CA1130820A - Preparation of olefins from crude methanol - Google Patents
Preparation of olefins from crude methanolInfo
- Publication number
- CA1130820A CA1130820A CA346,044A CA346044A CA1130820A CA 1130820 A CA1130820 A CA 1130820A CA 346044 A CA346044 A CA 346044A CA 1130820 A CA1130820 A CA 1130820A
- Authority
- CA
- Canada
- Prior art keywords
- olefins
- crude methanol
- zeolite
- dimethyl ether
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
O.Z. 0050/033725 Abstract of the disclosure: A process for the prepara-tion of C2-C5-olefins from crude methanol and/or dimethyl ether by catalytic conversion at an elevated temperature in the presence of a zeolite-containing catalyst, wherein the zeolite has been prepared from technical-grade water-glass with the aid of hexamethylenediamine, without addition of a metal salt. The raw material used for the process is undiluted crude methanol and/or dimethyl ether.
Description
- ~13~820 Preparation of olefins from crude methanol Recently, endeavors tQ use methanol for the pre-paration of olefins have aroused increasing interest.
Methanol can easily be prepared from coal by means of well-established technologies, via coal gasification and the preparation of synthesis gas. Should it prove possible to convert methanol economically to lower olefins, the further conversion processes which are at present conventionally used ' in the chemical industry could be retained if coal was used as the raw material. Hence, processes have been developed in recent years for preparing olefins from methanol and/or dimethyl ether. Such a process is described, for example, in German Laid-Open Application DOS 2,615,150 published on October 21, 1976. The catalyst used in this process is the aluminosilicate zeolite ZSM-5, which in fact is a catalyst foraromatization reactions. However, the reaction can be directed towards the formation of olefins by taking various measures, in particular by reducing the residence time. Other measures which favor olefin formation are the dilution of methanol or of dimethyl ether with inert gases,~
or the dilution of the catalyst with binders. Experience shows that high olefin yields can only be achieved if the methanol and/or dimethyl ether is very greatly diluted with inert gases. Hence, the process is uneconomical.
Other processes which have been disclosed have the dis-s advantage that the catalyst throughput is low, and that the catalyst carbonizes rapidly. There is therefore ~B ~
113~)820
Methanol can easily be prepared from coal by means of well-established technologies, via coal gasification and the preparation of synthesis gas. Should it prove possible to convert methanol economically to lower olefins, the further conversion processes which are at present conventionally used ' in the chemical industry could be retained if coal was used as the raw material. Hence, processes have been developed in recent years for preparing olefins from methanol and/or dimethyl ether. Such a process is described, for example, in German Laid-Open Application DOS 2,615,150 published on October 21, 1976. The catalyst used in this process is the aluminosilicate zeolite ZSM-5, which in fact is a catalyst foraromatization reactions. However, the reaction can be directed towards the formation of olefins by taking various measures, in particular by reducing the residence time. Other measures which favor olefin formation are the dilution of methanol or of dimethyl ether with inert gases,~
or the dilution of the catalyst with binders. Experience shows that high olefin yields can only be achieved if the methanol and/or dimethyl ether is very greatly diluted with inert gases. Hence, the process is uneconomical.
Other processes which have been disclosed have the dis-s advantage that the catalyst throughput is low, and that the catalyst carbonizes rapidly. There is therefore ~B ~
113~)820
- 2 - O.Z. 0050/03372s great interest in a simple process which permits complete conversion of crude methanol and/or dimethyl ether into hydrocarbons consisting in the maln of C2-C5-olefins.
We have found that C2-C5-olefins are obtained in a simple manner from crude methanol and/or dimethyl ether by catalytic conversion at an elevated temperature in the presence of a zeolite-containing catalyst, if the zeolite has been prepared from technical-grade waterglass with the aid of hexamethylenediamine, without addition of a metal salt.
In a preferred embodiment, crude methanol is re-acted over the zeolite catalyst according to the invention at between atmospheric pressure and about 30 bar, and at from 300 to 700C, preferably from 400 to 650C. Crude methanol for the purposes of the invention means methanol containing up to about 30% by weight of water, ie. the product formed in the synthesis of methanol. Other lower alcohols may also be present in the crude methanol.
The catalyst throughput, expressed in g of methanol and/or dimethyl ether/g of catalyst.h is advantageously selected to be such that the latter compounds are converted as completely as possible, thereby eliminating separation and recycling problems. In general, therefore, the throughput is of the order of from 2 to 50, preferably from 5 to 15, g/g of zeolite.h. However, it is poss-ible to select higher throughputs, or to dilute the starting materials with an inert gas, for example nitro-gen, without adverse effect on the composition of the hydrocarbon mixture formed. At the same time it is .
.
113~3ZO
a particular advantage of the invention that the conver-sion of crude methanol or dimethyl ether to C2-C5-olefins can be carried out without a diluent.
The zeolites described in German Patent Applica-tion P 28 31 344.0 published on March 15, 1979 can be used as zeolite catalysts. These catalysts are distinguished by particularly high activity and selectivity.
The example which follows illustrates the invention.
EXAMPLE
Preearation of the zeolite:
.
Three solutions are prepared. Solution 1 con-sists of 326.6 g of technical-grade waterglass (contain-ing 8~ by weight of Na2O and 28% by weight of SiO2~ and 352 g of water.
Solution 2 consists of 300 g of a 50 per cent strength aqueous hexamethylenediamine solution and solution 3 consists of 508.3 g of water and 24.7 g of 96 per cent strength sulfuric acid. Solutions 2 and 3 are successively added to solution 1, whilst stirring. The resulting solution is heated for 5 days at 150C under its autogenous pressure in a steel autoclave. The resulting product is filtered off, washed and dried at 100C.
Preparation of the catalyst from the zeolite:
The zeolite obtained is mixed with boehmite in a ratio such that the zeolite content in the mixture is about 65% by weight, based on anhydrous and amine-free ~ product. The mixture is then ;~
. ~
~, .
~ ` 113~8ZO
_ 4 _ o.Z. 0050/033725 - kneaded with water and extruded to form strands of 1 mm diameter. These are calcined at 540C, then treated with an aqueous ammonium sulfate solution at 80C, filtered off, washed and dried Conversion of crude methanol to olefins:
~ ~ .
20 g (dry weight) of this catalyst are introduced into a flow-tube reactor of 20 mm diameter and the acti-vity in respect of the conversion of crude methanol to olefins is tested. The reaction conditions and experi-mental results are shown in the Table which follows.
The reaction products wereanalyzed by gas chromatography.
Entry temperature 400C
Temperature rise 200C
Pressure 1.3 bar Throughput 170 g of crude methanol/h ; Total throughput 1,000 g Conversion 95-100%
The reaction product obtained has the following composition:
Liquid hydrocarbons, 18% by weight, based on CH2 employed Gaseous hydrocarbons, 82% by weight, based on CH2 employed, and containing the following:
Olefins C2 20% by volume C3 43% " ~I
C4 16% " "
Cs 5% "
Paraffins Cl 4 " "
C2 traces C3 2% by volume - C4 10% " "
We have found that C2-C5-olefins are obtained in a simple manner from crude methanol and/or dimethyl ether by catalytic conversion at an elevated temperature in the presence of a zeolite-containing catalyst, if the zeolite has been prepared from technical-grade waterglass with the aid of hexamethylenediamine, without addition of a metal salt.
In a preferred embodiment, crude methanol is re-acted over the zeolite catalyst according to the invention at between atmospheric pressure and about 30 bar, and at from 300 to 700C, preferably from 400 to 650C. Crude methanol for the purposes of the invention means methanol containing up to about 30% by weight of water, ie. the product formed in the synthesis of methanol. Other lower alcohols may also be present in the crude methanol.
The catalyst throughput, expressed in g of methanol and/or dimethyl ether/g of catalyst.h is advantageously selected to be such that the latter compounds are converted as completely as possible, thereby eliminating separation and recycling problems. In general, therefore, the throughput is of the order of from 2 to 50, preferably from 5 to 15, g/g of zeolite.h. However, it is poss-ible to select higher throughputs, or to dilute the starting materials with an inert gas, for example nitro-gen, without adverse effect on the composition of the hydrocarbon mixture formed. At the same time it is .
.
113~3ZO
a particular advantage of the invention that the conver-sion of crude methanol or dimethyl ether to C2-C5-olefins can be carried out without a diluent.
The zeolites described in German Patent Applica-tion P 28 31 344.0 published on March 15, 1979 can be used as zeolite catalysts. These catalysts are distinguished by particularly high activity and selectivity.
The example which follows illustrates the invention.
EXAMPLE
Preearation of the zeolite:
.
Three solutions are prepared. Solution 1 con-sists of 326.6 g of technical-grade waterglass (contain-ing 8~ by weight of Na2O and 28% by weight of SiO2~ and 352 g of water.
Solution 2 consists of 300 g of a 50 per cent strength aqueous hexamethylenediamine solution and solution 3 consists of 508.3 g of water and 24.7 g of 96 per cent strength sulfuric acid. Solutions 2 and 3 are successively added to solution 1, whilst stirring. The resulting solution is heated for 5 days at 150C under its autogenous pressure in a steel autoclave. The resulting product is filtered off, washed and dried at 100C.
Preparation of the catalyst from the zeolite:
The zeolite obtained is mixed with boehmite in a ratio such that the zeolite content in the mixture is about 65% by weight, based on anhydrous and amine-free ~ product. The mixture is then ;~
. ~
~, .
~ ` 113~8ZO
_ 4 _ o.Z. 0050/033725 - kneaded with water and extruded to form strands of 1 mm diameter. These are calcined at 540C, then treated with an aqueous ammonium sulfate solution at 80C, filtered off, washed and dried Conversion of crude methanol to olefins:
~ ~ .
20 g (dry weight) of this catalyst are introduced into a flow-tube reactor of 20 mm diameter and the acti-vity in respect of the conversion of crude methanol to olefins is tested. The reaction conditions and experi-mental results are shown in the Table which follows.
The reaction products wereanalyzed by gas chromatography.
Entry temperature 400C
Temperature rise 200C
Pressure 1.3 bar Throughput 170 g of crude methanol/h ; Total throughput 1,000 g Conversion 95-100%
The reaction product obtained has the following composition:
Liquid hydrocarbons, 18% by weight, based on CH2 employed Gaseous hydrocarbons, 82% by weight, based on CH2 employed, and containing the following:
Olefins C2 20% by volume C3 43% " ~I
C4 16% " "
Cs 5% "
Paraffins Cl 4 " "
C2 traces C3 2% by volume - C4 10% " "
Claims (2)
1. A process for the preparation of C2-C5-olefins from crude methanol and/or dimethyl ether by catalytic conversion at an elevated temperature in the presence of a zeolite containing catalyst, wherein the zeolite has been prepared from technical-grade waterglass with the aid of hexamethylenediamine, without addition of a metal salt.
2. A process as claimed in claim 1, wherein undilu-ted crude methanol and/or dimethyl ether is used as the starting material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792909927 DE2909927A1 (en) | 1979-03-14 | 1979-03-14 | METHOD FOR PRODUCING OLEFINES FROM RAW METHANOL |
| DEP2909927.2 | 1979-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1130820A true CA1130820A (en) | 1982-08-31 |
Family
ID=6065310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA346,044A Expired CA1130820A (en) | 1979-03-14 | 1980-02-20 | Preparation of olefins from crude methanol |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0016406B1 (en) |
| AT (1) | ATE1092T1 (en) |
| BR (1) | BR8001491A (en) |
| CA (1) | CA1130820A (en) |
| DE (2) | DE2909927A1 (en) |
| ES (1) | ES8200321A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6437208B1 (en) | 1999-09-29 | 2002-08-20 | Exxonmobil Chemical Patents Inc. | Making an olefin product from an oxygenate |
| US6444868B1 (en) | 1999-02-17 | 2002-09-03 | Exxon Mobil Chemical Patents Inc. | Process to control conversion of C4+ and heavier stream to lighter products in oxygenate conversion reactions |
| US6455749B1 (en) | 1997-10-03 | 2002-09-24 | Exxonmobil Chemical Patents, Inc. | Method for increasing light olefin yield by conversion of a heavy hydrocarbon fraction of a product to light olefins |
| US6482999B2 (en) | 1999-02-17 | 2002-11-19 | Exxonmobil Chemical Patents, Inc. | Method for improving light olefin selectivity in an oxygenate conversion reaction |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3117135A1 (en) * | 1981-04-30 | 1982-11-18 | Bayer Ag, 5090 Leverkusen | CRYSTALLINE ALUMOSILICATE, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF FOR CATALYTICALLY CONVERTING METHANOL AND / OR DIMETHYL ETHER IN HYDROCARBONS |
| DE3145712A1 (en) * | 1981-11-19 | 1983-05-26 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING OLEFINS BY REALIZING METHANOL AND / OR DIMETHYL ETHER |
| US4465889A (en) * | 1982-07-02 | 1984-08-14 | Summit Gas Systems Pte. Ltd. | Catalytic conversion of methanol, dimethyl ether and mixtures thereof to a hydrocarbon product rich in iso-C4 compounds and new catalysts therefor |
| US7414166B2 (en) | 2004-10-05 | 2008-08-19 | Exxonmobil Chemical Patents Inc. | Minimizing catalyst backflow in fluidized bed reactors |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1040187A (en) * | 1973-09-07 | 1978-10-10 | Mobil Oil Corporation | Method of preparing a crystalline aluminosilicate zeolite |
| US4066714A (en) * | 1975-12-08 | 1978-01-03 | Mobil Oil Corporation | Manufacture of light olefins |
| US4025572A (en) * | 1976-05-12 | 1977-05-24 | Mobil Oil Corporation | Manufacture of hydrocarbons |
| US4139600A (en) * | 1977-04-22 | 1979-02-13 | Mobil Oil Corporation | Synthesis of zeolite ZSM-5 |
| US4083889A (en) * | 1977-05-26 | 1978-04-11 | Mobil Oil Corporation | Process for manufacturing ethylene |
| DE2831334A1 (en) * | 1978-07-17 | 1980-02-07 | Basf Ag | METHOD FOR PRODUCING CRYSTALLINE ALUMINOSILICATE ZOLITHES |
| DE3244314A1 (en) * | 1982-11-30 | 1984-05-30 | Siemens AG, 1000 Berlin und 8000 München | Optical cable having a central strength member for high tensile stresses |
-
1979
- 1979-03-14 DE DE19792909927 patent/DE2909927A1/en not_active Withdrawn
-
1980
- 1980-02-20 CA CA346,044A patent/CA1130820A/en not_active Expired
- 1980-03-12 AT AT80101259T patent/ATE1092T1/en active
- 1980-03-12 EP EP80101259A patent/EP0016406B1/en not_active Expired
- 1980-03-12 DE DE8080101259T patent/DE3060461D1/en not_active Expired
- 1980-03-13 ES ES489507A patent/ES8200321A1/en not_active Expired
- 1980-03-13 BR BR8001491A patent/BR8001491A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455749B1 (en) | 1997-10-03 | 2002-09-24 | Exxonmobil Chemical Patents, Inc. | Method for increasing light olefin yield by conversion of a heavy hydrocarbon fraction of a product to light olefins |
| US6444868B1 (en) | 1999-02-17 | 2002-09-03 | Exxon Mobil Chemical Patents Inc. | Process to control conversion of C4+ and heavier stream to lighter products in oxygenate conversion reactions |
| US6482999B2 (en) | 1999-02-17 | 2002-11-19 | Exxonmobil Chemical Patents, Inc. | Method for improving light olefin selectivity in an oxygenate conversion reaction |
| US6437208B1 (en) | 1999-09-29 | 2002-08-20 | Exxonmobil Chemical Patents Inc. | Making an olefin product from an oxygenate |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8001491A (en) | 1980-11-11 |
| ATE1092T1 (en) | 1982-06-15 |
| EP0016406A1 (en) | 1980-10-01 |
| DE3060461D1 (en) | 1982-07-15 |
| EP0016406B1 (en) | 1982-05-26 |
| ES489507A0 (en) | 1981-11-01 |
| DE2909927A1 (en) | 1980-09-25 |
| ES8200321A1 (en) | 1981-11-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |