvement at process aspect afterwards, limited its development owing to its shortcoming is difficult to overcome.Ester exchange reaction
[2-3]Be reversible reaction, and the chemical equilibrium constant of reaction is less, when realizing that product separates, can because of concentration of alcohol reduce back reaction is speeded up, thereby reduce product yield.Because therefore problems such as the higher and selectivity of the price of carbonic ester own do not have cost advantage.Ethanol carbon dioxide direct synthesis technique is not preponderated on the thermodynamics, is difficult to realize industrialization at present.The synthetic DEC technology of oxidation of ethanol carbonyl comprises vapor phase method and liquid phase method.Liquid phase method
[4]In have serious equipment corrosion problem, still needing further solves.In addition the separating and isolation technics that recycling needs are complicated of product and catalyst in the liquid phase method, become the major defect of this method.
The synthetic DEC of ethanol gas phase oxidation carbonyl possesses special advantages, has both satisfied the requirement of green chemical industry, also has huge industrial value simultaneously.This technology overall reaction is as follows:
At present, increasing year by year about the report of this reaction system catalyst, wherein is to be the Wacker type catalyst of carrier with the active carbon mostly
[5], solid ion exchange molecular sieve catalyst
[6]Shortcomings such as the instability of Wacker type catalyst, life-span weak point; The obtained molecular sieve catalyst life-span of solid ion exchange process is better, but lower to ethanol conversion, selection of catalysts is also not ideal.To sum up, demand developing the new catalyst that a kind of activity is high, selectivity is good, the life-span is long urgently.
List of references
[1]I.E.Muskat，F.Strain，Preparation?of?Carbonic?Acid?Esters，US?Patent，2379250，1941-05-28
[2] Fang Yunjin, Luo Huping, Xiao Wende prepares the method for diethyl carbonate, Chinese patent, 01105860.9,2001-04-03
[3]P.T.Anastas，J.C.Warner，Green?Chemistry：Theory?and?Practice，London：OxfordUniversity?Press，1998：11～16
[4]R.Ugo，T.Renato，C.Gioacchino，et?al，Method?for?the?preparation?of?esters?of?carbonicacid，US?Patent，4218391，1979-05-05
[5]N.S.Roh，B.C.Dunn，E.M.Eyring，et?al，Procuction?of?diethyl?carbonate?from?ethanol?andcarbon?monoxide?over?a?heterogeneous?catalytic?flow?reactor，Fuel?Processing?Technology，2003，83：27～38
[6]S.T.King，J.Catal.161(1996)530-538.
Summary of the invention
The object of the present invention is to provide a kind of Catalysts and its preparation method that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation.With the prepared catalyst of this method have active high, selectivity is good, the characteristics of long service life, its preparation method process is simple.
The present invention is realized by following technical proposals, a kind of catalyst that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation, and described carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation is to be CO: O at the raw material raw materials components mole ratio
2=4: 1～17: 1, reaction temperature is 100～160 ℃, and reaction pressure is under 0.4～0.8MPa and the catalyst existence condition, and realization response is synthetic, it is characterized in that the carrier of the catalyst that is adopted is H β, HZSM-5 or HY; The activity of such catalysts component is CuCl, CuCl
2, Cu (NO
3)
2Or Cu (Ac)
2The mass content of active component accounts for the 10-60% of carrier; When the gas-phase feed air speed is 2000～5000h
-1The time, catalyst consumption is 0.5～2g.
Carrier is H β in the above-mentioned catalyst.
Above-mentioned catalyst activity component is CuCl.
Above-mentioned Preparation of catalysts method is characterized in that comprising following process: with CuCl, CuCl
2, Cu (NO
3)
2Or Cu (Ac)
2Join in the HCl solution of 0.5mol/l, be mixed with the copper salt solution that concentration is 0.5～2mol/l, and with the H β of drying, or HZSM-5 or HY carrier 2～8g impregnated in 30～80ml copper salt solution, dropwise drip NH
3H
2O makes the pH value of solution value reach 9～11, floods 3～10h down in 20～25 ℃.The gained impregnated carrier is sent in the interior quartz glass tube of tubular heater, with the flow velocity feeding N of 30～100ml/min
2Gas, and tube furnace is heated to 250～750 ℃ with 2-10 ℃/min heating rate.Behind constant temperature 4～24h, naturally cool to 20～25 ℃, stop to feed N then
2, can make catalyst.
The invention has the advantages that, make molecular sieve catalyst by adopting the precipitation exchange process, with other simple loaded catalyst such as CuCl
2-PdCl
2/ C compares, and the catalyst activity component is stable, and catalyst reaches more than the 80h service life, is four times of existing catalyst service life.Compare with the molecular sieve catalyst that simple solid ion exchange process makes in addition, improved the load capacity of its active component, improved activity of such catalysts to a great extent, the space-time yield of DEC can reach 86.3mgg
-1h
-1, compare the DEC space-time yield with existing C u/Y catalyst and improved 50%.
Come the present invention is further specified below by specific embodiment, but do not limit the present invention.
The specific embodiment
[embodiment 1]
5gCuCl is joined in the 50mlHCl solution of 0.5mol/l, and with the 10gH β carrier impregnation of drying in above-mentioned solution, dropwise drip NH
3H
2O makes the pH value of solution value reach 9～11, floods 5h down in 25 ℃.The gained impregnated carrier adds in the interior quartz glass tube of tubular heater, with the flow velocity feeding N of 80ml/min
2Gas is heated to 450 ℃ with 5 ℃/min heating rate with tube furnace.Constant temperature 6h naturally cools to 25 ℃, stops to feed N then
2, can make catalyst 15g.
[embodiment 2]
Under experiment condition and embodiment 1 identical situation, change CuCl content in the catalyst preparation process into 3g, carrier changes 10gHZSM-5 into, makes catalyst 13g.
[embodiment 3]
Under experiment condition and embodiment 1 identical situation, change just that sintering temperature is 550 ℃ in the Preparation of Catalyst condition, make catalyst 15g.
[embodiment 4-7]
Under experiment condition and embodiment 1 identical situation, change just that roasting time changes 4h, 8h, 12h, 20h respectively in the Preparation of Catalyst condition, make catalyst 15g respectively.
[embodiment 8-10]
Under experiment condition and embodiment 1 identical situation, active component is CuCl in the change catalyst preparation process
2, Cu (NO
3)
2And Cu (Ac)
24g, 650 ℃ of sintering temperatures, roasting time 10h makes catalyst 14g respectively.
[reaction embodiment 11-20]
In pressurization minisize reaction system, carry out the activity of such catalysts evaluation, feed reactant 80sccm CO, 10sccm O
2And carrier gas 50sccm N
2, ethanol adds reactor by the pressurization trace quantity pump with constant flow rate 0.1ml/min, uses Preparation of catalysts embodiment 1～10 each 1.5g of obtained catalyst respectively, and at 140 ℃, 0.7MPa reacts.Is index with ethanol conversion, ethanol to selectivity and the diethyl carbonate space-time yield of DEC, and the gained reactivity worth as shown in Table 1.
Table 1: the reaction result of catalyst oxidation carbonyl synthesizing diethyl carbonate
[reaction embodiment 21-25]
In reactor, feed reactant 80sccm CO, 8sccm O
2And carrier gas 50sccm N
2, ethanol adds reactor by the pressurization trace quantity pump with constant flow rate 0.1ml/min, uses Preparation of catalysts embodiment 1,3,5,8 and 10 each 1.5g of obtained catalyst respectively, and at 120 ℃, 0.6MPa reacts.Is index with ethanol conversion, ethanol to selectivity and the diethyl carbonate space-time yield of DEC, and the gained reactivity worth as shown in Table 2.
Table 2: the reaction result of catalyst oxidation carbonyl synthesizing diethyl carbonate
[Comparative Examples 1-2: the contrast of activity of such catalysts and life-span and existing catalyst]
In pressurization minisize reaction system, carry out the activity of such catalysts evaluation, feed reactant 80sccm CO, 10sccm O
2And carrier gas 50sccm N
2, ethanol adds reactor by the pressurization trace quantity pump with constant flow rate 0.1ml/min, uses existing Catalysts Cu Cl respectively
2-PdCl
2/ C, CuCl
2Each 1.5g of/C, at 140 ℃, 0.7MPa reacts.Is index with ethanol conversion, ethanol to selectivity and the diethyl carbonate space-time yield of DEC, and the gained reactivity worth as shown in Table 3.
Table 3: the reaction result that is used for oxidation carbonyl synthesizing diethyl carbonate of catalyst of the present invention and existing catalyst
The invention is not restricted to above embodiment, present patent application personnel can make various changes and distortion according to the present invention, only otherwise break away from spirit of the present invention, all should belong to scope of the present invention.
Claims (3)
1. catalyst that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation, described carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation is to be CO: O at the raw material raw materials components mole ratio
2=4: 1～17: 1, reaction temperature is 100～160 ℃, and reaction pressure is under 0.4～0.8MPa and the catalyst existence condition, and realization response is synthetic, and it is characterized in that: the carrier of the catalyst that is adopted is H β; The activity of such catalysts component is CuCl, CuCl
2, Cu (NO
3)
2Or Cu (Ac)
2The mass content of active component accounts for the 10-60% of carrier; When the gas-phase feed air speed is 2000～5000h
-1The time, catalyst consumption is 0.5～2g.
2. by the described catalyst that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation of claim 1, it is characterized in that described activity of such catalysts component is CuCl.
3. one kind prepares the described method that is used for the catalyst of carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation of claim 1, it is characterized in that comprising following process: with CuCl, CuCl
2, Cu (NO
3)
2Or Cu (Ac)
2Join in the HCl solution of 0.5mol/l, be mixed with the copper salt solution that concentration is 0.5～2mol/l, and the H β carrier 2～8g of drying be impregnated in 30～80ml copper salt solution, dropwise drip NH
3H
2O makes the pH value of solution value reach 9～11, and dipping 3～10h under 20～25 ℃, gained impregnated carrier send in the interior quartz glass tube of tubular heater, with the flow velocity feeding N of 30～100ml/min
2Gas, and tube furnace is heated to 250～750 ℃ with 2-10 ℃/min heating rate, behind constant temperature 4～24h, naturally cool to 20～25 ℃, stop to feed N then
2, can make catalyst.
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|---|---|---|---|
| CNB2007100603564A CN100551531C (en) | 2007-12-19 | 2007-12-19 | The Catalysts and its preparation method that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation |
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|---|---|---|---|
| CNB2007100603564A CN100551531C (en) | 2007-12-19 | 2007-12-19 | The Catalysts and its preparation method that is used for carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation |
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| CN100551531C true CN100551531C (en) | 2009-10-21 |
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| CN102059147B (en) * | 2010-11-25 | 2013-02-13 | 上海华谊（集团）公司 | Preparation method for synthesizing diethyl carbonate through catalytic oxidation carbonylation |
| CN102371180A (en) * | 2011-11-17 | 2012-03-14 | 江南大学 | Catalyst for use in gas-phase synthesis of diethyl carbonate and preparation method thereof |
| CN105797764A (en) * | 2014-12-31 | 2016-07-27 | 中国科学院兰州化学物理研究所 | Load type catalyst, preparation method and application thereof |
| CN111437877B (en) * | 2020-04-22 | 2023-03-10 | 陕西延长石油（集团）有限责任公司 | Cu/Zr bimetallic framework type high-silicon beta molecular sieve catalyst and preparation method and application thereof |
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