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：一种在催化剂和助催化剂的存在下将甲醇脱水为二甲醚产物的方法,其中所述催化剂是至少一种硅铝酸盐沸石,其中：-硅铝酸盐沸石选自：(i)具有2维骨架结构的沸石,其包含至少一个具有10元环的通道,并且具有至少4.8埃的最大自由球直径；(ii)具有3维骨架结构的沸石,其包含至少一个具有10元环的通道；或(iii)包含至少一个具有12元环的通道的沸石；-助催化剂选自式I的一种或多种化合物：(I)(I)其中Y选自C-(1)-C-(4)烃基取代基,并且其中每个X和任何或所有Z可独立地选自氢、卤素、取代或未取代的烃基取代基、或者式-CHO、-CO-(2)R、-COR或-OR的基团,其中R是氢或者取代或未取代的烃基取代基,并且其中助催化剂与甲醇的摩尔比保持在小于1。(A process for the dehydration of methanol to a dimethyl ether product in the presence of a catalyst and a promoter, wherein the catalyst is at least one aluminosilicate zeolite, wherein: -the aluminosilicate zeolite is selected from: (i) a zeolite having a 2-dimensional framework structure comprising at least one channel having 10-membered rings and having a maximum free sphere diameter of at least 4.8 angstroms; (ii) a zeolite having a 3-dimensional framework structure comprising at least one channel having 10-membered rings; or (iii) a zeolite comprising at least one channel having a 12-membered ring; -the cocatalyst is selected from one or more compounds of formula I: (I) (I) wherein Y is selected from C 1 ‑C 4 A hydrocarbyl substituent, and wherein each X and any or all Z can be independently selected from hydrogen, halogen, a substituted or unsubstituted hydrocarbyl substituent, or a compound 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 cocatalyst to methanol is maintained at less than 1.)

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

-said aluminosilicate zeolite is selected from: (i) a zeolite having a 2-dimensional framework structure comprising at least one channel having 10-membered rings and having a maximum free sphere diameter of at least 4.8 angstroms; (ii) a zeolite having a 3-dimensional framework structure comprising at least one channel having 10-membered rings; or (iii) a zeolite comprising at least one channel having a 12-membered ring;

-said cocatalyst is selected from one or more compounds of formula I:

wherein Y is selected from C₁-C₄A hydrocarbyl substituent, and wherein each X and any or all Z can be independently selected from hydrogen, halogen, a substituted or unsubstituted hydrocarbyl substituent, or a compound 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 said co-catalyst to said methanol is maintained at less than 1.

2. The process of claim 1 wherein the zeolite is an H-type zeolite.

3. A process according to claim 1 or claim 2 wherein the zeolite is selected from framework types MWW, MFS, TER, MFI and MEL.

4. A process according to claim 1 or claim 2, wherein the zeolite is selected from framework type MWW, MEL, MFI, BEA, MOR, or FAU.

5. A process according to claim 1 or claim 2 wherein the zeolite is selected from zeolite Y, mordenite, zeolite beta, ZSM-5, ZSM-11, PHS-3 and MCM-22.

6. A process according to any one of claims 1 to 5 wherein the zeolite is composited with a binder material.

7. The process according to any one of claims 1 to 6, wherein Y is selected from methyl, ethyl, n-propyl or n-butyl, preferably selected from methyl or ethyl, such as methyl.

8. The method of any one of claims 1 to 7, wherein X and/or any Z are independently selected from hydrogen, halogen, or a substituted or unsubstituted hydrocarbyl substituent comprising 1 to 11 carbon atoms.

9. The method of any one of claims 1 to 7, wherein X and/or any Z are independently selected from substituted or unsubstituted hydrocarbyl substituents.

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

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

12. The method of claim 11, wherein X and/or any Z are independently halogen-substituted hydrocarbyl groups.

13. The method of any one of claims 1 to 12, wherein all Z are hydrogen.

14. The process according to any one of claims 1 to 13, wherein the total amount of the co-catalyst is maintained in an amount of at least 1ppm relative to methanol.

15. The process of any one of claims 1 to 14, wherein the molar ratio of the cocatalyst to the methanol is maintained at 0.00001:1 to 0.2: 1.

16. The process of any one of claims 1 to 15, wherein the co-catalyst is added to the dehydration process.

17. The process of any one of claims 1 to 16, wherein the co-catalyst is generated in situ in the dehydration process.

18. The process of any one of claims 1 to 17, wherein the process is carried out at a temperature of from 100 ℃ to 300 ℃.

19. The process of any one of claims 1 to 18, wherein the process is carried out as a heterogeneous gas phase process.

20. 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, wherein:

-said aluminosilicate zeolite is selected from: (i) a zeolite having a 2-dimensional framework structure comprising at least one channel having 10-membered rings and having a maximum free sphere diameter of at least 4.8 angstroms; (ii) a zeolite having a 3-dimensional framework structure comprising at least one channel having 10-membered rings; or (iii) a zeolite comprising at least one channel having a 12-membered ring;

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:

wherein Y is selected from C₁-C₄A hydrocarbyl substituent, and wherein each X and any or all Z can be independently selected from hydrogen, halogen, a substituted or unsubstituted hydrocarbyl substituent, or a compound of the formula-CHO, -CO₂R, -COR, OR-OR, wherein R is hydrogen OR a substituted OR unsubstituted hydrocarbyl substituent.

21. A process for improving the productivity 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, wherein:

-said aluminosilicate zeolite is selected from: (i) a zeolite having a 2-dimensional framework structure comprising at least one channel having 10-membered rings and having a maximum free sphere diameter of at least 4.8 angstroms; (ii) a zeolite having a 3-dimensional framework structure comprising at least one channel having 10-membered rings; or (iii) a zeolite comprising at least one channel having a 12-membered ring;

-said cocatalyst is selected from one or more compounds of formula I:

wherein Y is selected from C₁-C₄A hydrocarbyl substituent, and wherein each X and any or all Z can be independently selected from hydrogen, halogen, a substituted or unsubstituted hydrocarbyl substituent, or a compound 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 said co-catalyst to said methanol is maintained at less than 1.

22. Use of a promoter in a process for the catalytic dehydration of methanol to dimethyl ether for improving the productivity of the dimethyl ether product, wherein the catalyst is at least one aluminosilicate zeolite, wherein:

-said aluminosilicate zeolite is selected from: (i) a zeolite having a 2-dimensional framework structure comprising at least one channel having 10-membered rings and having a maximum free sphere diameter of at least 4.8 angstroms; (ii) a zeolite having a 3-dimensional framework structure comprising at least one channel having 10-membered rings; or (iii) a zeolite comprising at least one channel having a 12-membered ring;

-and the cocatalyst is selected from one or more compounds of formula I:

wherein Y is selected from C₁-C₄A hydrocarbyl substituent, and wherein each X and any or all Z can be independently selected from hydrogen, halogen, a substituted or unsubstituted hydrocarbyl substituent, or a compound 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 said co-catalyst to said methanol is maintained at less than 1.

Examples

The zeolites and SAPOs used in the examples were used in their H-form. SAPO-34, ferrierite, PSH-3, ZSM-5 mordenite, beta and Y catalysts were obtained from Zeolyst International, and 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 represent 1-dimensional, 2-dimensional and 3-dimensional zeolite framework structures, respectively.

The methanol dehydration reaction of the examples was carried out using the following general reaction method and apparatus.

General reaction method and device

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

Throughout the reaction, each reactor was maintained at a temperature of 150 ℃ and a total pressure of 1100 kPa. A gaseous feed comprising 10 mole% methanol and an inert gas is introduced into the reactor and allowed to flow through the catalyst bed for at least 24 hours, after which a promoter compound is added to the feed. The methanol feed rate was kept constant at 45 mmol h throughout the reaction^-1. The effluent stream from each reactor was 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. Will be different to helpThe catalyst was added to the feed and the dimethyl ether yield was measured. When the promoter is introduced, the flow rate of the inert gas is adjusted to maintain a constant GHSV for the combined MeOH, promoter, and inert gas feed.

Example 1

This example demonstrates the effect of acetophenone co-feed (0.1 mole% relative to methanol fed) on methanol dehydration reactions with various catalysts. The methanol dehydration reaction is carried out using the above general reaction method and apparatus. The space-time yields observed for the 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 of DME STY decreased by more than 5% over a 12 hour period during the addition of the co-feed. DME STY without cocatalyst was withdrawn immediately before the cocatalyst addition. DME STY with co-feed (with catalyst of good stability) represents the DME productivity observed during the co-feed period. For catalysts with moderate stability, DME STY with co-feed was the maximum DME productivity observed during the co-feed period.

Example 2

This example demonstrates the effect of feeding acetophenone and derivatives (0.1 mole% relative to the methanol fed) on the methanol dehydration reaction. The methanol dehydration reaction was carried out using the above general reaction method and apparatus. The space-time yields observed for the dimethyl ether product are provided in table 3 below.

TABLE 3

。

DME STY without cocatalyst was withdrawn immediately before the first addition of cocatalyst. DME STY with co-feed represents the DME productivity observed during the co-feed period.