CN101168131B - Aluminium oxide catalyst for preparing dimethy ether by methanol gas phase dewatering - Google Patents
Aluminium oxide catalyst for preparing dimethy ether by methanol gas phase dewatering Download PDFInfo
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- CN101168131B CN101168131B CN2007101685576A CN200710168557A CN101168131B CN 101168131 B CN101168131 B CN 101168131B CN 2007101685576 A CN2007101685576 A CN 2007101685576A CN 200710168557 A CN200710168557 A CN 200710168557A CN 101168131 B CN101168131 B CN 101168131B
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Abstract
The invention provides an aluminum oxide catalyst used in the making of dimethyl ether by the gas phase dehydration of methanol. Gamma-Al2O3 is taken as a carrier when the catalyst prepares, salt of acid ion of SO42-, PO43- or F- is dissolved in the gamma-Al2O3, then the gamma-Al2O3 is soaked with salt of acid ion of SO42-, PO43- or F- and is added with dispersants. The invention has the advantages of moderate acidity, wide range of active temperature area, a small amount of carbon deposition, and high capability to prevent the alkaline materials from poisoning.
Description
Technical field
The present invention relates to a kind of catalyst, particularly relate to the catalyst that is used for methanol gas phase dewatering preparing dimethy ether.
Background technology
The dimethyl ether purposes is very extensive, can be used as industrial chemicals, aerosol, cold-producing medium, substitute fuel etc.Dimethyl ether combustion characteristics and liquefied petroleum gas (abbreviate liquefied gas as, english abbreviation is LPG) are similar, and be but safer than liquefied gas aspect storage, transportation and use, substitutes LPG as civilian and industrial fuel remarkable in economical benefits.As domestic fuel, the Ministry of Construction issues " city gas dimethyl ether " industry standard, and from enforcement on January 1 in 2008, dimethyl ether will formally be promoted as the alternative fuel of liquefied gas.As vehicle fuel, the dimethyl ether bus also begins to enter the Demonstration Application stage in Shanghai, also is expected to further popularization.Recently the oil crisis that grows in intensity is more facilitated cleaning, the effectively development of substitute fuel industry.
The production method of dimethyl ether mainly contains methanol liquid-phase dehydration method, one-step method from syngas and methanol gas phase dehydration method.The methanol liquid-phase dehydration method is under the catalysis of sulfuric acid or compound acid, methanol liquid-phase dehydration and generate dimethyl ether.Patent of invention CN1322704 and CN1111231A have reported with the liquid acid to be the method for Preparation of Catalyst dimethyl ether, and this method reaction temperature is low, and conversion ratio is higher, but because strong acid is big to the corrosivity of equipment material, raffinate and wastewater flow rate are big, and the raffinate processing method does not match, environment seriously polluted.Synthesis of dimethyl ether with synthesis gas one-step is that synthesis gas is had the bifunctional catalyst of dehydrating function, dimethyl ether synthesis under the synergy of catalyst again by existing synthesizing methanol function.Patent of invention CN1413767A, CN1085824, CN1087033, CN1090222 etc. disclose the preparation method that one-step method from syngas is produced dimethyl ether catalyst, but this method also is in the type approval test stage at present, the solution of still needing of many key technologies there is no corresponding large-scale industry device and puts into operation.
Adopted by domestic and international most of dimethyl ether factory at present, industrial the most ripe method is the methanol gas phase dehydration method.This method is methyl alcohol to be dewatered under the effect of catalyst with the form of steam generate dimethyl ether.Its reaction equation is as follows:
2CH
3OH→CH
3OCH
3+H
2O
Advantages such as this method has that raw material sources are extensive, flow process is short, operating condition is gentle, no equipment corrosion, the three wastes (waste water, waste gas and waste residue) discharging are low, the catalyst that therefore is used for methanol gas phase dewatering preparing dimethy ether becomes the focus of research.Patent of invention CN1036199A discloses with γ-Al
2O
3(preferably contain a spot of SiO
2) be the method for Catalyst Production pure Dimethyl ether, but this catalyst stability is bad, can not use for a long time.Patent of invention CN1125216A discloses a kind of method by preparing dimethyl ether from methanol, and that catalytic and dehydration reaction adopts is γ-Al
2O
3With the composite solid-acid catalyst of alumino-silicate crystallization, but this method preparation process complexity.Patent of invention CN1308987 discloses carried heteropoly acid catalyst and the production method thereof that is used for preparing dimethyl ether by dewatering methanol, is 240～320 ℃ in reaction temperature, and pressure is 0～1.0MPa, and mass space velocity is 1.0～3.5h
-1Reaction condition under, methanol conversion reaches 85%, the dimethyl ether selectivity is 99.99%.But need activation before this catalyst uses, warm area is narrower, when reaction temperature is high side reaction many, the easy carbon deposit of catalyst surface.Patent of invention CN1368493 relates to a kind of method of methyl alcohol catalytic dehydration preparing dimethy ether, and wherein dehydration is to contain SO
4 2-Solid acid catalyst exist and to carry out down, but conversion of methanol is not high.CN1613558 has introduced the modified alumina catalyst that is used for dimethyl ether synthesis, and this catalyst is at common γ-Al
2O
3In add a certain amount of SO with sulphate form
4 2-Because this catalyst has proper acidic, it is used for the methanol dehydration dimethyl ether-preparing reaction, can obtain high methanol conversion and dimethyl ether selectivity at a lower temperature, but alkaline matters such as the ammonia that contains in the methanol feedstock destroy the acid centre of catalyst easily, make the catalyst poisoning inactivation.
The methanol gas phase dehydration method need be used acidic catalyst.The acidity of catalyst is strong more, and dehydration speed is fast more, and active temperature is low more, and conversion of methanol is high more; But along with the raising of conversion ratio, the selectivity variation of target product dimethyl ether has more side reaction to take place, catalyst surface generation this moment carbon deposit, coking, and it is very fast to cause activity of such catalysts to descend.If acidity of catalyst a little less than, the catalyst activity temperature is low, then must improve reaction temperature and improve conversion of methanol, though dimethyl ether has very high selectivity, energy consumption is higher, the raising of unfavorable economic benefit.Though HZSM-5 molecular sieve, dealuminzation Y molecular sieve, 12 tungstophosphoric acids, aluminium titanates, super acids modified aluminas etc. have the advantage that active temperature is low, methanol conversion is high, but it is narrow to be suitable for warm area, the dimethyl ether poor selectivity, and side reaction is serious, and the easy carbon deposit of catalyst surface, active decline soon.Shortcomings such as it is good that though common aluminium oxide is made catalyst dimethyl ether selectivity, but exist low temperature active poor, and the high temperature carbon deposit is serious.All there is a common shortcoming in the commercial catalyst at present: when being raw material with thick methyl alcohol, alkaline matters such as the ammonia that wherein contains destroy the acid centre of catalyst easily, make the catalyst poisoning inactivation, and the commercial catalyst mostly is bar shaped greatly, is unfavorable for evenly filling in reactor.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of acidity suitable, and active warm area wide ranges, carbon deposit is few, the aluminium oxide catalyst that is used for preparing dimethyl ether by dewatering methanol that alkali resistance material poisoning capability is strong.
The technical solution adopted in the present invention is: be used for the aluminium oxide catalyst of methanol gas phase dewatering preparing dimethy ether, during preparation with γ-Al
2O
3Do carrier, promptly dissolving contains SO earlier
4 2-, PO
4 3-Or F
-The salt of acid ion is then with γ-Al
2O
3Dipping contains SO
4 2-, PO
4 3-Or F
-The salt of acid ion also adds dispersant, and the dipping back adds the water soluble salt that contains Ce in the gained intermediate carrier, and calcining obtains described aluminium oxide catalyst under 500～700 ℃ of conditions at last.
Active warm area wide ranges of the present invention, low temperature active is good, and carbon deposit is few, and alkali resistance material (as ammonia) poisoning capability is strong.Adopt the high-strength alumina spheric granules to do carrier, be convenient to evenly filling in the reactor, be fit to commercial Application.
The specific embodiment
The aluminium oxide catalyst that is used for methanol gas phase dewatering preparing dimethy ether is with γ-Al
2O
3Do carrier, must be with γ-Al
2O
3Dipping contains PO
4 3-Or F
-Deng the salt of acid ion so that the acid site to be provided.Contain PO
4 3-Or F
-Salt Deng acid ion can be selected NH for use
4F, (NH
4)
3PO
4Or AlF
3
The aluminium oxide catalyst that is used for methanol gas phase dewatering preparing dimethy ether can also γ-Al
2O
3Do carrier, dissolving contains SO
4 2-, PO
4 3-Or the salt of F acid ion, then with γ-Al
2O
3Dipping contains SO
4 2-, PO
4 3-Or F
-The salt of acid ion also adds dispersant.Dispersant can be selected citric acid for use, to improve the active component dispersiveness.Contain SO
4 2-Salt can select (NH for use
4)
2SO
4Or Al
2(SO
4)
3
Experiment showed, the catalyst of selecting the salt that contains F for use, light-off temperature is minimum, and methanol conversion is the highest, and the dimethyl ether selectivity is good.Contain F
-, PO
4 3-The content of salt count 0.1～10wt% with acid ion, contain SO
4 2-The content of salt count 0.1～3wt% with acid ion.
With γ-Al
2O
3Dipping contains SO
4 2-, PO
4 3-Or F
-After the salt Deng acid ion, the water soluble salt that the gained intermediate carrier can be added transition elements or rare earth element improves the high temperature anti-carbon deposition ability of catalyst, suppresses the generation of side reaction, can improve the performance of the alkali resistance material (as ammonia) of catalyst simultaneously.Described transition elements or rare earth element can be selected Ti, Co, Zr, Mo, Yb, La or Ce for use.
Experiment showed, the catalyst of selecting the water soluble salt that contains Ce for use, its anti-ammonia and anti-carbon deposition ability are best, the methanol conversion height.The content of Ce is 0.1～3wt% best results in transition elements or the rare earth element.
Above-mentioned γ-Al
2O
3Also can be sphere, so that evenly filling in the reactor is fit to commercial Application.
This is used for the aluminium oxide catalyst of methanol gas phase dewatering preparing dimethy ether, and its preferred for preparation method is:
1) dissolving contains SO
4 2-, PO
4 3-, F
-The salt of acid ion adds citric acid;
2) the mixed acid solution of step 1) is added spherical gamma-Al
2O
3Alumina support behind the dipping 12h, 120 ℃ of oven dry down, gets intermediate carrier;
3) water soluble salt of dissolving transition elements or rare earth element adds step 2) the gained intermediate carrier, behind the dipping 12h, 120 ℃ of oven dry down, the product after will dry is at last calcined 4h down in 500～700 ℃, promptly gets catalyst of the present invention.
Embodiment 1～5: take by weighing 10.3g (NH respectively
4)
2SO
4, 18.1g Al
2(SO
4)
318H
2O, 14.6gNH
4F, 18.5g (NH
4)
3PO
4, 11.1gAlF
3Add 1000ml distilled water, stirring and dissolving adds the 10.0g citric acid, and the dissolving back adds spherical gamma-Al
2O
3Carrier 750g, 40 ℃ of constant temperature dipping 12h are 120 ℃ of oven dry down.Get the 5.0g cerous nitrate then, be dissolved in the 500ml water, add above-mentioned dried intermediate carrier, 40 ℃ of constant temperature dipping 12h, 120 ℃ of oven dry down, the product after will drying at last gets the catalyst sample of embodiment 1～5 at 500～700 ℃ of calcining 4h.Assay method: take by weighing original catalyst particle size sample 30ml of the present invention, put into pressure reactor, be heated to 260 ℃, be preheating to 240 ℃ behind the methanol gasifying and import in the reactor, regulating system pressure to 0.7～0.8MPa, mass space velocity are 1.5h
-1, analyze exit gas and liquid composition with gas chromatograph, calculate the selectivity of conversion of methanol and dimethyl ether.Measurement result is as shown in table 1, and this table has also comprised the catalyst performance when not adding bisalt.
Table 1: the performance of catalyst when adding different bisalt
As can be seen from Table 1, flood an amount of SO that contains
4 2-, PO
4 3-, F
-Can both reduce the light-off temperature of methyl alcohol significantly Deng the salt of acid ion, improve conversion ratio, wherein flood NH
4The light-off temperature of methyl alcohol is minimum during F, and conversion ratio is the highest.
Embodiment 6～11: take by weighing 14.6gNH
4F adds 1000ml distilled water, and stirring and dissolving adds the 10.0g citric acid, and the dissolving back adds spherical gamma-Al
2O
3Carrier 750g, 40 ℃ of constant temperature dipping 12h are 120 ℃ of oven dry down.Get the nitrate compound of 5.0gTi, Co, Zr, Mo, Yb, La then respectively, be dissolved in the 500ml water, add above-mentioned dried intermediate carrier, 40 ℃ of constant temperature dipping 12h, 120 ℃ of oven dry down, at last gained is dried product gets embodiment 6～11 at 500～700 ℃ of calcining 4h catalyst sample.Methanol conversion and dimethyl ether optionally assay method with embodiment 1.With the methyl alcohol that contains ammonia 5% is raw material, moves 72h continuously, measures methanol conversion, represents its anti-ammonia activity; It in 400 ℃ of operation 72h, is investigated the carbon deposit phenomenon of catalyst.Measurement result is as shown in table 2.This table has also comprised the performance when not adding rare earth or transition elements water soluble salt.
Table 2: the performance of catalyst when adding different rare earths or transition elements water soluble salt
The adding of rare earth or transition elements can obviously improve the anti-ammonia and the anti-carbon deposition ability of catalyst as can be seen from Table 2, and the anti-ammonia and the anti-carbon deposition ability of catalyst are best when wherein flooding the soluble-salt of Ce.
Embodiment 12～19: get a certain amount of NH respectively
4F, control F
-Mass percent be 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 12%, all the other are with embodiment 2.Measurement result is as shown in table 3.
Table 3:F
-Content is the performance of catalyst simultaneously not
As can be seen from Table 3, when acid ion content was higher, the acidity of catalyst was stronger, had this moment side reaction to take place, and the selectivity of dimethyl ether reduces, so F
-Preferred range be 0.1～10%.
Embodiment 20～27: get a certain amount of Al respectively
2(SO
4)
3, control SO
4 2-Mass percent be 0.1%, 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3%, 3.5%, all the other are with embodiment 2.Measurement result is as shown in table 4.
Table 4:SO
4 2-Content is the performance of catalyst simultaneously not
As can be seen from Table 4, SO
4 2-Preferred range be 0.1～3%.
Embodiment 28～35: get a certain amount of (NH respectively
4)
3PO
4, control PO
4 3--Mass percent be 0.1%,, 1%, 2%, 4%, 6%, 8%, 10%, 12%, all the other are with embodiment 2.Measurement result is as shown in table 5.
Table 5:PO
4 3-Content is the performance of catalyst simultaneously not
As can be seen from Table 5, PO
4 3--Preferred range be 0.1～10%.
Embodiment 36～42: get a certain amount of cerous nitrate respectively, the mass percent of control cerium is 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, and all the other are with embodiment 10, and measurement result is as shown in table 6.
Table 6: rare earth or transition elements content is the performance of catalyst simultaneously not
Ce content＞3% o'clock as can be seen from Table 6, methanol conversion reduces, because the amount of the load C e of catalyst is more, causes acid centre to reduce.Therefore, suitable Ce content is 0.1-3%.
Claims (2)
1. the aluminium oxide catalyst that is used for methanol gas phase dewatering preparing dimethy ether, during preparation with γ-Al
2O
3Do carrier, promptly dissolving contains SO earlier
4 2-, PO
4 3-Or F
-The salt of acid ion is then with γ-Al
2O
3Dipping contains SO
4 2-, PO
4 3-Or F
-The salt of acid ion also adds dispersant, it is characterized in that: the dipping back adds the water soluble salt that contains Ce in the gained intermediate carrier, calcining obtains described aluminium oxide catalyst under 500～700 ℃ of conditions at last.
2. the aluminium oxide catalyst that is used for methanol gas phase dewatering preparing dimethy ether as claimed in claim 1 is characterized in that: the described F of containing
-, PO
4 3-The content of salt count 0.1～10wt% with acid ion, the described SO that contains
4 2-The content of salt count 0.1～3wt% with acid ion, the content of the water soluble salt of the described Ce of containing is counted 0.1～3wt% with Ce.
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|---|---|---|---|
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|---|---|---|---|
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| CN101168131B true CN101168131B (en) | 2010-06-16 |
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| CN103772165B (en) * | 2012-10-25 | 2016-05-18 | 中国石油化工股份有限公司 | By the method for paraformaldehyde polyoxymethylene dimethyl ethers processed |
| CN104151147B (en) * | 2013-05-16 | 2016-05-18 | 中国石油化工股份有限公司 | With the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers |
| CN104588056B (en) * | 2013-11-03 | 2017-07-14 | 中国石油化工股份有限公司 | Preparing dimethyl ether by dewatering methanol catalyst and preparation method thereof |
| CN103721716A (en) * | 2014-01-16 | 2014-04-16 | 浙江中烟工业有限责任公司 | Catalyst for selectively reducing release quantity of hydrogen cyanide in mainstream smoke of cigarettes based on cobalt oxide and preparation method of catalyst |
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Address after: 430070 Hubei Province, Wuhan city Wuchang District Wuluo Road No. 543-2 Patentee after: Wuhan Kelin Chemical Industry Group Co.,Ltd. Address before: 430070 Hubei Province, Wuhan city Wuchang District Wuluo Road No. 543-2 Patentee before: WUHAN KELIN FINE CHEMICAL Co.,Ltd. |
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