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 杨志强 于 2019-02-22 设计创作，主要内容包括：在催化剂和促进剂的存在下将甲醇脱水成二甲醚产物的方法,其中所述催化剂是至少一种铝硅酸盐沸石,且所述促进剂选自一种或更多种式I化合物：(I)其中X以及任何或所有的Y各自可独立地选自氢、卤素、取代或未取代的烃基取代基、或式-CHO、-CO-(2)R、-COR或-OR的化合物,其中R是氢或取代或未取代的烃基取代基,且其中将促进剂与甲醇的摩尔比保持在小于1。(I)。(A process for the dehydration of methanol to a product of dimethyl ether in the presence of a catalyst and a promoter, wherein the catalyst is at least one aluminosilicate zeolite and the promoter is selected from one or more compounds of formula I: (I) wherein X and any or all of Y may each be independently selected from hydrogen, halogen, substituted or unsubstituted hydrocarbyl substituents, or of the formula-CHO, -CO 2 R, -COR OR-OR, wherein R is hydrogen OR a substituted OR unsubstituted hydrocarbyl substituent, and wherein the molar ratio of promoter to methanol is maintained at less than 1.)

1. A process for the dehydration of methanol to a product of dimethyl ether in the presence of a catalyst and a promoter, wherein the catalyst is at least one aluminosilicate zeolite and the promoter is selected from one or more compounds of formula I:

(formula I)

Wherein X and any or all of Y may each be independently selected from hydrogen, halogen, substituted or unsubstituted hydrocarbyl substituents, or of the formula-CHO, -CO₂R, -COR OR-OR, wherein R is hydrogen OR a substituted OR unsubstituted hydrocarbyl substituent,

and wherein the molar ratio of promoter to methanol is maintained at less than 1.

2. The process of claim 1, wherein the catalyst is at least one aluminosilicate zeolite comprising at least one channel having a 10-membered ring.

3. The process of claim 2, wherein the catalyst is an aluminosilicate zeolite comprising at least one channel having a 10-membered ring.

4. The process of any one of claims 1-3, wherein the catalyst does not comprise any aluminosilicate zeolite comprising at least one channel having a 12-membered ring.

5. The process of any one of claims 1-4, wherein the zeolite is a H-type zeolite.

6. The process of any one of claims 1-5, wherein the zeolite is selected from the group consisting of framework-type CHA, TON, MTT, FER, MWW, MFI, MEL, MOR, BEA, and FAU.

7. The process of claim 6, wherein the zeolite is selected from framework-type FER, MWW, MFI or MEL.

8. The process of claim 7, wherein the zeolite is selected from ferrierite, PSH-3, ZSM-5, ZSM-11, ZSM-35 and MCM-22.

9. The method of any one of claims 1-8, wherein the zeolite is composited with a binder material.

10. The method of any one of claims 1-9, wherein X and/or any Y are independently selected from hydrogen, halogen, or a substituted or unsubstituted hydrocarbyl substituent comprising 1-11 carbon atoms.

11. The method of any one of claims 1-9, wherein X and/or any Y are independently selected from substituted or unsubstituted hydrocarbyl substituents.

12. The method of claim 11, wherein X and/or any Y are independently selected from unsubstituted hydrocarbyl substituents comprising 1-11 carbon atoms, preferably 1-9 carbon atoms, more preferably 1-7 carbon atoms, for example 1-6 carbon atoms.

13. The method of claim 11, wherein X and/or any Y are independently selected from substituted hydrocarbyl substituents comprising 1-11 carbon atoms, preferably 1-9 carbon atoms, more preferably 1-7 carbon atoms, for example 1-6 carbon atoms.

14. The method of claim 13, wherein X and/or any Y are independently a halogen-substituted hydrocarbyl group.

15. The method of any one of claims 1-14, wherein all Y are hydrogen.

16. A process according to any one of claims 1 to 15, wherein the promoter is maintained in an amount of at least 1 ppm relative to the total amount of methanol.

17. The process of any one of claims 1-16, wherein the molar ratio of promoter to methanol is maintained in the range of 0.00001: 1 to 0.2: 1.

18. The process of any one of claims 1-17, wherein the promoter is added to a dehydration process.

19. The method of any one of claims 1-18, wherein the promoter is generated in situ in a dehydration process.

20. The process of any one of claims 1-19, wherein the process is carried out at a temperature of 100-300 ℃.

21. The method of any one of claims 1-20, wherein the method is performed as a heterogeneous gas phase method.

22. A process for the dehydration of methanol to a dimethyl ether product in the presence of a catalyst, wherein the catalyst is at least one aluminosilicate zeolite, and wherein the catalyst has been impregnated with a promoter selected from one or more compounds of formula I prior to use in the dehydration process:

(formula I)

Wherein X and any or all of Y may each be independently selected from hydrogen, halogen, substituted or unsubstituted hydrocarbyl substituents, or of the formula-CHO, -CO₂R, -COR OR-OR, wherein R is hydrogen OR a substituted OR unsubstituted hydrocarbyl substituent.

23. A process for increasing the yield of dimethyl ether product in a process for the dehydration of methanol in the presence of a catalyst and a promoter, wherein the catalyst is at least one aluminosilicate zeolite and the promoter is selected from one or more compounds of formula I:

(formula I)

Wherein X and any or all of Y may each be independently selected from hydrogen, halogen, substituted or unsubstituted hydrocarbyl substituents, or of the formula-CHO, -CO₂R, -COR OR-OR, wherein R is hydrogen OR a substituted OR unsubstituted hydrocarbyl substituent,

and wherein the molar ratio of promoter to methanol is maintained at less than 1.

24. Use of a promoter in a process for the catalytic dehydration of methanol to dimethyl ether to increase the yield of dimethyl ether product, wherein the catalyst is at least one aluminosilicate zeolite and the promoter is selected from one or more compounds of formula I:

(formula I)

Wherein X and any or all of Y may each be independently selected from hydrogen, halogen, substituted or unsubstituted hydrocarbyl substituents, or of the formula-CHO, -CO₂R, -COR OR-OR, wherein R is hydrogen OR a substituted OR unsubstituted hydrocarbyl substituent,

and wherein the molar ratio of promoter to methanol is maintained at less than 1.

Examples

The zeolites and SAPOs used in the examples were utilized in their H form. SAPO-34, ferrierite, PSH-3, ZSM-5 mordenite, beta and Y catalysts were obtained from Zeolyst International, while SSZ-13 and ZSM-11 were obtained from ACS Materials. These catalysts were calcined in air at 500 ℃ for 4 hours prior to use. ZSM-22 and ZSM-23 were prepared according to literature procedures. Details of the zeolite are provided in table 1 below.

TABLE 1

Catalyst and process for preparing same	SAR*	Skeleton code	Maximum ring size	Structure (c)
					SAPO-34	n/a	CHA	8	3-D
SSZ-13	18	CHA	8	3-D
					ZSM-22	61	TON	10	1-D
ZSM-23	91	MTT	10	1-D
					Ferrierite and process for preparing same	20	FER	10	2-D
PSH-3	21	MWW	10	2-D
					ZSM-5 (23)	23	MFI	10	3-D
ZSM-5 (50)	50	MFI	10	3-D
					ZSM-5 (280)	280	MFI	10	3-D
ZSM-11	53	MEL	10	3-D
					Mordenite zeolite	20	MOR	12	1-D
Zeolite beta	25	BEA	12	3-D
					Zeolite Y	30	FAU	12	3-D

SAR represents the silica to alumina molar ratio of the zeolite.

-1-D, 2-D and 3-D show one-, two-and three-dimensional zeolite framework structures, respectively.

The methanol dehydration reaction of the example was carried out using the overall reaction method and apparatus described below.

Total reaction method and apparatus

A 16-pass parallel fixed bed stainless steel reactor system was used for the methanol dehydration reaction. Each reactor (10 mm ID) was charged with a catalyst bed (0.168 g catalyst diluted with 0.337g silica) mixed with a silica diluent. The catalyst and silica each had a particle size of 450 and 900 microns in diameter. The mixture was loaded on top of a 6.5 cm deep bed of inert material (quartz sand). The reactor space (volume) above the catalyst bed was also filled with quartz sand.

Each reactor was maintained at a temperature of 150 ℃ and a total pressure of 1100 kPa throughout the reaction. A gaseous feed comprising 10 mole% methanol and an inert gas is introduced into the reactor and the feed is flowed through the catalyst bed for at least 24 hours before the promoter compound is added to the feed. The methanol feed rate was kept constant at 45 mmol/h throughout the reaction. The effluent streams from the reactors were cooled to 5 ℃ in a condenser and the gas phase from the condenser was periodically analyzed by on-line gas chromatography to determine the yield of dimethyl ether product. Different promoters were added to the feed and the yield of dimethyl ether was determined. While introducing the promoter, the flow rate of the inert gas was adjusted to maintain a constant GHSV for the combined MeOH, promoter, and inert gas feeds.

Example 1

This example demonstrates the effect of 0.1 mole percent simultaneous feed of benzaldehyde relative to the methanol feed on methanol dehydration reactions using various catalysts. The overall reaction method and apparatus described above was used to perform the methanol dehydration reaction. The observed space time yields of dimethyl ether product are provided in table 2 below.

TABLE 2

Some catalysts have moderate stability during introduction of the catalyst co-feed, and the percentage reduction in DME STY during the 12 hour period during co-feed addition was greater than 5%. DME STY without accelerator was taken just before accelerator addition. DME STY co-fed over a catalyst with good stability represents the DME yield observed during co-feeding. For catalysts with moderate stability, DME STY with co-feed was the maximum DME yield observed during co-feed.

Example 2

This example demonstrates the effect of benzaldehyde concentration (% by mole relative to methanol feed) on methanol dehydration reactions using one-, two-, and three-dimensional zeolite catalysts, with the largest ring being 10-membered. The overall reaction method and apparatus described above was used to perform the methanol dehydration reaction. The observed space time yields of dimethyl ether product are provided in table 3 below.

Table 3.

DME STY without accelerator was taken just prior to the first addition of accelerator. DME STY with co-feed represents the DME yield observed during co-feed.

Example 3

This example demonstrates the effect of feed benzaldehyde and derivatives (0.1 mole% relative to the methanol feed) on the methanol dehydration reaction using a three-dimensional 10-membered ring zeolite catalyst, ZSM-5. The overall reaction method and apparatus described above was used to perform the methanol dehydration reaction. The observed space time yields of dimethyl ether product are provided in table 4 below.

Table 4.

DME STY without accelerator was taken just prior to the first addition of accelerator. DME STY with co-feed represents the DME yield observed during co-feed.