CN100500288C - Catalyst for ethanol vapor-phase carbonyl synthesis for diethyl carbonate and its preparation method - Google Patents
Catalyst for ethanol vapor-phase carbonyl synthesis for diethyl carbonate and its preparation method Download PDFInfo
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- CN100500288C CN100500288C CNB200710060355XA CN200710060355A CN100500288C CN 100500288 C CN100500288 C CN 100500288C CN B200710060355X A CNB200710060355X A CN B200710060355XA CN 200710060355 A CN200710060355 A CN 200710060355A CN 100500288 C CN100500288 C CN 100500288C
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- diethyl carbonate
- mesoporous carbon
- cucl
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Abstract
The invention discloses a catalyst used in synthesizing diethyl carbonate by ethanol carbonylation and a preparation method thereof. Active component of the catalyst is CuCl or CuCl2, a carrier is mesoporous carbon, and charge number accounts for 5 to 20 percent of the carrier. The preparation process comprises that: acid solvent which contains screened SBA-15 molecular in sucrose is processed by two-step carbonization treatment, high-temperature roasting process is adopted to carbonize finally, HF solvent is adopted to dispel molecular and the mesoporous carbon carrier is screened and prepared, the mesoporous carbon carrier is then soaked in copper solution, and the catalyst is prepared after evaporation drying. The invention has the advantages that the preparation process is simple and preparation cost is low; the catalyst is used in the ethanol carbonylation reaction to synthesize the diethyl carbonate, which has the advantages of high selectivity and stable catalytic activity of the production of the diethyl carbonate, etc.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for ethanol gas phase carbonyl synthesizing diethyl carbonate, belong to synthesizing diethyl carbonate gas phase synthesis catalytic technology.
Background technology
Diethyl carbonate (DEC) is a kind of environmental friendliness organic synthesis intermediate, and it is of many uses, is described as " green chemical ".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.
The synthesis technique of DEC mainly comprises phosgenation
[1], ester-interchange method
[2], ethanol carbon dioxide direct synthesis technique and oxidation of ethanol oxo synthesis etc.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
[3], solid ion exchange molecular sieve catalyst
[4]Active carbon is that the catalyst of carrier has active component and easily runs off shortcomings such as poor catalyst stability; 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.Therefore, demand developing a kind of new catalyst urgently.
In the recent period, mesoporous material is with its particular structure advantage, cause catalytic field scholar's extensive concern, with the carrier of mesoporous carbon as oxidation carbonyl synthesizing diethyl carbonate catalyst, can effectively utilize the meso-porous carbon material high-sequential, the specific surface height, aperture, the advantage that pore volume is big are improved activity of such catalysts and stability.
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]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
[4]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 catalyst that is used for ethanol gas phase carbonyl synthesizing diethyl carbonate.With the prepared catalyst of this method have active high, selectivity is good, long service life and the low characteristics of preparation cost, its preparation method process is simple.
The present invention is realized by following technical proposals, a kind of catalyst that is used for ethanol gas phase carbonyl synthesizing diethyl carbonate, and described carbonylsynthesizingdiethyl diethyl carbonate byethanol gas-phase oxidation is to be CO:O with the raw material raw materials components mole ratio
2=4:1～17:1, reaction temperature is 100～160 ℃, reaction pressure is under 0.4～0.8MPa and the catalyst existence condition, realization response is synthetic, institute adopt catalyst, it is characterized in that the carrier of catalyst is a meso-porous carbon material; The active component of load is CuCl or CuCl on the carrier
2The mass content of active component accounts for the 5-20% of carrier; When the gas-phase feed air speed is 2000～5000h
-1The time, catalyst consumption is 0.5～2g.
Above-mentioned Preparation of catalysts method is characterized in that comprising following process:
(1) preparation of mesoporous carbon carrier: 0.5～2g SBA-15, ZSM-5 or the agent of H β template are added in the water, and the template agent is 1:3～8 with the water quality ratio, is that 1:1 adds sucrose by template agent and sucrose mass ratio then, presses H simultaneously
2SO
4With the mass ratio of template agent be that 1:8～12 add H
2SO
4, making the suspension of template agent under the stirring condition, suspension is under 80～100 ℃, and evaporative removal moisture is placed 4～10h in 155～165 ℃ again and is carried out preliminary carbonization.The product of preliminary carbonization is added in the water, and the carbonized product amount is 1:3～8 with the water quality ratio, is that 1:1 adds sucrose by carbide and sucrose mass ratio then, presses H simultaneously
2SO
4With the mass ratio of carbide be that 1:8～12 add H
2SO
4, making the suspension of carbide under the stirring condition, suspension is under 80～100 ℃, and evaporative removal moisture is placed the further carbonization of 4～10h in 155～165 ℃ again, makes the silicon/carbon dioxide compound, and the silicon/carbon dioxide compound is at N
2Under the gas shiled, 5 ℃/min is warmed up to 750～950 ℃, and constant temperature keeps 3～6h, finishes whole carbonisation. and naturally cooling to 20～25 ℃, is that 4～6% HF solution is removed silica with mass fraction again, obtains the mesoporous carbon carrier.
(2) load of active component: with CuCl or CuCl and CuCl
22H
2O is dissolved in NH
3H
2O is mixed with concentration and is 3～12% copper salt solution, is that 8g/30ml～60ml adds the mesoporous carbon carrier by mesoporous carbon carrier quality and copper salt solution volume ratio, in 20～25 ℃ of dipping 4～6h down.Make mesoporous carbon load copper salt catalyst through evaporation and drying again.
The invention has the advantages that, be the catalyst of carrier by adopting the prepared mesoporous carbon of infusion process, and carrier aperture can be controlled at 3～8nm, and the aperture is evenly single and adjustable, the Stability Analysis of Structures of catalyst, thus effectively improved activity of such catalysts.With traditional active carbon be the Catalysts Cu Cl of carrier
2-PdCl
2/ C compares the loss that can effectively avoid active component, and the catalyst price is low, and the better life-span of stability is long, and the space-time yield of DEC can reach 110.3mgg
-1H
-1, with existing C uCl
2-PdCl
2/ C compares and has improved more than three times.
Come the present invention is further specified below by specific embodiment, but do not limit the present invention.
The specific embodiment
[embodiment 1]
The preparation method of mesoporous carbon carrier is as follows: SBA-15 is added in the 5g water with the agent of 1g template, adds 1g sucrose and 0.1g sulfuric acid then, under 90 ℃ of conditions, after water evaporates removed, places 6h again and carry out preliminary carbonization in 160 ℃ baking oven.The product of preliminary carbonization is dissolved in the 5g water, adds 1g sucrose and 0.1g H then
2SO
4, in 90 ℃ with water evaporates after, again in 160 ℃ of further carbonization 6h.At N
2Be warming up to 900 ℃ with 5 ℃/min under the atmosphere, constant temperature 4h is cooled to 25 ℃, and gained silicon/carbon dioxide combination product mass fraction is 5% HF solution washing removal silica, obtains the mesoporous carbon carrier after 120 ℃ of dryings.
The CuCl of 2g is dissolved in NH
3H
2O is mixed with concentration and is 8% copper salt solution, and mesoporous carbon carrier granular 8g be impregnated in the above-mentioned solution, in 25 ℃ of dipping 5h down.Evaporate to such an extent that catalyst is handled 10h in 120 ℃ of vacuum drying chambers, obtain catalyst 8.5g.
[embodiment 2]
Under Preparation of catalysts condition and embodiment 1 identical situation, only change template agent among the meso-porous carbon material preparation method into 1.5g ZSM-5, obtain catalyst 8.5g.
[embodiment 3]
Under Preparation of catalysts condition and embodiment 1 identical situation, only change template agent among the meso-porous carbon material preparation method into 1.25g H β, obtain catalyst 8.5g.
[embodiment 4]
Under Preparation of catalysts condition and embodiment 1 identical situation, only change template agent among the meso-porous carbon material preparation method into 1g H β, CuCl concentration changes 10% in the Preparation of catalysts, obtains catalyst 8.5g.
[embodiment 5]
Under Preparation of catalysts condition and embodiment 1 identical situation, only change CuCl concentration in the Preparation of catalysts into 12%, the mesoporous carbon carrier is 10g, obtains catalyst 10.5g.
[embodiment 6]
Under Preparation of catalysts condition and embodiment 1 identical situation, only change active component in the Preparation of catalysts into 5% CuCl and 5% CuCl
22H
2The mixed copper salting liquid of O, the mesoporous carbon carrier is 10g, obtains catalyst 10.5g.
[reaction embodiment 7-12]
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 embodiment 1～6 each 1.5g of obtained catalyst of Preparation of 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 13-16]
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 Catalyst embodiment 1,3,5,6 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]
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
2Each 1.5g of/C, at 140 ℃, 0.7MPa reacts.Obtain ethanol conversion and be 5.7%, ethanol is to the selectivity 80.7% of DEC, the space-time yield of diethyl carbonate is 29.9mgg
-1H
-1
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 (2)
1, a kind of catalyst that is used for ethanol gas phase carbonyl synthesizing diethyl carbonate, 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 ℃, reaction pressure is under 0.4～0.8MPa and the catalyst existence condition, realization response is synthetic, institute adopt catalyst, it is characterized in that the carrier of catalyst is a meso-porous carbon material; The active component of load is CuCl or CuCl on the carrier
2The mass content of active component accounts for 5～20% of carrier; Gas-phase feed air speed 2000～5000h
-1The time, catalyst consumption is 0.5～2g.
2, a kind of described method that is used for the catalyst of ethanol gas phase carbonyl synthesizing diethyl carbonate of claim 1 for preparing is characterized in that comprising following process:
(1) preparation of mesoporous carbon carrier: agent is added in the water as template with 0.5～2g SBA-15, ZSM-5 or H β, and template agent and water quality are 1:1 adding sucrose by template agent and sucrose mass ratio than being 1:3～8 then, press H simultaneously
2SO
4With the mass ratio of template agent be that 1:8～12 add H
2SO
4Make the suspension of template agent under the stirring condition, suspension is under 80～100 ℃, evaporative removal moisture, place 4～10h in 155～165 ℃ again and carry out preliminary carbonization, the product of preliminary carbonization is added in the water, carbonized product amount and water quality are than being 1:3～8, be that 1:1 adds sucrose by carbide and sucrose mass ratio then, press H simultaneously
2SO
4With the mass ratio of carbide be that 1:8～12 add H
2SO
4, making the suspension of carbide under the stirring condition, suspension is under 80～100 ℃, and evaporative removal moisture is placed the further carbonization of 4～10h in 155～165 ℃ again, makes the silicon/carbon dioxide compound, and the silicon/carbon dioxide compound is at N
2Under the gas shiled, 5 ℃/min is warmed up to 750～950 ℃, and constant temperature keeps 3～6h, finishes whole carbonisation, naturally cools to 20～25 ℃, is that 4～6% HF solution is removed silica with mass fraction again, obtains the mesoporous carbon carrier;
(2) load of active component: with CuCl or CuCl and CuCl
22H
2O is dissolved in NH
3H
2O is mixed with concentration and is 3～12% copper salt solution, is that 8g/30ml～60ml adds the mesoporous carbon carrier by mesoporous carbon carrier quality and copper salt solution volume ratio, in 20～25 ℃ of dipping 4～6h down, makes mesoporous carbon load copper salt catalyst through evaporation and drying again.
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| CNB200710060355XA CN100500288C (en) | 2007-12-19 | 2007-12-19 | Catalyst for ethanol vapor-phase carbonyl synthesis for diethyl carbonate and its preparation method |
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|---|---|---|---|
| CNB200710060355XA CN100500288C (en) | 2007-12-19 | 2007-12-19 | Catalyst for ethanol vapor-phase carbonyl synthesis for diethyl carbonate and its preparation method |
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| CN100500288C true CN100500288C (en) | 2009-06-17 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102614900B (en) * | 2012-03-08 | 2014-08-20 | 天津大学 | Mesoporous carbon-loaded catalyst for synthesizing diethyl carbonate by gas phase oxidation carbonyl of ethanol and preparation method thereof |
| CN105233825B (en) * | 2015-10-19 | 2017-06-06 | 太原理工大学 | A kind of fast preparation method of resin type carbon copper-loading catalyst |
| CN110127658B (en) * | 2019-07-01 | 2021-02-02 | 青海民族大学 | Mesoporous carbon nano composite electrode material for supercapacitor and preparation method thereof |
| CN113559921B (en) * | 2021-07-21 | 2023-08-25 | 东南大学 | Metal loaded mesoporous carbon-ZSM-5 molecular sieve shell-core catalyst and preparation and application methods thereof |
| CN116673054A (en) * | 2023-06-04 | 2023-09-01 | 太原理工大学 | Preparation of peanut shell nitrogen-doped carbon-supported copper catalyst and application of peanut shell nitrogen-doped carbon-supported copper catalyst in synthesis of diethyl carbonate |
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