MOLECULAR SIEVE CATALYST, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF

Abstract

Provided are a molecular sieve catalyst, a preparation method therefor, an application thereof. The molecular sieve catalyst contains a modified Na-MOR molecular sieve, and the modification comprises: organic ammonium salt exchange, dealumination treatment, and ammonium ion exchange. The catalyst obtained by the method is used in dimethyl ether for one-step production of methyl acetate. The catalyst has high activity and stable performance, and the needs of industrial production can be satisfied.

Claims

1-27. (canceled)

28. A molecular sieve catalyst comprising a modified Na-MOR molecular sieve; wherein a modification comprises: an organic ammonium salt exchange, a dealumination treatment and an ammonium ion exchange.

29. The molecular sieve catalyst according to claim 28, wherein the organic ammonium salt exchange is an alkyl ammonium halide salt exchange.

30. The method according to claim 29, wherein the alkyl ammonium halide salt is at least one of compounds having a chemical formula shown in Formula I, ##STR00002## wherein R.sup.1, R.sup.2 and R.sup.3 are independently selected from C.sub.1-C.sub.10 alkyl group; R.sup.4 is selected from one of C.sub.1 to C.sub.10 alkyl group and C.sub.6 to C.sub.10 aryl group; and X is selected from at least one of F, Cl, Br and I.

31. The molecular sieve catalyst according to claim 30, wherein R.sup.1, R.sup.2 and R.sup.3 in Formula I are independently selected from CH.sub.3—, CH.sub.3CH.sub.2—, CH.sub.3 (CH.sub.2).sub.nCH.sub.2—, (CH.sub.3).sub.2CH—, (CH.sub.3).sub.2CHCH.sub.2— or CH.sub.3CH.sub.2(CH.sub.3)CH—; R.sup.4 is CH.sub.3—, CH.sub.3—, CH.sub.3CH.sub.2—, CH.sub.3(CH.sub.2).sub.mCH.sub.2—, (CH.sub.3).sub.2CH—, (CH.sub.3).sub.2CHCH.sub.2—, CH.sub.3CH.sub.2 (CH.sub.3) CH—, C.sub.6H.sub.5—, CH.sub.3C.sub.6H.sub.4—, (CH.sub.3).sub.2C.sub.6H.sub.3— or C.sub.6H.sub.5CH.sub.2—; wherein, n and m are independently selected from 1, 2, 3 or 4.

32. The molecular sieve catalyst according to claim 28, wherein a silicon to aluminum atomic ratio of the Na-MOR molecular sieve ranges from 6 to 50; and the dealumination treatment comprises at least one of a high-temperature calcination treatment and an acid treatment.

33. A method for preparing the molecular sieve catalyst according to claim 28 comprising subjecting a Na-MOR molecular sieve to the organic ammonium salt exchange, the dealumination treatment, the ammonium ion exchange, and further calcination to obtain the molecular sieve catalyst.

34. The method for preparing the molecular sieve catalyst according to claim 33, wherein the method comprises following steps: (1) subjecting a Na-MOR molecular sieve to the organic ammonium salt exchange to obtain a precursor I; (2) subjecting the precursor I to an acid treatment to obtain a precursor II; (3) subjecting the precursor II to a high-temperature calcination treatment to obtain a precursor III; (4) subjecting the precursor III to the ammonium ion exchange to obtain a precursor IV; and (5) calcining the precursor IV to obtain the molecular sieve catalyst.

35. The method for preparing the molecular sieve catalyst according to claim 34, wherein the organic ammonium salt exchange in step (1) is carried out by placing the Na-MOR molecular sieve in an organic ammonium salt solution at a temperature ranging from 20 to 100° C. for a time ranging from 1 to 10 hours; a concentration of the organic ammonium salt solution ranges from 0.05 to 1 mol/L; and the number of times the organic ammonium salt exchange ranges from 2 to 8; and conditions for the organic ammonium salt exchange refers to a temperature ranging from 30 to 80° C., and a time ranging from 2 to 6 hours.

36. The method for preparing the molecular sieve catalyst according to claim 34, wherein an acid used in the acid treatment in step (2) is at least one of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and citric acid; and the acid treatment in step (2) is carried out in an acidic solution at a temperature ranging from 30 to 100° C. for a time ranging from 1 to 10 hours.

37. The method for preparing the molecular sieve catalyst according to claim 36, wherein the number of times the acid treatment ranges from 2 to 10; and the acid treatment is carried out in the acidic solution at a temperature ranging from 30 to 80° C. for a time ranging from 2 to 8 hours.

38. The method for preparing the molecular sieve catalyst according to claim 34, wherein the high-temperature calcination treatment in step (3) is carried out in an atmosphere with a steam concentration ranging from 0 to 100%, at a temperature ranging from 300 to 800° C. for a time ranging from 1 to 10 hours.

39. The method for preparing the molecular sieve catalyst according to claim 38, wherein the high-temperature calcination treatment is carried out in an atmosphere with a steam concentration ranging from 0 to 100%, at a temperature ranging from 350 to 750° C. for a time ranging from 2 to 6 hours.

40. The method for preparing the molecular sieve catalyst according to claim 34, wherein the ammonium ion exchange in step (4) is carried out at a temperature ranging from 20 to 100° C. for a time ranging from 1 to 10 hours.

41. The method for preparing the molecular sieve catalyst according to claim 40, wherein, the number of times the ammonium ion exchange ranges from 2 to 5; the ammonium ion exchange is carried out at a temperature ranging from 30 to 90° C. for a time ranging from 2 to 6 hours; and the ammonium ion exchange is carried out in an ammonium ion-containing solution, and the ammonium ion-containing solution is at least one of ammonium nitrate solution, ammonium chloride solution, ammonium sulfate solution, and ammonium acetate solution.

42. The method for preparing the molecular sieve catalyst according to claim 34, wherein the high-temperature calcination treatment in step (5) is carried out in an air atmosphere at a temperature ranging from 300 to 800° C. for a time ranging 2 to 8 hours; preferably, the high-temperature calcination treatment is carried out in the air atmosphere at a temperature ranging from 400 to 750° C. for a time ranging 4 to 6 hours.

43. The method for preparing the molecular sieve catalyst according to claim 34, wherein the method comprises following steps: a) subjecting a solid containing Na-MOR molecular sieve to an exchange treatment in an alkyl ammonium halide salt solution at a temperature ranging from 20 to 100° C. for a time ranging from 1 to 10 hours to obtain the precursor I, wherein the number of times the exchange treatment ranges from 2 to 8; b) treating the precursor I with an acidic solution at a temperature ranging from 30 to 100° C. for a time ranging from 1 to 10 hours to obtain the precursor II, wherein the number of times the treatment with the acidic solution is from 2 to 10 times; c) treating the precursor II in an atmosphere with a steam concentration ranging from 0% to 100%, at a temperature ranging from 300 to 800° C. for a time ranging from 1 to 10 hours to obtain the precursor III; d) subjecting the precursor III to an exchange treatment in an ammonium nitrate aqueous solution at a temperature ranging from 20 to 100° C. for a time ranging from 1 to 10 hours to obtain the precursor IV, wherein the number of times the exchange treatment ranges from 2 to 5 times; and e) calcining the precursor IV in an air atmosphere at a temperature ranging from 300 to 800° C. for a time ranging 2 to 8 hours to obtain the molecular sieve catalyst.

44. A method for producing methyl acetate by carbonylation of dimethyl ether comprising feeding dimethyl ether and a feeding gas containing carbon monoxide into a reactor equipped with a catalyst bed to contact with a catalyst to produce methyl acetate; wherein, the catalyst the molecular sieve catalyst prepared by the method according to claim 33.

45. The method for producing methyl acetate by carbonylation of dimethyl ether according to claim 44, wherein the reaction conditions refer to the followings: a reaction temperature ranges from 150 to 280° C., a reaction pressure ranges from 0.5 to 25.0 MPa, and a weight hourly space velocity of the feeding dimethyl ether ranges from 0.05 to 5 h.sup.−1; and a molar ratio of carbon monoxide to dimethyl ether ranges from 0.1:1 to 30:1.

46. The method for producing methyl acetate by carbonylation of dimethyl ether according to claim 45, wherein the reaction conditions refer to the followings: the reaction temperature ranges from 160 to 280° C., the reaction pressure ranges from 0.5 to 20.0 MPa, and the weight hourly space velocity of the feeding dimethyl ether ranges from 0.2 to 4.0 h.sup.−1; and the molar ratio of carbon monoxide to dimethyl ether ranges from 0.1:1 to 20:1; preferably, the reaction conditions refer to the followings: the reaction temperature ranges from 170 to 260° C., the reaction pressure ranges from 1.0 to 15.0 MPa, and the weight hourly space velocity of the feeding dimethyl ether ranges from 0.1 to 4.0 h.sup.−1; and the molar ratio of carbon monoxide to dimethyl ether ranges from 0.2:1 to 15:1.

47. The method for producing methyl acetate by carbonylation of dimethyl ether according to claim 44, wherein the feeding gas containing carbon monoxide comprises from 15% to 100% carbon monoxide by volume; and the feeding gas containing carbon monoxide further comprises at least one of hydrogen, nitrogen, helium, argon, carbon dioxide, methane and ethane.

Description

DETAILED DESCRIPTION

[0119] The present application will be described in detail below with reference to the examples, but the present application is not limited to these examples.

[0120] Unless otherwise specified, the raw materials in the examples of the present application are all commercially available, wherein Na-MOR is purchased from Nankai University Catalyst Co., Ltd.

[0121] The analysis methods in the examples of the present application are as follows.

[0122] The gas after reaction is introduced into the online chromatograph through the heated pipeline for online analysis. The chromatograph is an Agilent 7890A equipped with a PLOT Q capillary column and a TDX-1 packed column, wherein the outlet of the PLOT-Q capillary column is connected to an FID detector, and the outlet of the TDX-1 packed column is connected to a TCD detector.

[0123] The conversion rate and selectivity in the examples of the present application are calculated as follows:

[0124] In the examples of the present application, the conversion rate of dimethyl ether, the conversion rate of carbon monoxide, and the selectivity of methyl acetate are calculated as below.

[0125] In the examples, the conversion rate of dimethyl ether and the selectivity of methyl acetate are both calculated based on the number of carbon moles of dimethyl ether.

Conversion rate of dimethyl ether=[(the molar number of carbon of dimethyl ether in raw materials)−(the molar number of carbon of dimethyl ether in the product)]+(the molar number of carbon of dimethyl ether in the raw materials)×(100%)

Selectivity of methyl acetate=(2/3)×(the molar number of carbon of methyl acetate in the product)+[(the molar number of carbon of dimethyl ether in the feeding gas)−(the molar number of carbon of dimethyl ether in the product)]×(100%)

Conversion rate of carbon monoxide=[(the molar number of CO before reaction)−(the molar number of CO after reaction)]+(the molar number of CO before reaction)×(100%)

[0126] According to an embodiment of the present application, the catalyst for carbonylation of dimethyl ether to produce methyl acetate refers to the one containing H-MOR molecular sieve as an active component which is obtained by modification.

[0127] As an embodiment, the modified Na-MOR molecular sieve is prepared by successive (R.sub.1)(R.sub.2)(R.sub.3)(R.sub.4)NCl (i.e., alkyl ammonium chloride salt) exchange, acid and/or steam treatment, and ammonium nitrate exchange.

[0128] As an embodiment, the silicon to aluminum atomic ratio of the Na-MOR molecular sieve ranges from 6 to 50.

[0129] As an embodiment, R.sub.1, R.sub.2 and R.sub.3 in (R.sub.1)(R.sub.2)(R.sub.3)(R.sub.4)NCl (i.e., alkyl ammonium chloride salt) are independently selected from one of CH.sub.3—, CH.sub.3CH.sub.2—, CH.sub.3(CH.sub.2).sub.nCH.sub.2— (wherein 0≤n≤4), (CH.sub.3).sub.2CH—, (CH.sub.3).sub.2CHCH.sub.2—, and CH.sub.3CH.sub.2(CH.sub.3) CH—; and R.sub.4 therein is one of CH.sub.3—, CH.sub.3—, CH.sub.3CH.sub.2—, CH.sub.3(CH.sub.2).sub.nCH.sub.2— (wherein 0≤n≤4), (CH.sub.3).sub.2CH—, (CH.sub.3).sub.2CHCH.sub.2—, CH.sub.3CH.sub.2 (CH.sub.3)CH—, C.sub.6H.sub.5—, CH.sub.3C.sub.6H.sub.4—, (CH.sub.3).sub.2C.sub.6H.sub.3— and C.sub.6H.sub.5CH.sub.2—.

[0130] As an embodiment, the (R.sub.1)(R.sub.2)(R.sub.3)(R.sub.4)NCl salt is preferably one of tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, ethyl trimethyl ammonium chloride, diethyl dimethyl ammonium chloride, triethyl methyl ammonium chloride, phenyl trimethyl ammonium chloride, and benzyl trimethyl ammonium chloride, and any combination thereof.

[0131] As an embodiment, a method for preparing the catalyst for carbonylation of dimethyl ether to produce methyl acetate is characterized by comprising the following steps: [0132] a) subjecting a sample containing Na-MOR to an exchange treatment in (R.sub.1)(R.sub.2)(R.sub.3)(R.sub.4)NCl salt solution at a temperature ranging from 20 to 100° C. for a time ranging from 1 to 10 hours, then washing, filtering and drying the resulting product; and repeating the above step 2 to 8 times; [0133] b) treating the product obtained in step a) with an acidic solution at a temperature ranging from 30 to 100° C. for a time ranging from 1 to 10 hours, then washing, filtering, and drying the resulting product; and repeating the above step 2 to 10 times; [0134] c) treating the product obtained in step b) in a steam atmosphere at a temperature ranging from 300 to 800° C. for a time ranging from 1 to 10 hours; [0135] d) subjecting the product obtained in step c) to an exchange treatment in an ammonium nitrate aqueous solution at a temperature ranging from 20 to 100° C. for a time ranging from 1 to 10 hours, then washing, filtering and drying the resulting product; and repeating the above step 2 to 5 times; [0136] e) calcining the product obtained in step d) in an air atmosphere at a temperature ranging from 300 to 800° C. for a time ranging from 2 to 8 hours to obtain the catalyst.

[0137] As an embodiment, the concentration of the salt solution in step a) ranges from 0.05 to 1 mol/L.

[0138] As an embodiment, the temperature of the exchange treatment in step a) ranges from 30 to 80° C., and the time of the exchange treatment in step a) ranges from 2 to 6 hours.

[0139] As an embodiment, the acidic solution in step b) is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and citric acid.

[0140] As an embodiment, the temperature of the acid treatment in step b) ranges from 30 to 80° C., and the time of the acid treatment ranges from 2 to 8 hours.

[0141] As an embodiment, the step c) is carried out in the steam atmosphere at a temperature ranging from 350 to 750° C. for a time ranging from 2 to 6 hours.

[0142] As an embodiment, the step d) is carried out at a temperature ranging from 30 to 90° C. for a time ranging from 2 to 6 hours.

[0143] As an embodiment, the product obtained in step e) is calcined in an air atmosphere at a temperature ranging from 400 to 750° C. for a time ranging from 4 to 6 hours.

[0144] As an embodiment, the method for producing methyl acetate by carbonylation of dimethyl ether comprises: feeding dimethyl ether and a feeding gas containing carbon monoxide into a reactor to contact with the catalyst described in any one of the above or the catalyst for the carbonylation of dimethyl ether to produce methyl acetate prepared according to any one of methods mentioned above, to produce methyl acetate under the condition that the reaction temperature ranges from 150 to 280° C., the reaction pressure ranges from 0.5 to 25.0 MPa, and the space velocity of dimethyl ether ranges from 0.2 to 4 h.sup.−1; and the molar ratio of dimethyl ether to carbon monoxide in the raw materials ranges from 0.1:1 to 30:1.

[0145] As an embodiment, the carbonylation is carried out under the condition that a reaction temperature ranges from 160 to 280° C., a reaction pressure ranges from 0.5 to 20.0 MPa, a weight hourly space velocity of the feeing dimethyl ether ranges from 0.05 to 5 h.sup.−1, and the molar ratio of carbon monoxide to dimethyl ether ranges from 0.1:1 to 20:1.

[0146] As an embodiment, the reaction temperature ranges from 170 to 260° C., the reaction pressure ranges from 1.0 to 15.0 MPa, the weight hourly space velocity of the feeding dimethyl ether ranges from 0.1 to 4.0 h.sup.−1, and the molar ratio of carbon monoxide to dimethyl ether ranges from 0.2:1 to 15:1.

[0147] As an embodiment, in addition to carbon monoxide, the feeding gas containing carbon monoxide may comprise any one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, methane and ethane; preferably, based on the total volume content of the feeding gas containing carbon monoxide, the volume content of carbon monoxide ranges from 15% to 100%, and the volume content of other gases such as one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, methane and ethane ranges from 0 to 85%.

Example 1

[0148] 100 g Na-MOR (Si/Al=15) molecular sieve was added into 1000 mL 0.5 mol/L phenyltrimethylammonium chloride aqueous solution, and then was treated at 80° C. for 4 hours to undergo phenyltrimethylammonium chloride exchange treatment. After subsequent filtering, washing and drying steps, the above phenyltrimethylammonium chloride exchange process was repeated 5 times. Then, the resulting sample was added into 1000 mL 0.5 mol/L oxalic acid aqueous solution, and was treated at 60° C. for 3 hours to undergo acid treatment. After subsequent filtering, washing and drying steps, the above acid treatment process was repeated 3 times. Then, the resulting sample was treated in a dry air atmosphere at 650° C. for 4 hours to undergo the high temperature treatment. Then the sample obtained by the high temperature treatment was treated in 500 mL 1 mol/L ammonium nitrate aqueous solution at 70° C. for 4 hours to undergo ammonium nitrate solution exchange treatment. After washing and drying steps, the ammonium nitrate solution exchange treatment process was repeated 3 times. Then, the sample obtained finally was calcined at 550° C. for 4 hours in an air atmosphere to obtain 1 # catalyst.

Example 2

[0149] The phenyltrimethylammonium chloride was replaced with tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, ethyl trimethyl ammonium chloride, diethyl dimethyl ammonium chloride, triethyl methyl ammonium chloride, benzyl trimethyl ammonium chloride and a mixture of the described ammonium chloride salts with equal weight, respectively. All the rest preparation procedures are the same as those in Example 1 to correspondingly prepare 2 # catalyst, 3 # catalyst, 4 # catalyst, 5 # catalyst, 6 # catalyst, 7 # catalyst, and 8 # catalyst.

Example 3

[0150] The concentration of phenyltrimethylammonium chloride was changed to 0.05 mol/L, 0.1 mol/L, 0.3 mol/L, and 1 mol/L respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 9 # catalyst, 10 # catalyst, 11 # catalyst, and 12 # catalyst.

Example 4

[0151] The oxalic acid was replaced with hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, and an equimolar mixture of the described acids, respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 13 # catalyst, 14 # catalyst, 15 # catalyst, 16 # catalyst, 17 # catalyst and 18 # catalyst.

Example 5

[0152] The dry air atmosphere was changed to an air atmosphere with a steam concentration of 10%, an air atmosphere with a steam concentration of 40%, and an atmosphere with a steam concentration of 100%, respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 19 # catalyst, 20 # catalyst, and 21 # catalyst.

Example 6

[0153] The dry air atmosphere was changed to an air atmosphere with a steam concentration of 20%, the corresponding temperature was changed to 350° C., 500° C., 600° C., 750° C., 800° C., 300° C., respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 22 # catalyst, 23 # catalyst, 24 # catalyst, 25 # catalyst, 26 # catalyst and 27 # catalyst.

Example 7

[0154] After Na-MOR was treated in phenyltrimethylammonium chloride aqueous solution, it was subjected to the following separate treatment respectively: (1) treatment in oxalic acid aqueous solution; (2) calcination treatment in dry air; (3) treatment in the air atmosphere with a steam concentration of 10%, wherein the particular treatment conditions were the same as those of the corresponding treatment in Example 1. Then, the resulting samples were treated by an ammonium nitrate aqueous solution respectively, and the conditions thereof were also the same as those of in Example 1. Finally, the 28 # catalyst, 29 # catalyst, and 30 # catalyst were obtained.

Example 8

[0155] The silicon to aluminum atomic ratio of the Na-MOR was changed to 6.5, 10, 20, 30, 50 respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 31 # catalyst, 32 # catalyst, 33 #catalyst, 34 # catalyst, and 35 # catalyst.

Example 9

[0156] The treatment temperature in the phenyltrimethylammonium chloride solution was changed to 20° C., 60° C. and 100° C. respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 36 # catalyst, 37 # catalyst and 38 # catalyst.

[0157] The treatment time in the phenyltrimethylammonium chloride solution was changed to 1 hour, 2 hours, 6 hours, and 10 hours respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 39 # catalyst, 40 # catalyst, 41 # catalyst and 42 #catalyst.

[0158] The number of times the treatment in the phenyltrimethylammonium chloride solution was changed to 2 and 8 respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 43 # catalyst and 44 # catalyst.

Example 10

[0159] The temperature of the acid treatment was changed to 30° C., 80° C. and 100° C. respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 45 # catalyst, 46 # catalyst and 47 #catalyst.

[0160] The time of the acid treatment was changed to 1 hour, 2 hours, 8 hours, and 10 hours respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 48 # catalyst, 49 # catalyst, 50 #catalyst and 51 # catalyst.

[0161] The number of times the acid treatment was changed to 2 and 10 respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 52 # catalyst and 53 # catalyst.

Example 11

[0162] The treatment time in the dry air atmosphere was changed to 1 hour, 2 hours, 6 hours, and 10 hours respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 54 # catalyst, 55 #catalyst, 56 # catalyst and 57 # catalyst.

Example 12

[0163] The treatment temperature in the ammonium nitrate aqueous solution was changed to 20° C., 30° C., 90° C., and 100° C. respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 58 # catalyst, 59 # catalyst, 60 # catalyst and 61 # catalyst.

[0164] The treatment time in the ammonium nitrate aqueous solution was changed to 1 hour, 2 hours, 6 hours, and 10 hours respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 62 # catalyst, 63 # catalyst, 64 # catalyst and 65 # catalyst.

Example 13

[0165] The calcination time was changed to 2 hours, 6 hours, and 8 hours respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 66 # catalyst, 67 # catalyst and 68 # catalyst.

[0166] The calcination temperature was changed to 300° C., 400° C., 750° C., and 800° C. respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 69 # catalyst, 70 # catalyst, 71 # catalyst and 72 # catalyst.

Example 14

[0167] The ammonium nitrate aqueous solution was replaced with an ammonium chloride aqueous solution, an ammonium sulfate aqueous solution, and an ammonium acetate aqueous solution, respectively. All the rest preparation procedures were the same as those in Example 1 to correspondingly prepare 73 # catalyst, 74 # catalyst and 75 # catalyst.

Example 15

[0168] The catalytic performance of the above-mentioned catalyst was investigated under the following conditions.

[0169] 10 g catalyst was loaded into a fixed bed reactor with inner diameter of 28 mm, in which the temperature was raised to 550° C. at a rate of 5° C./min under a nitrogen atmosphere, and was maintained 4 hours. Then the temperature was lowered to 220° C. under the nitrogen atmosphere. The pressure in the reaction system was increased to 5 MPa by using CO. The reaction raw materials were passed through the catalyst bed from top to bottom. The space velocity of the feeding dimethyl ether was 1.50 h.sup.−1. The molar ratio of carbon monoxide to dimethyl ether was 2:1, and the feeding gas containing carbon monoxide does not comprise other gases. Under the reaction temperature was 220° C. and the catalytic reaction ran 100 hours, the reaction results were shown in Table 1.

TABLE-US-00001 TABLE 1 Reaction results of different catalysts for carbonylation of dimethyl ether Space-time Conversion Selec- Selec- yield of rate of CO tivity tivity methyl dimethyl Conversion of methyl of other acetate ether rate acetate product (gMAc/ Catalyst (%) (%) (%) (%) (gcat .Math. h))  1# 71.5 35.8 99.9 0.1 1.72  2# 47.3 23.7 99.8 0.2 1.14  3# 52.1 26.1 99.5 0.5 1.25  4# 54.5 27.3 99.3 0.7 1.31  5# 57.5 28.8 99.6 0.4 1.38  6# 56.9 28.5 99.5 0.5 1.37  7# 75.9 38.0 99.6 0.4 1.82  8# 79.3 40.0 99.5 0.5 1.90  9# 24.2 12.1 92.6 7.4 0.54 10# 80.8 40.4 94.5 5.5 1.84 11# 80.9 40.5 99.9 0.1 1.95 12# 81.8 40.9 99.9 0.1 1.97 13# 68.5 34.3 98.3 1.7 1.62 14# 70.8 35.4 98.4 1.6 1.68 15# 52.1 26.1 97.5 2.5 1.23 16# 75.6 37.8 98.8 1.2 1.80 17# 63.8 31.9 90.8 9.2 1.40 18# 73.5 36.8 98.9 1.1 1.75 19# 75.8 37.8 94.5 5.5 1.73 20# 82.9 41.4 99.9 0.1 2.00 21# 41.8 20.9 99.9 0.1 1.01 22# 0.8 0.4 91.3 8.7 0.02 23# 2.3 1.2 92.3 7.7 0.05 24# 32.9 16.5 95.8 4.2 0.76 25# 62.8 31.4 98.6 1.4 1.49 26# 36.8 18.4 91.9 8.1 0.82 27# 16.8 8.4 91.9 8.1 0.37 28# 63.5 31.8 99.9 0.1 1.53 29# 47.5 23.8 99.9 0.1 1.15 30# 62.5 31.2 99.9 0.1 1.51 31# 36.8 18.4 98.7 1.3 0.88 32# 49.3 24.7 99.3 0.7 1.18 33# 62.3 31.5 99.4 0.6 1.49 34# 45.9 23.0 99.1 0.9 1.10 35# 35.9 18.0 99.1 0.9 0.86 36# 68.5 35.8 99.9 0.1 1.65 37# 69.5 34.8 99.4 0.6 1.67 38# 57.8 28.9 99.1 0.9 1.38 39# 71.2 35.6 99.1 0.9 1.70 40# 71.3 35.7 99.9 0.1 1.72 41# 71.4 35.7 99.4 0.6 1.71 42# 71.6 35.8 99.1 0.9 1.71 43# 48.4 24.2 99.1 0.9 1.16 44# 76.8 38.4 99.9 0.1 1.85 45# 68.9 34.5 99.4 0.6 1.65 46# 68.9 34.5 99.1 0.9 1.65 47# 37.8 18.9 99.1 0.9 0.90 48# 66.5 33.3 99.9 0.1 1.60 49# 67.8 33.9 99.4 0.6 1.63 50# 56.8 28.4 99.1 0.9 1.36 51# 32.8 16.4 99.1 0.9 0.78 52# 68.7 34.4 99.9 0.1 1.66 53# 56.8 28.4 99.4 0.6 1.36 54# 61.3 30.7 99.1 0.9 1.47 55# 63.8 31.9 99.1 0.9 1.53 56# 66.8 33.4 99.9 0.1 1.61 57# 45.9 23.0 99.4 0.6 1.10 58# 71.3 35.7 99.1 0.9 1.71 59# 71.5 35.8 99.1 0.9 1.71 60# 71.6 35.8 99.9 0.1 1.73 61# 71.8 35.9 99.4 0.6 1.72 62# 71.6 35.8 99.1 0.9 1.71 63# 71.5 35.8 99.1 0.9 1.71 64# 71.5 35.8 99.9 0.1 1.72 65# 71.6 35.8 99.4 0.6 1.72 66# 34.5 17.3 99.1 0.9 0.83 67# 71.3 35.7 99.1 0.9 1.71 68# 71.3 35.7 99.9 0.1 1.72 69# 5.6 2.8 99.4 0.6 0.13 70# 24.5 12.3 99.1 0.9 0.59 71# 10.2 5.1 99.1 0.9 0.24 72# 1.8 0.9 99.9 0.1 0.04 73# 70.5 35.3 99.9 0.1 1.70 74# 51.5 25.5 99.9 0.1 1.24 75# 74.5 37.2 99.9 0.1 1.79

[0170] Through the evaluation of the catalyst performance in the reaction system, it can be found that the side reaction activity can be selectively eliminated by the technical solution. A catalyst with high activity and high stability can be obtained without using pyridine pre-adsorption which would cause poisoning.

Example 16

[0171] Reaction results of carbonylation of dimethyl ether at different reaction temperatures 10 g 1 # catalyst was loaded into the fixed-bed reactor with an inner diameter of 28 mm. The temperature was raised to 550° C. at a rate of 5° C./min under a nitrogen atmosphere, and was maintained for 4 hours. Then, the temperature was lowered to the reaction temperature under the nitrogen atmosphere. The pressure in the reaction system was increased to 5 MPa by using CO. The reaction raw materials were passed through the catalyst bed from top to bottom. The weight hourly space velocity of the feeding dimethyl ether was 1.50 h.sup.−1. The molar ratio of carbon monoxide to dimethyl ether was 1:1, and the feeding gas containing carbon monoxide does not comprise other gases. The reaction temperature was 170° C., 200° C., 230° C., 240° C. and 260° C. respectively. The reaction results of the catalytic reaction running for 100 hours were shown in Table 2.

TABLE-US-00002 TABLE 2 Reaction results at different reaction temperatures The temperature at the inlet of the reactor 170 200 230 240 260 Conversion rate of dimethyl ether (%) 15.7 42.1 76.0 87.8 95.8 CO conversion rate (%) 15.7 42.1 76.0 87.8 95.8 Selectivity of methyl acetate (%) 97.8 99.7 99.5 99.1 96.3 Selectivity of other product (%) 2.2 0.3 0.5 0.9 3.7

Example 17

[0172] Reaction Results of the Carbonylation of Dimethyl Ether Under Different Reaction Pressures

[0173] 1 # catalyst was used in this example. The reaction pressures were 1, 6, 10, and 15 MPa, the reaction temperature was 220° C. and other conditions were the same as those in Example 16. Under the reaction ran for 100 hours, the reaction results were shown in Table 3.

TABLE-US-00003 TABLE 3 Reaction results under different reaction pressures Reaction Pressure (MPa) 1 6 10 15 Conversion rate of dimethyl ether (%) 18.3 59.3 62.8 72.3 CO conversion rate (%) 18.3 59.3 62.8 72.3 Selectivity of methyl acetate (%) 98.7 99.9 99.9 99.9 Selectivity of other product (%) 1.3 0.1 0.1 0.1

Example 18

[0174] Reaction results of the carbonylation of dimethyl ether at different space velocities of dimethyl ether.

[0175] 1 # catalyst was used in this example. The weight hourly space velocities of the feeding dimethyl ether were 0.35 h.sup.−1, 1 h.sup.−1, 2.5 h.sup.−1 and 4 h.sup.−1 respectively, the reaction temperature was 200° C., and other conditions were the same as those in Example 15. Under the reaction ran for 100 hours, the reaction results were shown in Table 4.

TABLE-US-00004 TABLE 4 Reaction results under different space velocities of dimethyl ether Space velocity of the feeding dimethyl ether (h.sup.−1) 0.35 1 2.5 4 Conversion rate of dimethyl ether (%) 92.5 63.39 25.26 14.8 CO conversion rate (%) 92.5 63.39 25.26 14.8 Selectivity of methyl acetate (%) 99.9 99.8 99.2 98.7 Selectivity of other product (%) 0.1 0.2 0.8 1.3

Example 19

[0176] Reaction results of carbonylation of dimethyl ether under different molar ratios of carbon monoxide to dimethyl ether.

[0177] 1 # catalyst was used in this example. The weight hourly space velocity of the feeding dimethyl ether was 1.5 h.sup.−1, and the molar ratios of carbon monoxide to dimethyl ether were 0.2:1, 0.5:1, 2:1, 4:1, 8:1 and 12:1 respectively. The reaction temperature was 210° C., and other conditions were the same as those in Example 16. Under the reaction ran for 100 hours, the reaction results were shown in Table 5.

TABLE-US-00005 TABLE 5 Reaction results under different molar ratios of carbon monoxide to dimethyl ether Molar ratio of carbon monoxide to dimethyl ether 12:1 8:1 4:1 2:1 0.5:1 0.2:1 Conversion rate of 8.13 10.7 18.45 32.9 90.6 97.5 carbon monoxide (%) Conversion rate of 97.5 85.6 73.8 65.8 45.32 19.5 dimethyl ether (%) Selectivity of 97.8 98.1 99.5 99.4 99.3 99.3 methyl acetate (%)

Example 20

[0178] Reaction results of carbonylation of dimethyl ether under the feeding gas containing carbon monoxide comprises inert gas.

[0179] 23 # catalyst was used in this example. The weight hourly space velocity of the feeding dimethyl ether was 0.5 h.sup.−1. The feeding gas containing carbon monoxide comprises inactive gas, the molar ratio of the feeding gas containing carbon monoxide to dimethyl ether was 4:1, the reaction temperature was 225° C., and other conditions were the same as those in Example 16. Under the reaction ran for 4000 hours the reaction results were shown in Table 6.

TABLE-US-00006 TABLE 6 Reaction results under the feeding gas containing carbon monoxide comprises inert gas Feeding gas containing carbon monoxide Conversion Conversion Volume rate of rate of Selectivity Volume content content dimethyl carbon of methyl of inactive of CO ether monoxide acetate gas (%) (%) (%) (%) (%) 85 (N.sub.2) 15 40.0 88.9 99.8 70 (N.sub.2) 30 75.2 92.8 99.8 20 (N.sub.2) 80 86.3 35.5 99.7 0 100 98.5 28.3 99.2 28(N.sub.2) + 56 82.7 51.5 99.5 3(CO.sub.2) + 5(Ar) + 8(H.sub.2)

[0180] The above examples are only illustrative, and do not limit the present application in any form. Any change or modification, made by the skilled in the art based on the technical content disclosed above, without departing from the spirit of the present application, is equivalent example and falls within the scope of the present application.