CN105294643B - Ethylene oxide and carbon dioxide prepare the catalyst and its method of ethylene carbonate - Google Patents
Ethylene oxide and carbon dioxide prepare the catalyst and its method of ethylene carbonate Download PDFInfo
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- CN105294643B CN105294643B CN201410355839.7A CN201410355839A CN105294643B CN 105294643 B CN105294643 B CN 105294643B CN 201410355839 A CN201410355839 A CN 201410355839A CN 105294643 B CN105294643 B CN 105294643B
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Abstract
The present invention relates to catalyst and its method that a kind of ethylene oxide and carbon dioxide prepare ethylene carbonate, and mainly solving the problems, such as the prior art, there are heterogeneous catalysis activity is low.The present invention includes major catalyst and co-catalyst by using the catalyst；The major catalyst is metal mixing oxide AaOb/BcOd；Wherein, A is selected from least one of Cu, Mg, Zn, Ca, Co or Ni；B is selected from least one of Al, Fe, Cr or Zr；The co-catalyst Wei quaternary alkylphosphonium salts R1R2R3R4P+X‑；The technical solution that the weight ratio of co-catalyst and major catalyst is 0.1~10 preferably solves the problems, such as this, can be used in the industrial production of ethylene carbonate.
Description
Technical field
The present invention relates to catalyst and its method that a kind of ethylene oxide and carbon dioxide prepare ethylene carbonate.
Background technology
Ethylene carbonate is a kind of solvent and fine-chemical intermediate of function admirable, is that the potential basis of organic chemical industry is former
Material.CO simultaneously2It is a kind of greenhouse gases, how effectively fixation has become this century most challenging one of project, and
Pass through ethylene oxide and CO2It is exactly the good fixing means of one of which to react synthesizing ethylene carbonate.With recently with carbonic acid
Vinyl acetate is that raw material co-producing dimethyl carbonate and glycol reaction are of increasing concern, and CO is fixed by cyclic carbonate2Way
Diameter also receives more and more attention.
The heterogeneous catalyst for the production cyclic carbonate reported at present includes MgO, MgO/Al2O3With Cs/KX etc., these
Catalyst has that catalytic activity is low.
Yano etc. (Chem.Commu., 1997,1129-1130) uses MgO as catalyst, is used for propylene oxide and CO2
Reaction generates the reaction of propene carbonate, and 135 DEG C are reacted 12 hours, and the yield for obtaining propene carbonate is 41%.
Yamaguchi etc. (J.Am.Chem.Soc., 1999,121,4526-4527) uses MgO/Al2O3As catalyst,
For propylene oxide and CO2Reaction generates the reaction of propene carbonate, and 100 DEG C are reacted 24 hours, obtains obtaining for propene carbonate
Rate is 88%, but the mass ratio of catalyst and substrate propylene oxide is up to 2.2.
Tu etc. (J.Catal., 2001,199,85-91) uses Cs/KX as catalyst, is used for ethylene oxide and CO2Instead
The reaction of ethylene carbonate should be generated, after 150 DEG C are reacted 3 hours, the yield for obtaining ethylene carbonate is 14%.
Invention content
The first technical problem to be solved by the present invention is that the prior art has that heterogeneous catalysis activity is low, is carried
The catalyst of ethylene carbonate is prepared for a kind of new ethylene oxide and carbon dioxide.The spy that the catalyst has catalytic activity high
Point.The second technical problem to be solved by the present invention is to provide a kind of new ethylene oxide and carbon dioxide prepares ethylene carbonate
Method.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of ethylene oxide and titanium dioxide
Carbon prepares the catalyst of ethylene carbonate, including major catalyst and co-catalyst；
The major catalyst is metal mixing oxide AaOb/BcOd；Wherein, A is in Cu, Mg, Zn, Ca, Co or Ni
It is at least one；B is selected from least one of Al, Fe, Cr or Zr；A, b, c, d are respectively any integer in 1~4；With parts by weight
Number is counted, in metal mixing oxide, AaObNumber be 10~80 parts, BcOd20~90 parts of number；
The co-catalyst Wei quaternary alkylphosphonium salts R1R2R3R4P+X-；Wherein, R1、R2、R3、R4It is fat-based or aryl group
CxHy, x is any integer in 1~10, and y is any integer in 3~21, X Cl, Br or I；
The weight ratio of co-catalyst and major catalyst is 0.1~10.
In above-mentioned technical proposal, it is preferable that A is selected from least one of Cu, Zn, Ca or Ni.
In above-mentioned technical proposal, it is preferable that A is Cu and the mixture selected from least one of Mg, Zn, Ca, Co or Ni.
It is highly preferred that A is Cu and the mixture selected from least one of Zn, Ca or Ni.
In above-mentioned technical proposal, it is preferable that B is selected from least one of Al or Fe.
In above-mentioned technical proposal, it is preferable that mixed oxide AaOb/BcOdIn, AaObNumber be 20~70 parts, BcOd's
30~80 parts of number.
In above-mentioned technical proposal, it is preferable that the weight ratio of co-catalyst and catalyst is 0.2~5.
In above-mentioned technical proposal, it is preferable that R in quaternary alkylphosphonium salt1、R2、R3、R4For aromatic radical.It is highly preferred that the quaternary alkylphosphonium salt
Selected from methyl triphenyl phosphonium iodide, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, four tertiary butyl phosphonium chlorides or four n-Octyl Bromides
Hua Phosphonium.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：A kind of ethylene oxide and titanium dioxide
The method that carbon prepares ethylene carbonate is 50~200 DEG C in reaction temperature using ethylene oxide and carbon dioxide as raw material, reaction
Under conditions of pressure is 0.1~10.0MPa, reaction raw materials are contacted with catalyst generates ethylene carbonate；
The catalyst includes major catalyst and co-catalyst；
The major catalyst is metal mixing oxide AaOb/BcOd；Wherein, A is in Cu, Mg, Zn, Ca, Co or Ni
It is at least one；B is selected from least one of Al, Fe, Cr or Zr；A, b, c, d are respectively any integer in 1~4；With parts by weight
Number is counted, in metal mixing oxide, AaObNumber be 10~80 parts, BcOd20~90 parts of number；Major catalyst and epoxy second
The weight ratio of alkane is 0.0001~0.1；
The co-catalyst Wei quaternary alkylphosphonium salts R1R2R3R4P+X-；Wherein, R1、R2、R3、R4It is fat-based or aryl group
CxHy, x is any integer in 1~10, and y is any integer in 3~21, X Cl, Br or I；
The weight ratio of co-catalyst and major catalyst is 0.1~10.
In above-mentioned technical proposal, it is preferable that A is selected from least one of Cu, Zn, Ca or Ni.
In above-mentioned technical proposal, it is preferable that A is Cu and the mixture selected from least one of Mg, Zn, Ca, Co or Ni.
It is highly preferred that A is Cu and the mixture selected from least one of Zn, Ca or Ni.
In above-mentioned technical proposal, it is preferable that B is selected from least one of Al or Fe.
In above-mentioned technical proposal, it is preferable that mixed oxide AaOb/BcOdIn, AaObNumber be 20~70 parts, BcOd's
30~80 parts of number.
In above-mentioned technical proposal, it is preferable that the weight ratio of co-catalyst and catalyst is 0.2~5.
In above-mentioned technical proposal, it is preferable that R in quaternary alkylphosphonium salt1、R2、R3、R4For aromatic radical.It is highly preferred that the quaternary alkylphosphonium salt
Selected from methyl triphenyl phosphonium iodide, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, four tertiary butyl phosphonium chlorides or four n-Octyl Bromides
Hua Phosphonium.
In above-mentioned technical proposal, it is preferable that reaction temperature is 80~160 DEG C, and reaction pressure is 0.5~8.0MPa, main reminder
Agent and the weight ratio of ethylene oxide are 0.0005~0.05.
The preparation method of major catalyst is as follows in the present invention：
1) precipitating reagent is added into the metal mixed salt solution containing A, B, the metal salt containing A, B can be hydrochloride, bromic acid
Salt, iodate, sulfate, nitrate, precipitating reagent can be ammonium hydroxide, alkali carbonate and alkali metal hydroxide.
2) precipitation obtained by step 1) is collected, is dried after washing.
3) mixed metal oxide catalyst is obtained after roasting the precipitation that step 2) is dried.
The present invention is by adding quaternary alkylphosphonium salt R1R2R3R4P+X-As co-catalyst, it is surprisingly found by the inventors that co-catalyst with
Major catalyst AaOb/BcOdBetween there is apparent synergistic effect, catalytic activity greatly improves after adding co-catalyst.In main reminder
Agent is CuO/Al2O3(parts by weight 40/60), co-catalyst are methyl triphenyl phosphonium iodide, co-catalyst and major catalyst
Weight ratio is 0.5, reaction temperature is 120 DEG C, reaction pressure is 5.0 MPa, and the weight ratio of major catalyst and ethylene oxide is
It is reacted 4 hours under conditions of 0.01, for the conversion ratio of ethylene oxide up to 99.0%, the selectivity of ethylene carbonate is reachable
99.3%, achieve preferable technique effect.
The present invention will be further described below by way of examples.
Specific implementation mode
【Embodiment 1】
Weigh 12.1 g Cu (NO3)2·3H2O and 44.2 g Al (NO3)3·9H2O is dissolved in 300mL water, is added thereto
Enter to contain 25.2 g natrium carbonicum calcinatum 200mL aqueous solutions, collects obtained sediment, be washed with deionized 3 times, every time
500mL roasts 5 hours at 500 DEG C after obtained sediment is 24 hours dry in 120 DEG C of baking ovens, obtains CuO/Al2O3Mixing
Oxide catalyst MO-1, wherein CuO and Al2O3Parts by weight be respectively 40 and 60.
【Embodiment 2~23】
Mixed metal salt, the type of precipitating reagent and used amount used in changing, remaining condition is constant, and what is obtained is mixed
It is as shown in table 1 to close metal oxide catalyst.
Table 1
【Embodiment 24】
It is above-mentioned to weigh 0.50g【Embodiment 1】Obtained MO-1 catalyst and 0.25g methyl triphenyl phosphonium iodides is placed in
In 100mL stainless steel cauldrons, N is used2Air in replacement reaction kettle is then charged with 50.0g ethylene oxide, is passed through CO2, maintainer
System pressure is 1.0MPa, and stirring is warming up to 120 DEG C after 1 hour, CO is added2, system pressure 5.0MPa is kept, after reacting 4 hours
It is cooling, chromatography is carried out to reaction product, the conversion ratio for obtaining ethylene oxide is 99.0%, and the selectivity of ethylene carbonate is
99.3%.
【Embodiment 25~46】
It will【Embodiment 2~23】Obtained catalyst is used for ethylene oxide and CO2Reaction in, remaining condition with【It is real
Apply example 24】Identical, obtained reaction result is as shown in table 2.
Table 2
| Embodiment | Catalyst | Ethylene oxide conversion ratio, % | Ethylene carbonate selectivity, % |
| 25 | MO-2 | 90.2 | 98.9 |
| 26 | MO-3 | 83.2 | 97.6 |
| 27 | MO-4 | 92.3 | 97.4 |
| 28 | MO-5 | 74.7 | 96.2 |
| 29 | MO-6 | 54.3 | 97.9 |
| 30 | MO-7 | 67.4 | 87.8 |
| 31 | MO-8 | 76.5 | 95.9 |
| 32 | MO-9 | 91.3 | 94.8 |
| 33 | MO-10 | 41.5 | 74.8 |
| 34 | MO-11 | 79.3 | 93.4 |
| 35 | MO-12 | 64.5 | 84.3 |
| 36 | MO-13 | 92.2 | 98.3 |
| 37 | MO-14 | 76.5 | 98.2 |
| 38 | MO-15 | 95.1 | 97.8 |
| 39 | MO-16 | 78.3 | 97.2 |
| 40 | MO-17 | 60.1 | 97.1 |
| 41 | MO-18 | 73.4 | 89.4 |
| 42 | MO-19 | 80.2 | 97.1 |
| 43 | MO-20 | 92.4 | 95.4 |
| 44 | MO-21 | 52.3 | 79.8 |
| 45 | MO-22 | 80.9 | 92.3 |
| 46 | MO-23 | 74.3 | 86.5 |
【Embodiment 47~55】
Change used in quaternary alkylphosphonium salt type and used amount, remaining condition with【Embodiment 24】It is identical, it obtains
Reaction result is as shown in table 3.
Table 3
| Embodiment | Quaternary alkylphosphonium salt | Ethylene oxide conversion ratio, % | Ethylene carbonate selectivity, % |
| 47 | Methyl triphenyl phosphonium iodide 1.0g | 98.2 | 94.3 |
| 48 | Methyl triphenyl phosphonium iodide 2.0g | 99.1 | 93.4 |
| 49 | Methyl triphenyl phosphonium iodide 5.0g | 98.3 | 91.4 |
| 50 | Methyl triphenyl phosphonium iodide 0.1g | 45.3 | 90.1 |
| 51 | Methyl triphenyl phosphonium iodide 0.05g | 28.3 | 83.2 |
| 52 | 4-phenyl phosphonium bromide 0.25g | 76.4 | 98.1 |
| 53 | Ethyl triphenyl phosphonium iodide 0.25g | 81.2 | 98.9 |
| 54 | Four tertiary butyl phosphonium chloride 0.25g | 94.4 | 95.9 |
| 55 | Four n-octyl phosphonium bromide 0.25g | 83.5 | 98.7 |
【Comparative example 1~5】
Be used alone major catalyst or co-catalyst, remaining condition with【Embodiment 24】It is identical, obtained result such as table 4
It is shown.
Table 4
【Embodiment 56~60】
Change the dosage of major catalyst/co-catalyst, the weight of reaction temperature, reaction pressure, major catalyst and ethylene oxide
Measure ratio, remaining condition with【Embodiment 24】Identical, obtained reaction result is as shown in table 5.
Table 5
Claims (5)
1. a kind of ethylene oxide and carbon dioxide prepare the catalyst of ethylene carbonate, including major catalyst and co-catalyst；
The major catalyst is metal mixing oxide AaOb/BcOd；Wherein, A is Cu or A is Cu and in Mg, Zn, Ca
At least one mixture；B is selected from least one of Al, Fe；A, b, c, d are respectively any integer in 1~4；With weight
Number meter, in metal mixing oxide, AaObNumber be 10~80 parts, BcOd20~90 parts of number；
The co-catalyst Wei quaternary alkylphosphonium salts；The quaternary alkylphosphonium salt is selected from methyl triphenyl phosphonium iodide, 4-phenyl phosphonium bromide, ethyl triphen
Base phosphonium iodide, four tertiary butyl phosphonium chlorides or four n-octyl phosphonium bromides；
The weight ratio of co-catalyst and major catalyst is 0.1~10.
2. ethylene oxide and carbon dioxide prepare the catalyst of ethylene carbonate according to claim 1, it is characterised in that A is
Cu and mixture selected from least one of Zn, Ca.
3. ethylene oxide and carbon dioxide prepare the catalyst of ethylene carbonate according to claim 1, it is characterised in that mixed
Close oxide AaOb/BcOdIn, AaObNumber be 20~70 parts, BcOd30~80 parts of number.
4. ethylene oxide and carbon dioxide prepare the catalyst of ethylene carbonate according to claim 1, it is characterised in that help
The weight ratio of catalyst and major catalyst is 0.2~5.
5. a kind of method that ethylene oxide and carbon dioxide prepare ethylene carbonate, using ethylene oxide and carbon dioxide as raw material,
It it is 50~200 DEG C in reaction temperature, under conditions of reaction pressure is 0.1~10.0MPa, reaction raw materials contact generation with catalyst
Ethylene carbonate；
The catalyst includes major catalyst and co-catalyst；
The major catalyst is metal mixing oxide AaOb/BcOd；Wherein, A is Cu or A is Cu and in Mg, Zn, Ca
At least one mixture；B is selected from least one of Al, Fe；A, b, c, d are respectively any integer in 1~4；With weight
Number meter, in metal mixing oxide, AaObNumber be 10~80 parts, BcOd20~90 parts of number；Major catalyst and epoxy
The weight ratio of ethane is 0.0001~0.1；
The co-catalyst Wei quaternary alkylphosphonium salts；The quaternary alkylphosphonium salt is selected from methyl triphenyl phosphonium iodide, 4-phenyl phosphonium bromide, ethyl triphen
Base phosphonium iodide, four tertiary butyl phosphonium chlorides or four n-octyl phosphonium bromides；
The weight ratio of co-catalyst and major catalyst is 0.1~10.
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