CN105294643A - Catalyst and method for preparing ethylene carbonate from oxirane and carbon dioxide - Google Patents

Catalyst and method for preparing ethylene carbonate from oxirane and carbon dioxide Download PDF

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CN105294643A
CN105294643A CN201410355839.7A CN201410355839A CN105294643A CN 105294643 A CN105294643 A CN 105294643A CN 201410355839 A CN201410355839 A CN 201410355839A CN 105294643 A CN105294643 A CN 105294643A
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oxyethane
catalyzer
nsc
carbonic acid
acid gas
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CN105294643B (en
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陈梁锋
杨为民
何文军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a catalyst and a method for preparing ethylene carbonate from oxirane and carbon dioxide, and mainly solves the problem in the prior art that the heterogeneous catalyst is low in activity. The catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is metal mixed oxide AaOb/BcOd, A is selected from one or more of Cu, Mg, Zn, Ca, Co or Ni, and B is selected from one or more of Al, Fe, Cr or Zr; the cocatalyst is quaternary phosphonium salt R1R2R3R4P<+>X<->; the weight ratio of the cocatalyst to the main catalyst is 0.1-10. According to the technical scheme, the problem is better solved, and the catalyst can be used for industrial production of ethylene carbonate.

Description

Oxyethane and carbonic acid gas prepare catalyzer and the method thereof of NSC 11801
Technical field
The present invention relates to catalyzer and method thereof that a kind of oxyethane and carbonic acid gas prepare NSC 11801.
Background technology
NSC 11801 is a kind of solvent and fine-chemical intermediate of excellent property, is the potential basic material of organic chemical industry.CO simultaneously 2be a kind of greenhouse gases, how effectively fix and become one of challenging problem of most in this century, and by oxyethane and CO 2reactive Synthesis NSC 11801 is exactly wherein a kind of well fixing means.Along with being recently that raw material co-producing dimethyl carbonate and glycol reaction receive publicity, day by day by cyclic carbonate fixation of C O with NSC 11801 2approach also receive increasing attention.
The heterogeneous catalyst of the production cyclic carbonate reported at present comprises MgO, MgO/Al 2o 3with Cs/KX etc., these catalyzer all also exist the low problem of catalytic activity.
Yano etc. (Chem.Commu., 1997,1129-1130) use MgO as catalyzer, for propylene oxide and CO 2reaction generates the reaction of propylene carbonate, and 135 DEG C are reacted 12 hours, and the yield obtaining propylene carbonate is 41%.
Yamaguchi etc. (J.Am.Chem.Soc., 1999,121,4526-4527) use MgO/Al 2o 3as catalyzer, for propylene oxide and CO 2reaction generates the reaction of propylene carbonate, and 100 DEG C are reacted 24 hours, and the yield obtaining propylene carbonate is 88%, but the mass ratio of catalyzer and substrate propylene oxide is up to 2.2.
Tu etc. (J.Catal., 2001,199,85-91) use Cs/KX as catalyzer, for oxyethane and CO 2the reaction of reaction Formed vinyl acetate, 150 DEG C of reactions are after 3 hours, and the yield obtaining NSC 11801 is 14%.
Summary of the invention
One of technical problem to be solved by this invention is that prior art exists the active low problem of heterogeneous catalyst, provides a kind of new oxyethane and carbonic acid gas to prepare the catalyzer of NSC 11801.This catalyzer has the high feature of catalytic activity.Two of technical problem to be solved by this invention is to provide a kind of method that new oxyethane and carbonic acid gas prepare NSC 11801.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of oxyethane and carbonic acid gas prepare the catalyzer of NSC 11801, comprises Primary Catalysts and promotor;
Described Primary Catalysts is metal mixing oxide A ao b/ B co d; Wherein, A is selected from least one in Cu, Mg, Zn, Ca, Co or Ni; B is selected from least one in Al, Fe, Cr or Zr; A, b, c, d are respectively the arbitrary integer in 1 ~ 4; With weight parts, in metal mixing oxide, A ao bnumber be 10 ~ 80 parts, B co dnumber 20 ~ 90 parts;
Described promotor Wei quaternary alkylphosphonium salt R 1r 2r 3r 4p +x -; Wherein, R 1, R 2, R 3, R 4be fatty group or aromatic yl group C xh y, x is the arbitrary integer in 1 ~ 10, and y is the arbitrary integer in 3 ~ 21, and X is Cl, Br or I;
The weight ratio of promotor and Primary Catalysts is 0.1 ~ 10.
In technique scheme, preferably, A is selected from least one in Cu, Zn, Ca or Ni.
In technique scheme, preferably, A is Cu and the mixture being selected from least one in Mg, Zn, Ca, Co or Ni.More preferably, A is Cu and the mixture being selected from least one in Zn, Ca or Ni.
In technique scheme, preferably, B is selected from least one in Al or Fe.
In technique scheme, preferably, mixed oxide A ao b/ B co din, A ao bnumber be 20 ~ 70 parts, B co dnumber 30 ~ 80 parts.
In technique scheme, preferably, the weight ratio of promotor and catalyzer is 0.2 ~ 5.
In technique scheme, preferably R in ， quaternary alkylphosphonium salt 1, R 2, R 3, R 4for aromatic base.More preferably, described quaternary alkylphosphonium salt is selected from methyl triphenyl phosphonium iodide, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, four tertiary butyl phosphonium chlorides or four n-octyl phosphonium bromides.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of oxyethane and carbonic acid gas prepare the method for NSC 11801, with oxyethane and carbonic acid gas for raw material, it is 50 ~ 200 DEG C in temperature of reaction, reaction pressure is under the condition of 0.1 ~ 10.0MPa, reaction raw materials and catalyst exposure Formed vinyl acetate;
Described catalyzer comprises Primary Catalysts and promotor;
Described Primary Catalysts is metal mixing oxide A ao b/ B co d; Wherein, A is selected from least one in Cu, Mg, Zn, Ca, Co or Ni; B is selected from least one in Al, Fe, Cr or Zr; A, b, c, d are respectively the arbitrary integer in 1 ~ 4; With weight parts, in metal mixing oxide, A ao bnumber be 10 ~ 80 parts, B co dnumber 20 ~ 90 parts; The weight ratio of Primary Catalysts and oxyethane is 0.0001 ~ 0.1;
Described promotor Wei quaternary alkylphosphonium salt R 1r 2r 3r 4p +x -; Wherein, R 1, R 2, R 3, R 4be fatty group or aromatic yl group C xh y, x is the arbitrary integer in 1 ~ 10, and y is the arbitrary integer in 3 ~ 21, and X is Cl, Br or I;
The weight ratio of promotor and Primary Catalysts is 0.1 ~ 10.
In technique scheme, preferably, A is selected from least one in Cu, Zn, Ca or Ni.
In technique scheme, preferably, A is Cu and the mixture being selected from least one in Mg, Zn, Ca, Co or Ni.More preferably, A is Cu and the mixture being selected from least one in Zn, Ca or Ni.
In technique scheme, preferably, B is selected from least one in Al or Fe.
In technique scheme, preferably, mixed oxide A ao b/ B co din, A ao bnumber be 20 ~ 70 parts, B co dnumber 30 ~ 80 parts.
In technique scheme, preferably, the weight ratio of promotor and catalyzer is 0.2 ~ 5.
In technique scheme, preferably R in ， quaternary alkylphosphonium salt 1, R 2, R 3, R 4for aromatic base.More preferably, described quaternary alkylphosphonium salt is selected from methyl triphenyl phosphonium iodide, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, four tertiary butyl phosphonium chlorides or four n-octyl phosphonium bromides.
In technique scheme, preferably, temperature of reaction is 80 ~ 160 DEG C, and reaction pressure is 0.5 ~ 8.0MPa, and the weight ratio of Primary Catalysts and oxyethane is 0.0005 ~ 0.05.
In the present invention, the preparation method of Primary Catalysts is as follows:
1) add precipitation agent to containing in the metal-salt mixing solutions of A, B, the metal-salt containing A, B can be hydrochloride, bromate, iodate, vitriol, nitrate, and precipitation agent can be ammoniacal liquor, alkaline carbonate and alkali metal hydroxide.
2) by step 1) precipitation of gained collects, washing post-drying.
3) by step 2) obtain described mixed metal oxide catalyst after the precipitation roasting of drying.
The present invention is by adding quaternary alkylphosphonium salt R 1r 2r 3r 4p +x -as promotor, contriver is surprised to find promotor and Primary Catalysts A ao b/ B co dbetween there is significantly synergy, after adding promotor, catalytic activity improves greatly.Be CuO/Al at Primary Catalysts 2o 3(parts by weight 40/60), promotor are that the weight ratio of methyl triphenyl phosphonium iodide, promotor and Primary Catalysts is 0.5, temperature of reaction is 120 DEG C, reaction pressure is 5.0MPa, the weight ratio of Primary Catalysts and oxyethane is react 4 hours under the condition of 0.01, the transformation efficiency of oxyethane can reach 99.0%, the selectivity of NSC 11801 can reach 99.3%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Take 12.1gCu (NO 3) 23H 2o and 44.2gAl (NO 3) 39H 2o is dissolved in 300mL water, adds containing the 25.2g anhydrous sodium carbonate 200mL aqueous solution wherein, collects the throw out obtained, with deionized water wash 3 times, each 500mL, the throw out obtained is in 120 DEG C of baking ovens after dry 24 hours, 500 DEG C of roastings 5 hours, obtain CuO/Al 2o 3mixed oxide catalyst MO-1, wherein CuO and Al 2o 3parts by weight be respectively 40 and 60.
[embodiment 2 ~ 23]
The mixed metal salt that change uses, the kind of precipitation agent and the amount used, all the other conditions are constant, and the mixed metal oxide catalyst obtained is as shown in table 1.
Table 1
[embodiment 24]
Take MO-1 catalyzer obtained by 0.50g above-mentioned [embodiment 1] and 0.25g methyl triphenyl phosphonium iodide is placed in 100mL stainless steel cauldron, use N 2air in replacement reaction kettle, is then filled with 50.0g oxyethane, passes into CO 2, keeping system pressure is 1.0MPa, stirs and is warmed up to 120 DEG C after 1 hour, add CO 2, keeping system pressure 5.0MPa, react after 4 hours and cool, carry out stratographic analysis to reaction product, the transformation efficiency obtaining oxyethane is 99.0%, and the selectivity of NSC 11801 is 99.3%.
[embodiment 25 ~ 46]
Catalyzer obtained by [embodiment 2 ~ 23] is used for oxyethane and CO 2reaction in, all the other conditions are identical with [embodiment 24], and the reaction result obtained is as shown in table 2.
Table 2
Embodiment Catalyzer Oxyethane transformation efficiency, % NSC 11801 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 the kind using quaternary alkylphosphonium salt and the amount used, all the other conditions are identical with [embodiment 24], and the reaction result obtained is as shown in table 3.
Table 3
Embodiment Quaternary alkylphosphonium salt Oxyethane transformation efficiency, % NSC 11801 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 Primary Catalysts or promotor, all the other conditions are identical with [embodiment 24], and the result obtained is as shown in table 4.
Table 4
[embodiment 56 ~ 60]
Change the weight ratio of the consumption of Primary Catalysts/promotor, temperature of reaction, reaction pressure, Primary Catalysts and oxyethane, all the other conditions are identical with [embodiment 24], and the reaction result obtained is as shown in table 5.
Table 5

Claims (10)

1. oxyethane and carbonic acid gas prepare a catalyzer for NSC 11801, comprise Primary Catalysts and promotor;
Described Primary Catalysts is metal mixing oxide A ao b/ B co d; Wherein, A is selected from least one in Cu, Mg, Zn, Ca, Co or Ni; B is selected from least one in Al, Fe, Cr or Zr; A, b, c, d are respectively the arbitrary integer in 1 ~ 4; With weight parts, in metal mixing oxide, A ao bnumber be 10 ~ 80 parts, B co dnumber 20 ~ 90 parts;
Described promotor Wei quaternary alkylphosphonium salt R 1r 2r 3r 4p +x -; Wherein, R 1, R 2, R 3, R 4be fatty group or aromatic yl group C xh y, x is the arbitrary integer in 1 ~ 10, and y is the arbitrary integer in 3 ~ 21, and X is Cl, Br or I;
The weight ratio of promotor and Primary Catalysts is 0.1 ~ 10.
2. oxyethane and carbonic acid gas prepare the catalyzer of NSC 11801 according to claim 1, it is characterized in that A is selected from least one in Cu, Zn, Ca or Ni.
3. oxyethane and carbonic acid gas prepare the catalyzer of NSC 11801 according to claim 1, it is characterized in that A is Cu and the mixture being selected from least one in Mg, Zn, Ca, Co or Ni.
4. oxyethane and carbonic acid gas prepare the catalyzer of NSC 11801 according to claim 3, it is characterized in that A is Cu and the mixture being selected from least one in Zn, Ca or Ni.
5. oxyethane and carbonic acid gas prepare the catalyzer of NSC 11801 according to claim 1, it is characterized in that B is selected from least one in Al or Fe.
6. oxyethane and carbonic acid gas prepare the catalyzer of NSC 11801 according to claim 1, it is characterized in that mixed oxide A ao b/ B co din, A ao bnumber be 20 ~ 70 parts, B co dnumber 30 ~ 80 parts.
7. oxyethane and carbonic acid gas prepare the catalyzer of NSC 11801 according to claim 1, it is characterized in that the weight ratio of promotor and Primary Catalysts is 0.2 ~ 5.
8. oxyethane and carbonic acid gas prepare the catalyzer of NSC 11801 according to claim 1, it is characterized in that R in described quaternary alkylphosphonium salt 1, R 2, R 3, R 4for aromatic base.
9. oxyethane and carbonic acid gas prepare the catalyzer of NSC 11801 according to claim 8, it is characterized in that described quaternary alkylphosphonium salt is selected from methyl triphenyl phosphonium iodide, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, four tertiary butyl phosphonium chlorides or four n-octyl phosphonium bromides.
10. an oxyethane and carbonic acid gas prepare the method for NSC 11801, with oxyethane and carbonic acid gas for raw material, be 50 ~ 200 DEG C in temperature of reaction, reaction pressure is under the condition of 0.1 ~ 10.0MPa, reaction raw materials and catalyst exposure Formed vinyl acetate;
Described catalyzer comprises Primary Catalysts and promotor;
Described Primary Catalysts is metal mixing oxide A ao b/ B co d; Wherein, A is selected from least one in Cu, Mg, Zn, Ca, Co or Ni; B is selected from least one in Al, Fe, Cr or Zr; A, b, c, d are respectively the arbitrary integer in 1 ~ 4; With weight parts, in metal mixing oxide, A ao bnumber be 10 ~ 80 parts, B co dnumber 20 ~ 90 parts; The weight ratio of Primary Catalysts and oxyethane is 0.0001 ~ 0.1;
Described promotor Wei quaternary alkylphosphonium salt R 1r 2r 3r 4p +x -; Wherein, R 1, R 2, R 3, R 4be fatty group or aromatic yl group C xh y, x is the arbitrary integer in 1 ~ 10, and y is the arbitrary integer in 3 ~ 21, and X is Cl, Br or I;
The weight ratio of promotor and Primary Catalysts is 0.1 ~ 10.
CN201410355839.7A 2014-07-24 2014-07-24 Ethylene oxide and carbon dioxide prepare the catalyst and its method of ethylene carbonate Active CN105294643B (en)

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