CN104591976B - A kind of method of preparing dimethyl ether by dewatering methanol - Google Patents
A kind of method of preparing dimethyl ether by dewatering methanol Download PDFInfo
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- CN104591976B CN104591976B CN201310532062.2A CN201310532062A CN104591976B CN 104591976 B CN104591976 B CN 104591976B CN 201310532062 A CN201310532062 A CN 201310532062A CN 104591976 B CN104591976 B CN 104591976B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
Abstract
A kind of method that the invention discloses preparing dimethyl ether by dewatering methanol.The method includes two beds i.e. catalyst A and catalyst B, catalyst A composition is as follows: active component heteropoly acid, auxiliary agent lanthana and/or cerium oxide, alumina catalyst support, catalyst B composition is as follows: active component ammonium heteropoly acids, auxiliary agent lanthana and/or cerium oxide, alumina catalyst support.The present invention uses above two catalyst to cooperate, and gives full play to respective advantage, makes the combined reaction performance of reaction system be improved, has higher higher activity, selectivity and stability.
Description
Technical field
A kind of method that the present invention relates to preparing dimethyl ether by dewatering methanol, particularly relate to a kind of use combination catalyst for
The method of preparing dimethyl ether by dewatering methanol.
Background technology
Dimethyl ether (Dimethy Ether, abridge DME) is a kind of colourless, non-toxic gas under normal temperature and pressure state, can be through
Boil down to liquid.Dimethyl ether is important Organic Chemicals and chemical intermediate, can be used for aerosol, cold-producing medium, alkylation
The industries such as agent, pharmacy, cosmetics, fuel.
Dimethyl ether is prepared by after the side-product rectification in high-pressure process methanol production the earliest, quickly develops into methanol dehydration and conjunction
Gas is become to be directly synthesized two kinds of techniques.Liquid phase methanol dewatering preparing dimethy ether, reaction is carried out in the liquid phase, and major defect is that equipment is rotten
Erosion is serious, operating condition is severe, and environmental pollution is serious, and product post processing is relatively difficult gradually to be eliminated.And synthesis gas is straight
Being bonded into dimethyl ether and remain in the experimentation stage, the dominating process route producing dimethyl ether the most in the world remains gas
Phase method methanol dehydration.
At present, the catalyst that methanol dehydration uses is usually Al2O3Or molecular sieve, wherein conventional molecular sieve have aluminum phosphate,
HZSM-5, HY, SAPO etc., they have a respective shortcoming: although as aluminium oxide stability is high, but reaction temperature is high, to instead
The equipment requirements answered is the highest, causes high expensive；Molecular sieve catalysts acidity is relatively strong, and initial temperature is low, but there is also by-product
Thing carbon distribution many, easy, the shortcoming of easy in inactivation.The shortcoming that there is self due to above catalyst so that the preparation of dimethyl ether, investment
Greatly, cost is high, causes the production of dimethyl ether and use to be restricted.
CN00102506.6 discloses the catalyst of a kind of preparing dimethyl ether by dewatering methanol.This catalyst is with aluminium oxide for carrying
Body, the active component of load is heteropoly acid, and anti-carbon deposit component is titanium dioxide and lanthanum sesquioxide, uses infusion process to prepare.King
Keep [molecular science journals 2001,2 (17): 99-104] such as states and report entitled H4SiW12O40-La2O3/γ-Al2O3Catalysis first
Dehydration of alcohols prepares the article of dimethyl ether, and wherein catalyst is also to use infusion process to prepare.Above-mentioned catalyst has relatively in the reaction
High catalysis activity and selectivity, the optimum load amount of silico-tungstic acid is 10wt% ~ 16wt%, at ambient pressure, is used for processing pure methanol
During raw material, its selectivity is higher and active higher, but when aqueous methanol feedstock, its stability is bad, selectivity and work
Property declines the most therewith.
When using hydrophilic solid acid catalyst, water is easily absorbing on their surface, causes reducing them
Active sites, thus reduce they catalysis activity.Therefore, in Dehydration of methanol device, it will usually find reactor head
Beds demonstrate effective dehydration activity, but substantially reduce in the beds activity of reactor bottom, thus
Affect the activity of integer catalyzer, selectivity and stability.
Summary of the invention
In order to overcome weak point of the prior art, a kind of method that the invention provides preparing dimethyl ether by dewatering methanol.
The method, when preparing dimethyl ether by dewatering methanol, has the advantages such as methanol conversion height, selectivity and good stability.
The method of preparing dimethyl ether by dewatering methanol of the present invention, including two beds i.e. catalyst A and catalyst B, its
Middle methanol feedstock first contacts with catalyst A, contacts with catalyst B the most again；
The composition of catalyst A is as follows: active component is heteropoly acid, and auxiliary agent is lanthana and/or cerium oxide, and carrier is oxidation
Aluminum, on the basis of the weight of catalyst, the content of heteropoly acid is 5% ~ 20%, and auxiliary agent content in terms of oxide is 3% ~ 10%,
Al2O3Content be 70 % ~ 92 %；
The composition of catalyst B is as follows:
Active component is that ammonium heteropoly acids is shown in formula (1), and auxiliary agent is lanthana and/or cerium oxide, and carrier is aluminium oxide；To urge
On the basis of the weight of agent, the content of ammonium heteropoly acids is 1% ~ 20%, preferably 5% ~ 18%, and auxiliary agent content in terms of oxide is
1% ~ 10%, Al2O3Content be 70% ~ 98%, preferably 72% ~ 94%；
Hm(NH4)nYX12O40(1)
Wherein X represents W or Mo, Y and represents Si or P；When Y represents Si, m+n=4, n value is 0.05 ~ 1.0；When Y represents
During P, m+n=3, n value is 0.05 ~ 1.0.
In the present invention, catalyst A can use conventional infusion process to prepare, including:
I, presoma and the heteropoly acid of auxiliary agent are joined in aqueous solution, obtain mixed solution A；
II, alumina support is joined in solution A, stir at 60 DEG C ~ 90 DEG C to solution and be evaporated；
III, solid step II obtained, at 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then 300 DEG C ~ 450 DEG C roastings 2
H ~ 6 h, obtains catalyst A.
In step I, described auxiliary agent presoma is one or more in Lanthanum (III) nitrate, cerous nitrate；Described heteropoly acid is
One or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
In step II, described alumina support is to be obtained through molding, dry and roasting by boehmite.Described plan
Boehmite can use conventional method to prepare, such as: Alchlor process, aluminum sulfate method, carbonizatin method etc..Described roasting condition: roasting
Burning temperature is 400 DEG C ~ 700 DEG C, and roasting time is 2 h ~ 10 h.
In the present invention, the preparation method of catalyst B, including:
(1) presoma of auxiliary agent is joined containing in organic aqueous acid, obtain solution A；
(2) alumina support is joined in solution A, stir at 50 DEG C ~ 90 DEG C to solution and be evaporated；
(3) solid that step (2) obtains joined in the alkaline solution containing ammonium impregnate, then filter, 40 DEG C ~
It is dried at 100 DEG C, or solid step (2) obtained adsorbs ammonia at 40 DEG C ~ 100 DEG C；
(4) solid step (3) obtained, joins in the aqueous solution of heteropoly acid, stirs to solution at 50 DEG C ~ 90 DEG C
It is evaporated；
(5) solid that step (4) is obtained, drying, then at 300 DEG C ~ 550 DEG C roasting 2 h ~ 6 h, obtain catalysis
Agent B.
In step (1), described auxiliary agent presoma is one or more in Lanthanum (III) nitrate, cerous nitrate；Described organic acid can
Oxygen in alumina support used by one or more in citric acid, tartaric acid, malic acid, described organic acid and step (2)
The mol ratio changing aluminum is 0.05 ~ 0.5.
In step (2), described alumina support is to be obtained through molding, dry and roasting by boehmite.Described
Boehmite can use conventional method to prepare, such as: Alchlor process, aluminum sulfate method, carbonizatin method etc..Described roasting condition:
Sintering temperature is 400 DEG C ~ 700 DEG C, and roasting time is 2 h ~ 10 h.
In step (3), the solid that step (2) obtains is joined in the alkaline solution containing ammonia and impregnates, dip time
Generally 5 min ~ 30 min.Solid absorption ammonia step (2) obtained, adsorption time is generally 5 min ~ 30 min.
In step (3), the described alkaline solution containing ammonium is the one in ammonia, sal volatile, ammonium bicarbonate soln
Or it is multiple.
In step (3), described ammonia can use pure ammonia, it would however also be possible to employ the gaseous mixture containing ammonia, in mixed gas
In addition to ammonia, other is noble gas such as one or more in nitrogen, argon etc..
In step (4), described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
In step (4), the solid that step (3) is obtained, join in the aqueous solution of heteropoly acid and impregnate, dip time
Generally 5 min ~ 30 min.In step (4), it is to being evaporated by solution stirring.
In step (5), described drying condition is as follows: 90 DEG C ~ 120 DEG C are dried 5 h ~ 12 h.
Described catalyst A and the admission space of catalyst B are than for 5:1 ~ 1:5.
The method of methanol dehydration dimethyl ether-preparing of the present invention, reaction condition is as follows: reaction pressure is 0 ~ 3.0 MPa, preferably
Being 0 ~ 2.5 MPa, mass space velocity is 0.5 h-1~3.5 h-1, preferably 1.0 h-1~3.0 h-1, reaction temperature is 240 DEG C ~ 300
DEG C, preferably 240 DEG C ~ 280 DEG C.
Compared with prior art, the invention have the advantages that
In the inventive method, use catalyst B to be seated in the downstream of catalyst A, make catalyst A and catalyst B phase interworking
Conjunction gives full play to respective advantage, while making catalyst entirety have higher activity, selectivity and coking resistivity, improves
The stability of catalyst, can extend the service life of catalyst, make the combined reaction performance of reaction system improve, have more
High product yield.During for processing aqueous higher methanol feedstock, still there is higher activity and selectivity.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
(1) prepared by catalyst:
Prepared by catalyst A
Weigh 13.3g Lanthanum (III) nitrate and 15.6g phosphotungstic acid joins in deionized water, be made into mixed solution；By 80g aluminium oxide
Carrier joins in mixed solution, stirs to solution and be evaporated at 70 DEG C；8 h, roasting 3 at 350 DEG C it is dried at 110 DEG C
H, prepares H3PW12O40-La2O3/Al2O3Catalyst, wherein La2O3Content is 5wt%, H3PW12O40Content is 15wt%.
Prepared by catalyst B
Weigh 21.3g Lanthanum (III) nitrate and 43.5g citric acid joins in deionized water, be made into mixed solution；By 77g aluminium oxide
Carrier joins in mixed solution, stirs to solution and be evaporated at 70 DEG C, wherein citric acid and Al2O3Mol ratio be 0.3；Will
Dipping 10min in sal volatile put into by gained solid, is dried after filtration at 60 DEG C；Gained solid is joined containing
In the aqueous solution of 15.6g phosphotungstic acid, stir at 70 DEG C and be evaporated to solution, at 110 DEG C, be dried 8 h, roasting at 470 DEG C
3 h, prepare (NH4)0.5H2.5PW12O40-La2O3/Al2O3Catalyst, wherein La2O3Content is 8wt%, (NH4)0.5H2.5PW12O40
Content is 15wt%.
(2) evaluation of catalyst:
The reaction of methanol (technical grade, >=98.5%) dewatering preparing dimethy ether is carried out in fixed-bed tube reactor, methanol feedstock
First contacting with catalyst A, contact with catalyst B, wherein the admission space of catalyst A and catalyst B ratio is for 3:1, common
20 mL, reaction condition is normal pressure, mass space velocity 1.2h-1, reaction temperature 260 DEG C, before reaction, catalyst is at N2Under protection in
400 DEG C of activation 2 h, are then down to reaction temperature and start to react 4 h and 100 h, and product is analyzed by gas chromatogram, calculates
Selectivity and conversion ratio, the results are shown in Table 1.
Embodiment 2
Selecting in embodiment 1 catalyst A and B admission space ratio for 1:1, reaction condition is pressure 1.0MPa, mass space velocity
2.0h-1, reaction temperature 250 DEG C, other appreciation condition is constant, and conversion ratio and dimethyl ether selectivity the results are shown in Table 1.
Embodiment 3
Selecting in embodiment 1 catalyst A and B admission space ratio for 1:3, reaction condition is pressure 2.0MPa, mass space velocity
2.8h-1, reaction temperature 270 DEG C, other appreciation condition is constant, and conversion ratio and dimethyl ether selectivity the results are shown in Table 1.
Embodiment 4
Select the catalyst A in embodiment 1；
The preparation of catalyst B:
Weigh 13.3g Lanthanum (III) nitrate and 31.3g citric acid joins in deionized water, be made into mixed solution；By 83g aluminium oxide
Carrier joins in mixed solution, stirs to solution and be evaporated at 70 DEG C, wherein citric acid and Al2O3Mol ratio be 0.2；Will
Dipping 10min in sal volatile put into by gained solid, is dried after filtration at 60 DEG C；Gained solid is joined containing
In the aqueous solution of 12.5g phosphotungstic acid, stir at 70 DEG C and be evaporated to solution, at 110 DEG C, be dried 8 h, roasting at 500 DEG C
3 h, prepare (NH4)0.1H2.9PW12O40-La2O3/Al2O3Catalyst, wherein La2O3Content is 5wt%, (NH4)0.1H2.9PW12O40
Content is 12wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, conversion ratio and dimethyl ether selectivity.
Embodiment 5
In embodiment 1, changing phosphotungstic acid into silico-tungstic acid, remaining is H with embodiment 1, gained catalyst A4SiW12O40-
La2O3/Al2O3Catalyst, wherein La2O3Content is 5wt%, H4SiW12O40Content is 15wt%.Catalyst B is (NH4)0.5H3.5SiW12O40-La2O3/Al2O3Catalyst, wherein La2O3Content is 8wt%, (NH4)0.5H3.5SiW12O40Content is 15wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, conversion ratio and dimethyl ether selectivity.
Comparative example 1
Being used alone catalyst A, the evaluation of catalyst the results are shown in Table 1 with embodiment 1, conversion ratio and dimethyl ether selectivity.
Comparative example 2
The catalyst B being used alone in embodiment 1, the evaluation of catalyst is with embodiment 1, conversion ratio and dimethyl ether selectivity
The results are shown in Table 1.
The conversion ratio of table 1 each example catalyst and selectivity
Claims (12)
1. a method for preparing dimethyl ether by dewatering methanol, including two beds i.e. catalyst A and catalyst B, Qi Zhongjia
Raw polyol first contacts with catalyst A, contacts with catalyst B the most again；
The composition of catalyst A is as follows: active component is heteropoly acid, and auxiliary agent is lanthana and/or cerium oxide, and carrier is aluminium oxide,
On the basis of the weight of catalyst, the content of heteropoly acid is 5% ~ 20%, and auxiliary agent content in terms of oxide is 3% ~ 10%, Al2O3's
Content is 70% ~ 92%；Described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid；
The composition of catalyst B is as follows:
Active component is that ammonium heteropoly acids is shown in formula (1), and auxiliary agent is lanthana and/or cerium oxide, and carrier is aluminium oxide；With catalyst
Weight on the basis of, the content of ammonium heteropoly acids is 1% ~ 20%, and auxiliary agent content in terms of oxide is 1% ~ 10%, Al2O3Content
It is 70% ~ 98%；
Hm(NH4)nYX12O40(1)
Wherein X represents W or Mo, Y and represents Si or P；When Y represents Si, m+n=4, n value is 0.05 ~ 1.0；When Y represents P,
M+n=3, n value is 0.05 ~ 1.0.
The most in accordance with the method for claim 1, it is characterised in that: described catalyst B, on the basis of the weight of catalyst,
The content of ammonium heteropoly acids is 5% ~ 18%, and auxiliary agent content in terms of oxide is 1% ~ 10%, Al2O3Content be 72% ~ 94%.
The most in accordance with the method for claim 1, it is characterised in that: the admission space ratio of described catalyst A and catalyst B is
5:1 ~1:5。
The most in accordance with the method for claim 1, it is characterised in that: catalyst B adopts and prepares with the following method, including:
(1) presoma of auxiliary agent is joined containing in organic aqueous acid, obtain solution A；
(2) alumina support is joined in solution A, stir at 50 DEG C ~ 90 DEG C to solution and be evaporated；
(3) solid that step (2) obtains is joined in the alkaline solution containing ammonium impregnate, then filter, 40 DEG C ~ 100
It is dried at DEG C, or solid step (2) obtained adsorbs ammonia at 40 DEG C ~ 100 DEG C；
(4) solid step (3) obtained, joins in the aqueous solution of heteropoly acid, stirs to solution steaming at 50 DEG C ~ 90 DEG C
Dry；
(5) solid that step (4) is obtained, drying, then at 300 DEG C ~ 550 DEG C roasting 2 h ~ 6 h, obtain catalyst.
The most in accordance with the method for claim 4, it is characterised in that: in step (2), described alumina support is by intending thin water
Aluminum stone obtains, described roasting condition through molding, dry and roasting: sintering temperature is 400 DEG C ~ 700 DEG C, and roasting time is 2
h~10 h。
The most in accordance with the method for claim 4, it is characterised in that: in step (1), described auxiliary agent presoma be Lanthanum (III) nitrate,
One or more in cerous nitrate；Described organic acid is one or more in citric acid, tartaric acid, malic acid.
The most in accordance with the method for claim 4, it is characterised in that: in step (1), described organic acid is used with step (2)
In alumina support, the mol ratio of aluminium oxide is 0.05 ~ 0.5.
The most in accordance with the method for claim 4, it is characterised in that: in step (3), the described alkaline solution containing ammonium is ammonia
One or more in water, sal volatile, ammonium bicarbonate soln；Described ammonia uses pure ammonia or uses containing ammonia
Gaseous mixture, in mixed gas in addition to ammonia, other is one or more in inert nitrogen gas, argon.
The most in accordance with the method for claim 4, it is characterised in that: in step (4), described heteropoly acid is phosphotungstic acid, silicon tungsten
One or more in acid, phosphomolybdic acid.
The most in accordance with the method for claim 4, it is characterised in that: in step (5), described drying condition is as follows: 90 DEG C ~
120 DEG C are dried 5 h ~ 12 h.
11. in accordance with the method for claim 1, it is characterised in that: the reaction condition of methanol dehydration dimethyl ether-preparing is as follows: anti-
Answering pressure is 0 ~ 3.0 MPa, and mass space velocity is 0.5 h-1~3.5 h-1, reaction temperature is 240 DEG C ~ 300 DEG C.
12. in accordance with the method for claim 1, it is characterised in that: the reaction condition of methanol dehydration dimethyl ether-preparing is as follows: anti-
Answering pressure is 0 ~ 2.5 MPa, and mass space velocity is 1.0 h-1~3.0 h-1, reaction temperature is 240 DEG C ~ 280 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308987A (en) * | 2000-02-17 | 2001-08-22 | 东北师范大学 | Carried heteropoly acid catalyst for preparing dimethyl ether by dewatering methanol and its preparing process |
| CN1837170A (en) * | 2006-02-21 | 2006-09-27 | 汪荣华 | Process for preparing dimethyl enther by vapour catalytic dehydration of methanol with high-activity dipping-type heteropoly acid as catalyst |
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| WO2009117851A1 (en) * | 2008-03-26 | 2009-10-01 | 中国石油化工股份有限公司 | A process for producing dimethyl ether from methanol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308987A (en) * | 2000-02-17 | 2001-08-22 | 东北师范大学 | Carried heteropoly acid catalyst for preparing dimethyl ether by dewatering methanol and its preparing process |
| CN1837170A (en) * | 2006-02-21 | 2006-09-27 | 汪荣华 | Process for preparing dimethyl enther by vapour catalytic dehydration of methanol with high-activity dipping-type heteropoly acid as catalyst |
Non-Patent Citations (2)
| Title |
|---|
| γ- Al2O3 负载杂多酸催化合成二甲醚;年瑞华等;《东北师大学报自然科学版》;19971231(第4期);第37-39页 * |
| 氧化铝负载杂多酸催化甲醇脱水制备二甲醚;王守国等;《现代化工》;20001130;第20卷(第11期);第39-41页 * |
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