阅读说明：本技术 方法 (Method ) 是由 B·J·丹尼斯-史密瑟斯 J·G·森利 F·杰克逊 于 2020-02-14 设计创作，主要内容包括：在催化剂和助催化剂存在下用于将C-(2)+醇脱水为醚产物的方法,其中所述催化剂为至少一种硅铝酸盐沸石催化剂,所述硅铝酸盐沸石催化剂为具有3维骨架结构的中孔沸石,并且所述助催化剂为一种或多种有机羰基化合物或其衍生物,并且其中助催化剂与C-(2)+醇的摩尔比保持在小于1。(In the presence of a catalyst and a cocatalyst 2 A process for the dehydration of an alcohol to an ether product wherein the catalyst is at least one aluminosilicate zeolite catalyst which is a mesoporous zeolite having a 3-dimensional framework structure and the promoter is one or more organic carbonyl compounds or derivatives thereof and wherein the promoter is reacted with C 2 The molar ratio of + alcohol is kept below 1.)

1. In the presence of a catalyst and a cocatalyst₂A process for the dehydration of an alcohol to an ether product wherein the catalyst is at least one aluminosilicate zeolite catalyst which is a mesoporous zeolite having a 3-dimensional framework structure and the promoter is one or more organic carbonyl compounds or derivatives thereof and wherein the promoter is reacted with C₂The molar ratio of + alcohol is kept below 1.

2. The method of claim 1, wherein the co-catalyst is one or more compounds selected from the group consisting of:

(i) formula R^A1Aldehyde of CHO (formula I), R^A1CHO, wherein R^A1Is hydrogen, C₁-C₁₁Alkyl, C wherein 3 or more carbon atoms are bonded to form a ring₃-C₁₁An alkyl group, or an optionally substituted aromatic group;

(ii) acetal derivatives of aldehydes of formula I;

(iii) formula R^K1COR^K2(formula II) ketones, wherein R^K1And R^K2Are the same or different and are each C₁-C₁₁Alkyl, C wherein 3 or more carbon atoms are bonded to form a ring₃-C₁₁Alkyl, or optionally substituted aromatic group, and furthermore R^K1And R^K2Together with the carbonyl carbon atom to which they are bonded may form a cyclic ketone;

(iv) a ketal derivative of a ketone of formula II;

(v) formula R^E1CO₂R^E2(ester of formula III) wherein R^E1And R^E2Are the same or different and are each C₁-C₁₁Alkyl, C wherein 3 or more carbon atoms are bonded to form a ring₃-C₁₁An alkyl group, or an optionally substituted aromatic group; and

(vi) formula R^E1(CO₂R^E2)₂(of the formula IV) wherein R^E1And R^E2The same or differentAnd are each C₁-C₁₁Alkyl, C wherein 3 or more carbon atoms are bonded to form a ring₃-C₁₁An alkyl group, or an optionally substituted aromatic group.

3. The process of claim 1 or claim 2 wherein the aluminosilicate zeolite catalyst is a medium pore zeolite having a 3-dimensional framework structure.

4. The process of claim 3, wherein the aluminosilicate zeolite catalyst is selected from framework types MFI and MEL.

5. The process of claim 4, wherein the aluminosilicate zeolite catalyst is selected from ZSM-5 or ZSM-11.

6. The process of any one of claims 1-5, wherein the aluminosilicate zeolite is composited with a binder material.

7. The method of any one of claims 1-6, wherein the C to be dehydrated₂+ an alcohol containing C₂-C₆Alkyl and hydroxyl primary alcohols.

8. The method of any one of claims 1-7, wherein the C to be dehydrated₂+ alcohol is one or more alcohols selected from ethanol, n-propanol and n-butanol.

9. The method of any one of claims 1-8, wherein the C to be dehydrated₂+ alcohol being a single C₂+ alcohol species.

10. The method of any one of claims 1-9, wherein the cocatalyst is reacted with C₂The molar ratio of + alcohol is maintained in the range of 0.00001:1 to 0.2: 1.

11. The process of any one of claims 1-10, wherein the co-catalyst is generated in situ in the dehydration process.

12. The process of any one of claims 1-11, wherein the process is carried out at a temperature of 100 ℃ to 300 ℃.

13. The process of any one of claims 1-12, wherein the process is carried out as a heterogeneous gas phase process.

14. In the presence of a catalyst and a cocatalyst₂A process for improving the ether product productivity in a process for dehydration of an alcohol wherein the catalyst is at least one aluminosilicate zeolite catalyst which is a mesoporous zeolite having a 3-dimensional framework structure and the co-catalyst is one or more organic carbonyl compounds or derivatives thereof and wherein the co-catalyst is with C₂The molar ratio of + alcohol is kept below 1.

15. The cocatalyst is used for reacting C₂Use in a process for the catalytic dehydration of an alcohol to an ether product to improve the productivity of the ether product, wherein the catalyst is at least one aluminosilicate zeolite catalyst which is a mesoporous zeolite having a 3-dimensional framework structure and the promoter is one or more organic carbonyl compounds or derivatives thereof, and wherein the promoter is in combination with C₂The molar ratio of + alcohol is kept below 1.

16. In the presence of a catalyst for the reaction of C₂A process for the dehydration of an alcohol to an ether product, wherein the catalyst is at least one aluminosilicate zeolite catalyst which is a mesoporous zeolite having a 3-dimensional framework structure, and wherein the catalyst has been impregnated with a co-catalyst which is an organic carbonyl compound or derivative thereof prior to use of the catalyst in the dehydration process.

Examples

The ZSM-5 catalyst used in examples 1-11 was obtained from Zeolyst International in the ammonium form. The ZSM-11 catalyst used in example 12 was obtained from ACS Material in ammonium form. The ZSM-5 and ZSM-11 catalysts were used in their H form after conversion by calcination in air at 500 ℃.

General reaction method and apparatus I

The ethanol dehydration reaction was carried out using a 16-pass parallel fixed bed stainless steel reactor system. Each reactor (2 mm internal diameter) was heated to maintain a temperature of 150 ℃ or 200 ℃. Each reactor packed 25 mg of catalyst bed (particle size scale 100 and 200 micron diameter) supported on top of a bed of inert material (corundum) 6cm deep. The reactor volume above the catalyst was also filled with silicon carbide. The reactor was installed in a downflow configuration.

Throughout the reaction, each reactor was maintained at a temperature of 150 ℃ and a total pressure of 1100 kPa. The gaseous feed comprising 10 mol% ethanol and inert gas was fed at 13 mmol h^-1Is introduced into the reactor and is allowed to flow through the catalyst bed for a period of at least 24 hours. Various concentrations of co-catalyst were added to the feed to determine the effect on ether yield. While the cocatalyst was added, the flow rate of the inert gas was reduced to maintain a constant gas hourly space velocity and the ethanol flow rate was maintained at 13 mmol h^-1。

The effluent stream from each reactor was diluted with inert gas (nitrogen) and periodically analyzed by on-line gas chromatography to determine the yield of diethyl ether product.

General reaction method and apparatus II

The n-hexanol dehydration reaction was performed using a single pass fixed bed stainless steel reactor system. The reactor encapsulates 350 mg of a ZSM-5 catalyst bed having a silica to alumina ratio (SAR) of 80. The catalyst had a particle size fraction of 250-500 micron diameter. The catalyst was supported in a front bed of less than 170 mg of inert material (silicon carbide) and a back bed of more than 600 mg of inert material (silicon carbide).

Throughout the reaction, the reactor was maintained at a temperature of 160 ℃ and a pressure of 20 barg.

Example 1

This example demonstrates the effect of ethyl formate on the dehydration of ethanol over different ZSM-5 catalysts at a reaction temperature of 150 ℃.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 150 ℃. The observed space-time yields of the ether product are provided in table 1.

TABLE 1

SAR indicates the silica to alumina molar ratio of the zeolite

The results in table 1 show that the use of ethyl formate enhances the space-time yield of diethyl ether.

Example 2

This example demonstrates the effect of ethyl formate on the dehydration of ethanol over different ZSM-5 catalysts at a reaction temperature of 200 ℃.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 200 ℃. The observed space-time yields of the ether product are provided in table 2.

TABLE 2

SAR indicates the silica to alumina molar ratio of the zeolite

The results in table 2 show that the use of ethyl formate enhances the space-time yield of diethyl ether.

Example 3

This example demonstrates the effect of ethyl n-butyrate on the dehydration of ethanol over a different ZSM-5 catalyst.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 150 ℃. The observed space-time yields of the ether product are provided in table 3.

TABLE 3

SAR indicates the silica to alumina molar ratio of the zeolite

The results in Table 3 show that the use of ethyl n-butyrate enhances the space-time yield of diethyl ether.

Example 4

This example demonstrates the effect of dimethyl adipate on the dehydration reaction of ethanol over a different ZSM-5 catalyst.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 150 ℃. The observed space-time yields of the ether product are provided in table 4.

TABLE 4

SAR indicates the silica to alumina molar ratio of the zeolite

The results in table 4 show that the use of dimethyl adipate enhances the space-time yield of diethyl ether.

Example 5

This example demonstrates the effect of 5-nonanone on the dehydration of ethanol over a different ZSM-5 catalyst.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 150 ℃. The observed space-time yields of the ether product are provided in table 5.

TABLE 5

SAR indicates the silica to alumina molar ratio of the zeolite

The results in Table 5 show that the use of 5-nonanone enhances the space-time yield of diethyl ether.

Example 6

This example demonstrates the effect of acetone on ethanol dehydration over different ZSM-5 catalysts.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 150 ℃. The observed space-time yields of the ether product are provided in table 6.

TABLE 6

SAR indicates the silica to alumina molar ratio of the zeolite

The results in table 6 show that the use of acetone enhances the space-time yield of diethyl ether.

Example 7

This example demonstrates the effect of 1, 1-diethoxyethane on the dehydration reaction of ethanol over a different ZSM-5 catalyst.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 150 ℃. The observed space-time yields of the ether product are provided in table 7.

TABLE 7

SAR indicates the silica to alumina molar ratio of the zeolite

The results in Table 7 show that the use of 1, 1-diethoxyethane enhances the space-time yield of diethyl ether.

Example 8

This example demonstrates the effect of benzaldehyde on the dehydration of ethanol over a different ZSM-5 catalyst.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 150 ℃. The observed space-time yields of the ether product are provided in table 8.

TABLE 8

SAR indicates the silica to alumina molar ratio of the zeolite

The results in table 8 show that the use of benzaldehyde enhances the space-time yield of diethyl ether.

Example 9

This example demonstrates the effect of n-butyraldehyde on the ethanol dehydration reaction over different ZSM-5 catalysts.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 150 ℃. The observed space-time yields of the ether product are provided in table 9.

TABLE 9

SAR indicates the silica to alumina molar ratio of the zeolite

The results in Table 9 show that the use of n-butyraldehyde enhances the space-time yield of diethyl ether.

Example 10

This example demonstrates the effect of benzaldehyde on hexanol dehydration over a ZSM-5 catalyst.

The n-hexanol dehydration reaction was carried out using the general reaction method and apparatus II described above. At a rate of 0.08 ml min^-1The liquid feed was introduced into the reactor at a constant flow rate to achieve 10 mL_cat ^-1 h^-1Liquid Hourly Space Velocity (LHSV). The reactor was installed in a downflow configuration. The liquid samples were analyzed by off-line Gas Chromatography (GC) at 3.5 h production time (ToS).

At 3.5 h ToS, the liquid feed became a liquid feed consisting of 1 mol% benzaldehyde (1.06 g) in n-hexanol (101.14 g); all other variables remain the same. At 5.5 h ToS, the liquid samples were analyzed by off-line GC. The observed space time yields of dihexyl ether and hexene products are provided in table 10.

Watch 10

The results in table 10 show that the use of benzaldehyde enhances the space-time yield of dihexyl ether.

Example 11

This example demonstrates the effect of 4-trifluorobenzaldehyde on the dehydration of hexanol over a ZSM-5 catalyst.

The n-hexanol dehydration reaction was carried out using the general reaction method and apparatus II described above. At a rate of 0.08 ml min^-1The liquid feed was introduced into the reactor at a constant flow rate to achieve 10 mL_cat ^-1 h^-1Liquid Hourly Space Velocity (LHSV). The reactor was installed in a downflow configuration. The liquid samples were analyzed by off-line Gas Chromatography (GC) at 4.25 h production time (ToS).

At 4.25 h ToS, the liquid feed became a liquid feed consisting of 1 mole% 4-fluorobenzaldehyde (1.746 g) in n-hexanol (101.14 g); all other variables remain the same. At 6.25 h ToS, the liquid samples were analyzed by off-line GC. The observed space time yields of dihexyl ether and hexene products are provided in table 11.

TABLE 11

The results in table 11 show that the use of 4-trifluorobenzaldehyde enhances the space time yield of dihexyl ether.

Example 12

This example demonstrates the effect of ethyl formate on the dehydration of ethanol over ZSM-5 and ZSM-11 catalysts at a reaction temperature of 150 ℃.

The ethanol dehydration reaction was carried out using the general reaction method and apparatus I described above at a reaction temperature of 150 ℃. The observed space-time yields of the ether product are provided in table 12.

TABLE 12

SAR indicates the silica to alumina molar ratio of the zeolite

The results in table 12 show that the use of ethyl formate enhances the space-time yield of diethyl ether.