CN105080543A - Catalyst and method for preparation of ethylene carbonate - Google Patents

Abstract

The present invention relates to a catalyst and a method for the preparation of ethylene carbonate, and mainly solves the problem of low heterogeneous catalyst activity in the prior art. The catalyst comprises a main catalyst and a cocatalyst; the main catalyst is a mixed metal oxide AaOb / BcOd; wherein A is selected from at least one of Cu, Mg, Zn, Ca, Co or Ni; B is selected from at least one of Al, Fe, Cr or Zr; and the cocatalyst is organic phosphine R1R2R3P; the cocatalyst and main catalyst weight ratio is 0.1 to 10, and by the technical scheme, the problem is well solved, and the catalyst can be used for industrial production of preparation of ethylene carbonate from ethylene oxide and carbon dioxide.

Description

Prepare catalyst and the method thereof of ethylene carbonate

Technical field

The present invention relates to a kind of catalyst and the method thereof of preparing ethylene carbonate.

Background technology

Ethylene carbonate is a kind of solvent and fine-chemical intermediate of function admirable, 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 oxirane and CO ₂reactive Synthesis ethylene carbonate 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 ethylene carbonate 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 catalyst all also exist the low problem of catalytic activity.

Yano etc. (Chem.Commu., 1997,1129-1130) use MgO as catalyst, for expoxy propane and CO ₂reaction generates the reaction of propene carbonate, and 135 DEG C are reacted 12 hours, and the yield obtaining propene carbonate is 41%.

Yamaguchi etc. (J.Am.Chem.Soc., 1999,121,4526-4527) use MgO/Al ₂o ₃as catalyst, for expoxy propane and CO ₂reaction generates the reaction of propene carbonate, and 100 DEG C are reacted 24 hours, and the yield obtaining propene carbonate is 88%, but the mass ratio of catalyst and substrate expoxy propane is up to 2.2.

Tu etc. (J.Catal., 2001,199,85-91) use Cs/KX as catalyst, for oxirane and CO ₂the reaction of reaction Formed vinyl acetate, 150 DEG C of reactions are after 3 hours, and the yield obtaining ethylene carbonate is 14%.

Summary of the invention

One of problem to be solved by this invention is that prior art exists the active low problem of heterogeneous catalysis, provides a kind of catalyst preparing ethylene carbonate newly.Two of problem to be solved by this invention is to provide a kind of method preparing ethylene carbonate, and the method has the high feature of catalytic activity.

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 catalyst preparing ethylene carbonate, comprises major catalyst and co-catalyst;

Described major catalyst 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 co-catalyst is organic phosphine R ₁r ₂r ₃p; Wherein, R ₁, R ₂, R ₃be fat-based or aromatic yl group C _xh _y, x is the arbitrary integer in 1 ~ 10, and y is the arbitrary integer in 3 ~ 21;

The weight ratio of co-catalyst and major catalyst 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 co-catalyst and major catalyst is 0.2 ~ 5.

In technique scheme, preferably, described organic phosphine R ₁r ₂r ₃in P, R ₁, R ₂, R ₃for aryl radical.More preferably, described organic phosphine R1R2R3P is triphenylphosphine, ethyldiphenylphosphine, allyldiphenylphosphine, tri-n-octyl phosphine or tributylphosphine.

For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of method preparing ethylene carbonate, with oxirane and carbon dioxide for raw material, it is 50 ~ 200 DEG C in reaction temperature, reaction pressure is under the condition of 0.1 ~ 10.0MPa, reaction raw materials and catalyst exposure Formed vinyl acetate; Described catalyst comprises major catalyst and co-catalyst;

Described major catalyst 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 major catalyst and oxirane is 0.0001 ~ 0.1;

Described co-catalyst is organic phosphine R ₁r ₂r ₃p; Wherein, R ₁, R ₂, R ₃be fat-based or aromatic yl group C _xh _y, x is the arbitrary integer in 1 ~ 10, and y is the arbitrary integer in 3 ~ 21;

The weight ratio of co-catalyst and major catalyst is 0.1 ~ 10.

In technique scheme, preferably, reaction temperature is 80 ~ 160 DEG C, and reaction pressure is 0.5 ~ 8.0MPa, and the weight ratio of major catalyst and oxirane is 0.0005 ~ 0.05.

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 co-catalyst and major catalyst is 0.2 ~ 5.

In technique scheme, preferably, described organic phosphine R ₁r ₂r ₃in P, R ₁, R ₂, R ₃for aryl radical.More preferably, described organic phosphine R1R2R3P is triphenylphosphine, ethyldiphenylphosphine, allyldiphenylphosphine, tri-n-octyl phosphine or tributylphosphine.

In the inventive method, the preparation method of catalyst is as follows:

1) add precipitating reagent to containing in the slaine mixed solution of A, B, the slaine containing A, B can be hydrochloride, bromate, iodate, sulfate, nitrate, and precipitating reagent can be ammoniacal liquor, alkali 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 organic phosphine R ₁r ₂r ₃p is as co-catalyst, and inventor is surprised to find co-catalyst and major catalyst A _ao _b/ B _co _dbetween there is significantly synergy, after adding co-catalyst, catalytic activity improves greatly.Be CuO/Al at major catalyst ₂o ₃(parts by weight 40/60), co-catalyst are that the weight ratio of triphenylphosphine, co-catalyst and major catalyst is 0.5, reaction temperature is 120 DEG C, reaction pressure is 5.0MPa, the ratio of major catalyst and oxirane is react 4 hours under the condition of 0.01, the conversion ratio of oxirane can reach 97.5%, the selective of ethylene carbonate reaches 99.3%, achieves good technique effect.

Below by embodiment, the invention will be further elaborated.

Detailed description of the invention

[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 natrium carbonicum calcinatum 200mL aqueous solution wherein, collects the sediment obtained, spend deionized water 3 times, each 500mL, the sediment 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 precipitating reagent 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

Continued 1

[embodiment 24]

Take MO-1 catalyst obtained by 0.50g above-mentioned [embodiment 1] and 0.25g triphenylphosphine is placed in 100mL stainless steel cauldron, use N ₂air in replacement reaction kettle, is then filled with 50.0g oxirane, 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 chromatography to product, the conversion ratio obtaining oxirane is 97.5%, and the selective of ethylene carbonate is 99.3%.

[embodiment 25 ~ 46]

Catalyst obtained by [embodiment 2 ~ 23] is used for oxirane 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	Major catalyst	Oxirane conversion ratio, %	Ethylene carbonate is selective, %
				25	MO-2	69.8	97.4
26	MO-3	71.4	99.5
				27	MO-4	89.5	97.5
28	MO-5	82.4	98.7
				29	MO-6	67.8	99.1
30	MO-7	71.9	89.8
				31	MO-8	68.7	96.5
32	MO-9	86.8	97.4
				33	MO-10	57.6	82.5
34	MO-11	85.6	97.1
				35	MO-12	63.4	89.9
36	MO-13	72.2	96.5
				37	MO-14	68.9	98.0
38	MO-15	90.2	98.0
				39	MO-16	84.3	98.9
40	MO-17	68.9	99.2
				41	MO-18	73.1	88.8
42	MO-19	71.2	97.2
				43	MO-20	87.9	98.1
44	MO-21	62.3	87.2
				45	MO-22	88.8	96.6
46	MO-23	71.5	89.2

[embodiment 47 ~ 55]

The kind changing the organic phosphine used 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	Organic phosphine	Oxirane conversion ratio, %	Ethylene carbonate is selective, %
				47	Triphenylphosphine 1.0g	95.4	99.1
48	Triphenylphosphine 2.0g	98.2	95.6
				49	Triphenylphosphine 5.0g	99.1	92.4
50	Triphenylphosphine 0.1g	45.6	94.5
				51	Triphenylphosphine 0.05g	31.0	84.4
52	Ethyldiphenylphosphine 0.25g	81.2	97.7
				53	Allyldiphenylphosphine 0.25g	91.2	98.3
54	Tri-n-octyl phosphine 0.25g	95.4	96.7
				55	Tributylphosphine 0.25g	82.6	98.1

[comparative example 1 ~ 5]

Be used alone major catalyst or co-catalyst, 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 major catalyst/co-catalyst, reaction temperature, reaction pressure, major catalyst and oxirane, 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. prepare a catalyst for ethylene carbonate, comprise major catalyst and co-catalyst;

Described major catalyst 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 co-catalyst is organic phosphine R ₁r ₂r ₃p; Wherein, R ₁, R ₂, R ₃be fat-based or aromatic yl group C _xh _y, x is the arbitrary integer in 1 ~ 10, and y is the arbitrary integer in 3 ~ 21;

The weight ratio of co-catalyst and major catalyst is 0.1 ~ 10.

2. prepare the catalyst of ethylene carbonate according to claim 1, it is characterized in that A is selected from least one in Cu, Zn, Ca or Ni.

3. prepare the catalyst of ethylene carbonate 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. prepare the catalyst of ethylene carbonate 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. prepare the catalyst of ethylene carbonate according to claim 1, it is characterized in that B is selected from least one in Al or Fe.

6. prepare the catalyst of ethylene carbonate 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. prepare the catalyst of ethylene carbonate according to claim 1, it is characterized in that the weight ratio of co-catalyst and major catalyst is 0.2 ~ 5.

8. prepare the catalyst of ethylene carbonate according to claim 1, it is characterized in that described organic phosphine R ₁r ₂r ₃in P, R ₁, R ₂, R ₃for aryl radical.

9. prepare the catalyst of ethylene carbonate according to claim 8, it is characterized in that described organic phosphine R1R2R3P is triphenylphosphine, ethyldiphenylphosphine, allyldiphenylphosphine, tri-n-octyl phosphine or tributylphosphine.

10. prepare a method for ethylene carbonate, with oxirane and carbon dioxide for raw material, be 50 ~ 200 DEG C in reaction temperature, reaction pressure is under the condition of 0.1 ~ 10.0MPa, reaction raw materials and catalyst exposure Formed vinyl acetate; Described catalyst comprises major catalyst and co-catalyst;

Described major catalyst 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 major catalyst and oxirane is 0.0001 ~ 0.1;

Described co-catalyst is organic phosphine R ₁r ₂r ₃p; Wherein, R ₁, R ₂, R ₃be fat-based or aromatic yl group C _xh _y, x is the arbitrary integer in 1 ~ 10, and y is the arbitrary integer in 3 ~ 21;

The weight ratio of co-catalyst and major catalyst is 0.1 ~ 10.