CN85101847A - A kind of ether synthetic Preparation of catalysts method that is used for - Google Patents
A kind of ether synthetic Preparation of catalysts method that is used for Download PDFInfo
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- CN85101847A CN85101847A CN 85101847 CN85101847A CN85101847A CN 85101847 A CN85101847 A CN 85101847A CN 85101847 CN85101847 CN 85101847 CN 85101847 A CN85101847 A CN 85101847A CN 85101847 A CN85101847 A CN 85101847A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 25
- 238000002360 preparation method Methods 0.000 title description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 47
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 23
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 238000003795 desorption Methods 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims abstract 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 29
- 239000010457 zeolite Substances 0.000 claims description 29
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 11
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 230000000694 effects Effects 0.000 description 22
- 239000002585 base Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- JQOAZIZLIIOXEW-UHFFFAOYSA-N zinc;chromium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Cr+3].[Cr+3].[Zn+2] JQOAZIZLIIOXEW-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
According to the present invention, a kind of being used for produced the alumina silicate catalyst that the dehydration of alcohols house etherealizes by following steps.Be in 800 ℃ with on the next temperature with one or more nitrogenous base contacts, 320-800 ℃ crystalline aluminosilicate preferably, up to the absorption that maximum possible takes place, then, the crystalline aluminosilicate of handling is like this carried out aftertreatment, it is included in 320-800 ℃, preferably comes the absorbed nitrogenous base part of desorption by a kind of inert gas on it under 400-600 ℃ of temperature, and aftertreatment proceeds to no longer always and takes place till the desorption.
Description
FIELD OF THE INVENTION
The present invention relates to the preparation method of alumina silicate catalyst, this catalyzer is used for the processing method of synthetic its integral part of formation of the synthetic or ether of ether.More particularly, the present invention relates to a method of producing this catalyzer with nitrogenous base processing crystalline aluminosilicate.
The background technology of invention
Known to have severally to be referred to as acidic dehydration catalyst for alcohol being converted to the catalyzer that ether has catalytic activity, for example, known acidic dehydration catalyst aluminum oxide is as gama-alumina; Silicon-dioxide; Aluminium oxide-silicon oxide mixture and crystalline aluminosilicate are as zeolite and montmorillonite.Most of known to industrial application have enough highly active acidic dehydration catalyst since promptly lose activity and the life-span not long.Another defective of most of known acidic dehydration catalysts is their also some pairs of catalysis reactions simultaneously, causes the high-content of undesirable pair of product in the ether of producing.
Produces ether from alcohol and under the condition that said acidic dehydration catalyst exists, under high temperature, high pressure, carry out, and it is to be undertaken by following general reactive mode:
R wherein
1And R
2Can be identical or different, and they each optionally represent the alkyl, the aryl or aralkyl group that replace.But, in above-mentioned desired response (1), undesirable pair of reaction also takes place, cause hydrocarbon formation and owing to deposited by polymkeric substance and or the what is called " Jiao " formed of carbon used catalyzer is lost activity.In the middle of the ether of producing, do not wish to contain hydrocarbon in its inside, it is much serious still to cause that owing to deposition is burnt catalyzer loses activity, because this has quickened the very fast process that needs replacement or regenerated catalyst.People have carried out extensive studies, particularly for find to the formation of ether and still less coking tendency have more catalyzer and definite optimum process condition of highly selective.For example, with regard to crystalline aluminosilicate,, produce improved characteristic aspect and made many reward examinations by changing its vesicular structure and/or by making other atoms of elements form its lattice integral part.But how many successes these effort do not obtain so far.
Previously, carried out many relating to and used all ingredients, be i.e. nitrogenous base, handle the experiment that various crystal are crystalline aluminosilicate, in these experiments, proved that nitrogenous base is connected to the acid activity position of (obstruction) catalyzer, thereby hindered the catalyst activity of catalyzer to a great extent.So just know that handling crystalline aluminosilicate with nitrogenous base causes these have catalytic activity to top reaction (1) under the state of being untreated catalyzer, no longer has this activity or has only very low activity.And, stop up this activity site with nitrogenous base and reach degree very completely, thereby, for example the catalyzer that contains the acid activity position with ammonia treatment also is utilized in analytical chemistry, because for example can determine number (N.Tops φ e, the K.Pedersen of relevant catalyst acid activity site quite exactly to the absorbed dose of ammonia, E.G Derouane, the catalyzer magazine, 41~52 pages of 70 volumes, 1981)
Have now found that, by special processing to known crystalline aluminosilicate as catalyzer, can give its lower deactivation rate thereby a longer life-span is just arranged, can utilize such catalyzer to obtain to have the resultant of reaction of lower pair of product content simultaneously.
More particularly, made us finding uncannily: can realize the part obstruction of activity site in the crystalline aluminosilicate with nitrogenous base, thereby a selectivity of various acid activities position is stopped up in the acquisition catalyzer, promptly main the generation forming the obstruction of the activity site that hydrocarbon works, and those activity sites that form according to top reaction formula (1) catalysis ether are blocked with much smaller degree.
Summary of the invention is according to the present invention, change into the alumina silicate catalyst that uses in the catalytic dehydration of ether at alcohol, can prepare through follow procedure: (a) be lower than under 800 ℃ the temperature, preferably 320-800 ℃ with one or more nitrogenous bases contact crystalline aluminosilicate, reaches till the greatest limit until sorption.Then,
(b) processed crystalline aluminosilicate is under 320-800 ℃ temperature, and preferably 400-600 ℃ is carried out aftertreatment, in aftertreatment, feeds a kind of inert gas, receives a part of nitrogenous base of having inhaled so that separate, and stops until desorb.
Detailed description of the invention
The processing of crystalline aluminosilicate can perhaps a lower temperature, then be heated to 320~800 ℃ under 320-800 ℃ of temperature, undertaken by it is contacted with one or more nitrogenous bases or one or more their solution or thin liquid.The treatment time that needs is depended on the kind of pure aluminium silicate, the kind and the concentration of used one or more nitrogenous bases, used temperature and pressure.Pressure for example can be from 1 to 100 crust, and is unessential except influential to the treatment time.Useful nitrogenous base generally include its molecule can infiltrate the nitrogenous base, particularly ammonia that goes in the porous system of crystalline aluminosilicate greatly and resemble the alkylamine that contains 1-6 carbon atom in the molecule such than low-alkylamine.
Nitrogenous base can use with the form of the pure form or the aqueous solution, but preferably by with becoming the gas dilution thing, for example contains from 0.5 to 10%(mole) alkali.As solvent, can be with inactive low-molecular-weight inorganic or organic solvent, for example water.As diluent for gases, can be used in inactive low-molecular-weight organic or inorganic compound under the used temperature and pressure, in reactant gases, as hydrogen or nitrogen.
After handling with nitrogenous base, then be aftertreatment, in aftertreatment, processed crystalline aluminosilicate washs it by an inert gas flow on it.If handle to be to carry out under the temperature in 320-800 ℃ of temperature range, aftertreatment is also carried out on the temperature in this scope in a similar manner, if handle to be to carry out on 320 ℃ the temperature being lower than, aftertreatment is carried out on a temperature in the 320-800 ℃ of scope.
The concentration of handling the nitrogenous base of usefulness is not crucial, make the treatment time short because the fact is high concentration, but will carry out the washing of long period with rare gas element, and the low concentration treatment time is long, but washing time is shorter.
As will be appreciated that, the temperature when finishing aftertreatment is crucial processing parameter.
Desired catalyst property is depended in the selection of the treatment temp in 320-800 ℃ of scope, low treatment temp provides a low deactivation rate and ether is synthesized relatively low activity, and a high treatment temp, then provide a higher deactivation rate, but provide simultaneously the synthetic higher activity of ether.Find that in practice in most of the cases, the 400-600 ℃ of treatment temp that scope is interior is with the catalyzer that provides to have desired characteristic.
The processing of being undertaken by foregoing invention provides one and ether formed to have almost constant activity but hydrocarbon formed to have reduces active and reduce the catalyzer of deactivation rate greatly strongly.
This advantageous effects of handling can not reckon with according to prior art, because people can't reckon with that the part of crystalline aluminosilicate activity site stops up, can produce simultaneously one and desired response had the catalyzer that has improved selective action, in other words, can not reckon with that the desorption to nitrogenous base is selectively, just on the definite activated position that ether is formed catalyzer, produce one and optionally remove obstruction.
As mentioning, known and used nitrogenous base, for example ammonia is handled crystalline aluminosilicate and can be caused the obstruction of catalyst activity position under a lesser temps, make and be used for the activity of such catalysts reduction that ether forms, and active the reduction is very significant, makes that catalyzer is with inoperative in practice.Therefore, can by the present invention with an alkali under not high temperature, as handling the virtually completely activity site of blocking catalyst under the room temperature, then by be heated to set up on 320-800 ℃ a certain temperature catalyzer to ether form specific, selectively active, this is unexpected.
Be suitable for comprising zeolite and stratified clay pit, so-called montmorillonite by the crystalline aluminosilicate that the inventive method is handled.
Based on a kind of permutite, obtain by the ZSM-5 zeolite by a kind of very useful catalysts of manufacturing of the present invention, this zeolite is described in detail in US Patent specification 3702886.In the example of this specification sheets, this zeolite is called with H-ZSM-5, and this shows that it is a hydrogen formula ZSM-5 zeolite, has explained this exchange that its normal metal ingredient and hydrogen can take place in second hurdle of US Patent specification 3702886 emphatically.
Another permutite that provides ether synthetic catalyst of great use is called as the Y-zeolite.
Also have, the natural montmorillonite of montmorillonite, particularly interlinkage can provide the very useful catalysts that alcohol is converted to ether.A kind of montmorillonite of interlinkage preferably can be produced by a kind of montmorillonite of interlinkage by US Patent specification 3798177.This catalyzer is used in the 8 described experiments of this specification sheets example.
The catalyzer of producing by the method for the invention is applicable to from alcohol produces ether, because this catalyzer has low inactivation tendency, might carry out the conversion from alcohol to ether under outlet temperature higher when adopting typical catalyst.This higher outlet temperature is favourable, because it allows to utilize the heat of reaction to produce high pressure steam.
Yet under some occasion, it is useful that the process that preparation is pure combines with the technological process that further alcohol is converted to ether.It is a kind of like this in conjunction with examples of applications producing synthin (for example gasoline) by raw mineral materials.This preparation is undertaken by the successive processing step, and one of them is that the synthesis gas that will contain carbon monoxide and hydrogen converts methyl alcohol (MeOH) to, and another step is to convert methyl alcohol to dme (DME).This two step is undertaken by following reaction formula:
Automatically set up an equilibrium state according to following skew reaction:
Show in the US Patent specification 4481305 that under the condition that has suitable catalyst to exist, will react (2), (3) and (4) lump together, and are useful in same reactor.The oxide compound of zinc and chromium, the oxide compound of zinc and aluminium, copper, chromium zinc oxide or copper, zinc, aluminum oxide are some examples of reaction (2) and (4) known catalyzer, above-mentioned metal oxide can be used with physical mixture, perhaps can utilize two kinds or three kinds of oxide compounds chemically and/or physically being bonded to a complex oxide in the oxidation structure.Some examples of the well-known catalysts that is used for reaction (3) will be mentioned in the front.But to reaction (3), utilize a catalyzer of the present invention, will find out like that as following, will the great benefit of acquisition.
Catalyzer can have active a kind of granules of catalyst and contains reacting the form of mixtures of (3) activated granules of catalyst of the present invention reaction (2) and (4) with comprising, perhaps can be with the particle form that comprises these two types of catalyzer.
Below will further describe by means of example to invention:
Example 1:
H-ZSM-5 zeolite (3 gram) is placed in the glass reactor, at an atmospheric pure N
2In the air-flow under 550 ℃, roasting one hour, the temperature in the glass reactor is adjusted to 250 ℃ afterwards, just NH
3Treatment temp, depress in that this temperature is gentle, import and comprise 0.5%NH by volume
3N
2Air-flow, this processing NH in effluent stream
3Concentration reaches by volume at 0.5% o'clock and continues half an hour, disconnects additional NH then
3, under same temperature and pressure, use pure N
2Wash this reactor assembly, until going out no longer to detect NH in the port system
3Till.Reactor cooling to room temperature, is repeated this routine described method to 10 other H-ZSM-5 samples, use NH but in 275-650 ℃ of scope, change
3The temperature of handling.
After this processing, analyze all these catalyst n H
3Content, such analytical results is indicated in the table 1, in table 1 and later table, concentration is by weight with p.p.m given.
Table 1
Treatment temp NH
3Content
℃????p.p.m
250????3860
275????2850
300????2820
325????1590
350????955
400????795
450????620
500????535
550????260
600????245
650????185
Example 2:
H-ZSM-5 zeolite (3 gram) in a glass reactor at an atmospheric pure N
2In the air-flow under 550 ℃, roasting 1 hour.
The DME catalyzer that obtains thus mixes with 1: 1 weight ratio with the MeOH catalyzer of a copper base, and it is that after the MeOH catalyst reduction, it is tested under the following conditions in 10 millimeters the microreactor that this catalyst mixture is placed in an internal diameter:
Pressure: 60Kg/Cm
2g
Temperature: 280 ℃ of constant temperature
Flow: 5, the 5Nl/h/g catalyzer
Feed gas: by volume per-cent is 5.0%CO, 3.5%CO
2,
3.0%Ar, 88.5%H
2Mixture
Experimental result is indicated on the table 2
Table 2
Time CO+CO
2The distance D ME that is transformed into the MeOH equilibrium state
Hour % ℃ of volume %
30????51.8????1????2.9
239????38.4????33????2.0
355????31.0????58????1.3
509????26.2????65????1.1
Below be applicable to table 2 and corresponding later on table.
First tabulation is shown from experiment and is begun elapsed time.
Secondary series is represented by CO that is converted during the reactor and CO
2The ratio of total content.
The distance of MeOH equilibrium state is shown in the 3rd tabulation, promptly deducts actual temperature corresponding to the equilibrium temperature by the gas composition behind the reactor path.
The content of DME in the reformed gas is shown in the 4th tabulation
Example 3:
In H-ZSM-5 zeolite (3500 gram) is placed in through being that this catalyzer is at an atmospheric pure N in 100 millimeters the tubular reactor
2Be heated to 540 ℃ in the air-flow, under same temperature and pressure, with NH
3Be added to N
2In the gas, make to obtain a volume percent and be approximately 2% NH
3The air-flow of content.This processing NH in exit flow
3Concentration reach 2% back and continued 1/2 hour, disconnect then and add NH
3, reactor assembly is used N under same temperature and pressure
2Washing no longer detects NH in going out port system
3Till.After this, with the catalyzer cool to room temperature, NH in this zeolite
3Content is about 545p.p.m by analysis.
The DME catalyzer of producing thus mixes with 2: 3 weight ratio with the MeOH catalyzer of copper base, this catalyzer is put into a reactor assembly as example 2, and test under same condition, and experimental result is indicated on the table 3.
Table 3
Time CO+CO
2The distance D ME that is transformed into the MeOH equilibrium state
Hour % ℃ of volume %
52????71.3????-5????2.9
296????68.6????-6????2.8
437????68.1????-2????2.8
725????68.1????-3????2.7
Example 4:
H-ZSM-5 zeolite (3 gram) is at one 525 ℃ NH
3As example 1, handle under the treatment temp.The DME catalyzer of producing thus mixes with the part by weight of the MeOH catalyzer of a copper base with 1: 1, and this catalyst mix image example 2 is tested like that, and experimental result is indicated on the table 4
Table 4
Time CO+CO
2The distance D ME that is transformed into the MeOH equilibrium state
Hour % ℃ of volume %
19????69.2????-7????3.1
202????67.2????-3????2.9
409????68.5????-1????2.7
Example 5:
H-ZSM-5 zeolite (1.5 gram) is in a glass reactor, in a dry hydrogen air-flow, be heated to 500 ℃, this temperature is held one hour, afterwards, catalyzer still is cooled to room temperature in the dry hydrogen air-flow, at room temperature, this air-flow is saturated with normal-butyl base amine, add altogether 0.5 milliliter just-butylamine, when exit flow not just-during butylamine, catalyzer is heated to 250 ℃ (post-processing temperatures) in the dry hydrogen air-flow, this temperature is held 1/2 hour, later cooled catalyst.After the processing, N content in the zeolite is 4200p.p.m. by analysis, the N content that is untreated in the zeolite is that the DME catalyzer that 100p.p.m produces like this mixes with the part by weight of a kind of MeOH catalyzer with 40: 60 by analysis, in mode same in the example 2 this catalyzer is tested, experimental result is indicated on the table 5.
Table 5
Time CO+CO
2The distance D ME that is transformed into the MeOH equilibrium state
Hour % ℃ of volume %
3????65.5????-5????2.5
103????61.3????-2????2.1
246????60.4????-3????2.0
416????58.9????-2????1.8
605????56.3????-1????1.6
Example 6:
H-ZSM-5 zeolite (1.5 gram) is handled in example 5 same modes, and post-processing temperature is 500 ℃.
After the processing, the N content in the zeolite is 1330p.p.m. by analysis, and the N content of untreated zeolite is 100p.p.m. by analysis.The DNE catalyzer of producing like this mixes with the part by weight of a kind of MeOH catalyzer with 40: 60, the method test identical of this catalyzer with example 2, and experimental result is indicated on the table 6.
Table 6
Time CO+CO
2The distance D ME that is transformed into the MeOH trim point
Hour % ℃ of volume %
5????69.2????-7????2.9
159????67.6????0????2.7
603????67.7????-1????2.5
940????65.5????5????2.5
Example 7:
Y-zeolite (10 gram) is to handle NH in the zeolite as the mode of H-ZSM-5 zeolite in the example 3
3Content be 1890p.p.m. by analysis, the DME catalyzer of producing like this and a kind of MeOH catalyzer are tested this catalyzer with 1: 1 mixed as the mode of example 2, experimental result is indicated on the table 7
Expression
Time CO+CO
2The distance D ME that is transformed into the MeoH equilibrium state
Hour % ℃ of volume %
17????68.6????-6????2.7
250????65.5????1????2.5
358????66.6????-1????2.7
484????65.0????3????2.6
894????59.4????11????2.3
Example 8:
Hydrogen formula montmorillonite (10 gram) is handled as the mode of H-ZSM-5 zeolite by example 3, and the DME catalyzer of producing like this mixes with the part by weight of a kind of MeoH catalyzer with 60: 40, and as example 2 detecting catalysts, its experimental result is indicated on the table 8.
Table 8
Time CO+CO
2The distance D ME that is transformed into the MeoH equilibrium state
Hour % ℃ of volume %
6????67.8????-5????2.6
154????58.3????-4????1.6
322????58.7????-5????1.6
581????57.9????-6????1.6
Example 1 has shown NH
3Absorbed dose be how to depend on temperature.
Example 2 is reference examples, shows that untreated H-ZSM-5 is deactivated with what kind of speed.
Example 3 and example 4 have shown uses NH
3The H-ZSM-5 that handles has low deactivation rate, and one is with pilot scale, and one is with laboratory scale.
Example 5 and example 6 have shown with n-butylamine the influence to the gained catalyst property of the processing of H-ZSM-5 and post-processing temperature.
Example 7 has represented to use another kind of zeolite, the result that the Y-zeolite treatment obtains.
Example 8 has shown handles the result that montmorillonite obtains.
Claims (13)
1, a kind of producing is used for the method that the catalytic alcohol dehydration becomes the alumina silicate catalyst of ether, it is characterized in that:
(a) on a temperature below 800 ℃, contact a kind of crystalline aluminosilicate, till the absorption that maximum possible takes place, then with one or more nitrogenous bases
(b) crystalline aluminosilicate that will handle like this carries out aftertreatment, and it is included under the 320-800 ℃ of temperature on crystalline aluminosilicate the part nitrogenous base that comes desorption to go out to be absorbed by an inert gas flow, and this aftertreatment proceeds to no longer and takes place till the desorption.
2, by the method for claim 1 regulation, it is characterized in that utilizing ammonia as nitrogenous base.
3, by the method for claim 1 regulation, it is characterized in that utilizing one or more low alkanamines as nitrogenous base.
4, by the method for claim 3 regulations, it is characterized in that utilizing the normal-butyl alkanamine as nitrogenous base.
5, by the method for above arbitrary claim regulation, it is characterized in that utilizing a kind of zeolite as crystalline aluminosilicate.
6, by the method for claim 5 regulations, it is characterized in that utilizing the H-ZSM-5 zeolite as said zeolite.
7, by the method for claim 5 regulations, it is characterized in that utilizing the Y-zeolite as said zeolite.
8, by the method for claim 1 to 3 any regulation, it is characterized in that utilizing montmorillonite as crystalline aluminosilicate.
9, by the method for claim 8 regulation, it is characterized in that said montmorillonite is an interlinkage natural montmorillonite.
10, by the method for above arbitrary claim regulation, it is characterized in that said absorption step (a) is to carry out on a temperature of 320-800 ℃.
11, by the method for above arbitrary claim regulation, it is characterized in that said desorption step (b) is to carry out on a temperature of 400-600 ℃.
12,, it is characterized in that said absorption step (a) under atmospheric pressure carries out by the method for above arbitrary claim regulation.
13,, it is characterized in that said desorption step (b) under atmospheric pressure carries out by the method for above arbitrary claim regulation.
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CN 85101847 CN85101847A (en) | 1984-01-10 | 1985-04-01 | A kind of ether synthetic Preparation of catalysts method that is used for |
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CN101687656B (en) * | 2007-06-29 | 2012-07-18 | Ifp公司 | Crystalline solid IZM-2 and method for the preparation thereof |
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CN101687656B (en) * | 2007-06-29 | 2012-07-18 | Ifp公司 | Crystalline solid IZM-2 and method for the preparation thereof |
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