CN1067710C - Process for preparing denitrifying oxide catalyst containing ZSM-5 zeolite - Google Patents
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Abstract
The present invention relates to a preparation method of a denitrification oxide catalyst, which comprises: a porous metal carrier contacts zeolite synthesized liquid which is crystallized to obtain a composite material of ZSM-5 zeolite and porous metal, and the porous metal carrier at least contains one porous nickel-aluminum alloy, one porous ferrum-aluminum alloy or one copper-aluminium alloy; the obtained composite material is exchanged with an ammonium ion containing solution and treated in a gas atmosphere containing inert gas or in a gas atmosphere containing the inert gas and oxygen at the temperature of higher than 650 to 1000DEG C for at least 0.5 hour and/or treated in a gas atmosphere containing water vapor at the temperature of 400 to 700DEG C for at least 0.5 hour.
Description
The invention relates to a kind of preparation method who contains the denitrifying oxide catalyst of crystal silicon-aluminate zeolite, more specifically say so about a kind of preparation method of denitrifying oxide catalyst of the ZSM-5 of containing zeolite.
The aluminosilicate zeolite in-situ crystallization is prepared the matrix material that contains zeolite become a very active research field on porous support.Under different condition zeolite crystallization can be prepared different in kind, the different matrix material that contains zeolite of purposes on different porous carrier materials, the report of this respect is existing a lot.As US3,244, the 643 disclosed methods that silico-aluminate loaded on the solid cage shape carrier with certain porosity and effective bore dia, US3,730,910 is disclosed with zeolite-loaded method on Si oxide and/or aluminum oxide, US4,511,667 disclosed zeolite-asbestos matrix materials and preparation method thereof, US4,800,187 is disclosed with the method for zeolite crystallization on monolithic ceramic matrix, US5,019, the molecular screen membrane that 263 disclosed zeolites and imporosity matrix composite form, EP0,511, the zeolite crystal film of the disclosed crystallization of 739A1 on porous matrix, the disclosed method for preparing molecular screen membrane of WO93/17781, WO93/19840 is disclosed to be deposited on zeolite method for preparing zeolite membrane on the porous support etc.
The report of matrix material that the aluminosilicate zeolite in-situ crystallization is prepared into zeolite and metal on metallic substance is also a lot.
US4,578,372 disclose the method for a kind of zeolite layer of preparation on a kind of matrix that is different from zeolite at crystalline structure, and this method comprises this matrix is contacted with a kind of reaction mixture that can form zeolite that the reacting by heating mixture makes it to form zeolite.In heat-processed, this matrix is rolled in reaction mixture zeolite is preferentially generated on stromal surface.Wherein said " zeolite " not only comprises the zeolite that silico-aluminate forms, also comprise low aluminium or be substantially free of aluminium, have zeolite structured silicate, and the four-coordination aluminium in zeolite structured is by one or more elements, as the analogue of the silico-aluminate that gallium, boron or iron replaced.Described zeolite can be y-type zeolite, A type zeolite, zeolite L, mordenite, omega zeolite or ZSM-5 zeolite.Described matrix can be metal or nonmetal.Described metal also can be the agglomerating metallic substance as being aluminium, iron, steel, stainless steel, nickel or titanium.Preferred matrix is magnetizable matrix, particularly magnetizable particle.The zeolite that obtains and the composition of matrix can be used as sorbent material in magnetic stablizing bed.
EP0,481,658A1 discloses a kind of method that deposits zeolitic material on a kind of porous support, this method comprises that the energy crystallization is immersed at least one surface of porous support to be become in the synthesized gel rubber of crystalline zeolite section bar material, make described gel crystallization, and making zeolite type material crystallization on described carrier, the surface of described carrier comprises the coatingsurface of nickel, cobalt or a molybdenum or oxide form.Suitable porous carrier materials can be a kind of porous metal, pottery, ceramal, glass, mineral, carbon, polymkeric substance etc.Typical metal such as stainless steel, Inconel(nickel alloys) etc.Adopt this method can prepare the molecular screen membrane that a kind of length and width are far longer than thickness.This molecular screen membrane mesolite section bar material directly contact also direct and carrier keyed jointing with the surface of carrier, though it be unclear that need not any caking agent between (may be chemical bond and/secondary or physical bond) zeolite and the carrier for the character of this key.
EP0,481,659A1 discloses the another kind of method that deposits a kind of zeolite type material on Lacunaris metal carrier, this method comprises at least one surface impregnation of Lacunaris metal carrier can crystallization become in the gel of crystalline zeolite section bar material, make described gel crystallization so that zeolite type material crystallization on carrier.Wherein, in being immersed in gel before, with the surface of acid treatment metallic carrier.The molecular screen membrane and the EP0 that adopt this method to prepare, the molecular screen membrane of 481658A1 preparation has close character.
EP0,481,660A1 discloses a kind of molecular screen membrane, and it contains the crystal of the zeolite type material that loads on the porous support, described zeolite type material crystals is grown on the hole of carrier basically continuously, and this zeolite type material direct crystallization is also direct and carrier keyed jointing on carrier.
People such as J.C.Jansen (Proceedings of the 9th International ZeoliteConference, Eds.R.von Ballmoos et al.PP247～254, Montreal, 1992) metallic carriers such as aluminium flake, aluminium sheet, nickel plate, copper coin, iron plate or stainless (steel) wire is earlier clean with washing with alcohol, be placed on again in the withstand voltage still of teflon lined, add zeolite synthesis liquid, make zeolite crystallization on metallic carrier, form a kind of zeolite membrane, demonstrate stronger keyed jointing power between zeolite membrane and carrier with MFI structure.
The described methods of people such as people such as H.P.Calis (February 1995 for The Canadian Journal of Chemical EngineeringVolume 73, PP119～128) employing J.C.Jansen are prepared a kind of zeolite membrane that loads on the stainless (steel) wire.The zeolite membrane that obtains after 10 hours, with the exchange of the neutralized verdigris aqueous solution, at last 100 ℃ of dryings, must be contained the catalyzer of 96.5 heavy % stainless (steel) wires, 3.5 heavy %ZSM-5 zeolites and 0.1 heavy % copper 500 ℃ of roastings.The activity of this catalyzer denitrifying oxide is much higher than commercial widely used amorphous V-Ti/SiO
2Catalyzer.
As everyone knows, the framework dealumination phenomenon easily takes place in general zeolite under hydrothermal condition, as y-type zeolite or ZSM-5 zeolite are carried out hydrothermal treatment consists at 600 ℃, all framework dealumination can take place, and this has just limited the application of zeolite catalyst in the reaction of moisture vapor atmosphere.Though disclose the matrix material of many kinds of zeolites and (porous) metal in the above-mentioned prior art, according to its description, in the matrix material of some zeolite and (porous) metal, the keyed jointing that also has certain form between zeolite and the metallic carrier, but existing zeolite but fails to solve the problem that framework dealumination easily takes place zeolite with the matrix material of (porous) metal.Simultaneously, in the matrix material of existing zeolite and (porous) metal, the bonded firmness is still undesirable between zeolite and the carrier, and this also makes existing zeolite less with the charge capacity of the matrix material mesolite of (porous) metal, just forms a kind of very thin zeolite membrane (or claiming coating) on carrier.Can more have a strong impact on its firmness if zeolite membrane is too thick.Thereby existing zeolite is general only as sorbent material or separation membrane with the matrix material of (porous) metal, and when as catalytic material, effect is undesirable.
CuZSM-5 and FeZSM-5 zeolite have the active and carbon monoxide of good decompose nitrogen oxides, OXIDATION OF HYDROCARBONS activity, are a kind of novel denitrifying oxide catalytic materials.Yet its heat, hydrothermal stability and activity stability are relatively poor, and as previously mentioned, its application in the reaction of moisture vapor atmosphere also is subjected to very big restriction.In addition, the deficiency that also has difficult forming as practical environmental protection catalyst.
Among the Catalysis Today 26,99～128,1995, the CuZSM-5 zeolite is contained NO 300ppm, CO 300ppm, C as in the nitrogen
3H
6800ppm, O
25%, H
2O 10%, CO
213% atmosphere take off the nitrogen protoxide catalyzer.Under the condition of 120 liters/hour of weight hourly space velocitys/gram, the nitrogen protoxide transformation efficiency reaches maximum value (about 40%) at about about 425 ℃.Yet with the rising of temperature of reaction, the nitrogen protoxide transformation efficiency descends gradually.There is the shortcoming of hydrothermal stability difference and activity stability difference in this explanation CuZSM-5 zeolite.
Journal of catalysis 157,603～610,1995 and Zeolites 13,602～606,1993 result of study shows, the CuZSM-5 zeolite has relatively poor heat and hydrothermal stability, and high-temperature heat treatment or hydrothermal treatment consists can cause that all the zeolite dealuminzation causes zeolite structured destruction, thereby causes forfeiture of acid position and Cu on the zeolite
2+Assemble, make catalyst deactivation.
For solving zeolite the not high shortcoming of bonded firmness between framework dealumination, zeolite and the carrier takes place easily, the applicant has invented denitrifying oxide catalyst of a kind of ZSM-5 zeolite and porous metal composite material and preparation method thereof and a kind of ZSM-5 of containing zeolite and preparation method thereof.And respectively at submitting patent application (number of patent application is 97122091.3 and 971,258 01.5) to Patent Office of the People's Republic of China on December 23rd, 1997.Described ZSM-5 zeolite and porous metal composite material contain Lacunaris metal carrier and the ZSM-5 zeolite of direct crystallization on this Lacunaris metal carrier.Wherein, described Lacunaris metal carrier contains a kind of nickel porous-aluminium, iron-aluminium or copper-aluminium alloy at least.The preparation method of described matrix material comprises a kind of Lacunaris metal carrier is contacted with a kind of zeolite synthesis liquid, and make zeolite synthesis liquid crystallization under the conventional crystallization condition of synthetic ZSM-5 zeolite, wherein, described Lacunaris metal carrier contains a kind of nickel porous-aluminium, pincers-aluminium or copper-aluminium alloy at least.The described Lacunaris metal carrier that contains a kind of nickel porous-aluminium, iron-aluminium or copper-aluminium alloy at least can adopt following method preparation: will contain the precursor of the Lacunaris metal carrier of a kind of nickel-aluminium, iron-aluminium or copper-aluminium alloy at least, handle with sodium hydroxide solution, to remove part aluminium wherein; In the described precursor, in nickel-aluminium, iron-aluminium or copper-aluminium alloy, aluminium content 10～70 heavy %; The described condition of handling precursor with sodium hydroxide solution should make that (in nickel porous-aluminium, iron-aluminium or copper-aluminium alloy weight) contains aluminium 0.1～20 heavy % in the Lacunaris metal carrier that is prepared into, in nickel porous-aluminium, copper-aluminium or iron-aluminium alloy, the specific surface of Lacunaris metal carrier is greater than 5 meters
2/ gram, pore volume is greater than 0.5 milliliter/gram.Described denitrifying oxide catalyst contains a kind of Lacunaris metal carrier and the ZSM-5 zeolite of direct crystallization on this Lacunaris metal carrier, and wherein, described Lacunaris metal carrier contains a kind of nickel porous-aluminium, iron-aluminium or copper-aluminium alloy at least.This catalyzer also contains the metal ion of a kind of IB of being selected from family metal, VIII family metal or its mixture.Described Preparation of catalysts method comprises a kind of Lacunaris metal carrier is contacted with a kind of zeolite synthesis liquid, and make zeolite synthesis liquid crystallization under the conventional crystallization condition of synthetic ZSM-5 zeolite, obtain a kind of ZSM-5 zeolite and porous metal composite material, in ZSM-5 zeolite that obtains and porous metal composite material, introduce IB family metal ion, VIII family metal ion or its mixture.
In described matrix material and the catalyzer, the ZSM-5 zeolite combines more firm than prior art with Lacunaris metal carrier, and zeolite framework aluminium is highly stable, and described catalyzer has unique catalytic performance.For example, submit the copper of changing 0.9 heavy % at described matrix material, prepare fresh CuZSM-5 and nickel porous-aluminium alloy catalytic material, the catalytic material that this is fresh respectively under 900 ℃ of air atmospheres roasting 10 hours or 600 ℃ with the argon gas hydrothermal treatment consists that contains 3 heavy % water 10 hours, make respectively 900 ℃ after the thermal treatment catalytic material and the catalytic material after 600 ℃ of hydrothermal treatment consists.Catalytic material after catalytic material after above-mentioned fresh catalytic material, the 900 ℃ of thermal treatment and the 600 ℃ of hydrothermal treatment consists is used separately as takes off nitric oxide production catalyzer under the differing temps, the result shows, catalytic material after 600 ℃ of hydrothermal treatment consists is compared with fresh catalytic material, when temperature of reaction is higher than 550K, have higher catalytic activity, particularly under each temperature of reaction, all have higher catalytic activity through the catalytic material after 900 ℃ of thermal treatment.The rule of existing C uZSM-5 catalyzer then fully in contrast.
The objective of the invention is on the basis of the applicant's foregoing invention, to provide a kind of preparation method of new denitrifying oxide catalyst.Catalyzer with this method preparation has higher activity and activity stability.
Preparation of catalysts method provided by the invention comprises a kind of Lacunaris metal carrier contacted with a kind of zeolite synthesis liquid, and makes zeolite synthesis liquid crystallization under the conventional crystallization condition of synthetic ZSM-5 zeolite, obtains a kind of ZSM-5 zeolite and porous metal composite material; Wherein, described Lacunaris metal carrier contains a kind of nickel porous-aluminium, iron-aluminium or copper-aluminium alloy at least; This method comprises that also will obtain ZSM-5 zeolite and porous metal composite material uses the solution that contains ammonium ion to exchange, and, handle with at least a method as described below:
(1) in the atmosphere that contains rare gas element or rare gas element and oxygen, under greater than 650 to 1000 ℃ temperature, handled at least 0.5 hour;
(2) in containing water vapor atmosphere, under 400～700 ℃ temperature, handled at least 0.5 hour.
According to Preparation of catalysts method provided by the invention, concrete steps are as follows:
(1) preparation of Lacunaris metal carrier.
At least the precursor that contains the Lacunaris metal carrier of a kind of nickel-aluminium, iron-aluminium or copper-aluminium alloy is handled with sodium hydroxide solution,, be prepared into the Lacunaris metal carrier that contains a kind of nickel porous-aluminium, iron-aluminium or copper-aluminium alloy at least to remove part aluminium wherein.In the weight of nickel-aluminium, iron-aluminium or copper-aluminium alloy, aluminum content can be 10～70 heavy % in the described precursor, and aluminium content should drop to 0.1～20 heavy % in the Lacunaris metal carrier that forms behind the dealuminzation, preferred 0.1～10 heavy %; Specific surface (in nickel porous-aluminium, iron-aluminium or copper-aluminium alloy) should be greater than 5 meters
2/ gram is preferably greater than 10 meters
2/ gram; Pore volume should be preferably greater than 0.7 milliliter/gram greater than 0.5 milliliter/gram.The more preferred iron-aluminium alloy of the precursor of described Lacunaris metal carrier, the more preferred porous iron-aluminium alloy of described Lacunaris metal carrier.
Wherein, the concentration of sodium hydroxide solution can change in a big way, for example, can be at the range changing of 0.5～10 mol, the scope of more preferred 1～8 mol.With sodium-hydroxide treatment nickeliferous-temperature of the precursor of aluminium, iron-aluminium or copper-aluminium alloy can and give the amount that removes aluminium according to concentration, the consumption of sodium hydroxide solution and change., large usage quantity higher when concentration of sodium hydroxide solution, give remove aluminium amount hour, treatment temp can be lower, otherwise, can be higher.Treatment temp generally changes in 30～250 ℃ of scopes, more preferred 50～200 ℃.Handling the pressure of nickeliferous-aluminium, iron-aluminium or copper-aluminium alloy precursor with sodium hydroxide solution can be at normal pressure, be higher than normal pressure or be lower than under the normal pressure and carry out.The consumption of sodium hydroxide solution can change according to giving the amount that removes aluminium, and when giving the amount that removes aluminium when big, the consumption of sodium hydroxide solution should be bigger, otherwise should be less.In general, the consumption of sodium hydroxide is excessive with respect to giving the amount that removes aluminium.The time of handling can be according to the height of concentration of sodium hydroxide solution, consumption, treatment temp, give the amount that removes aluminium changes.In general, the time of processing can 0.5 hour to hundreds of hour, preferred 1～70 hour, also available other solubility highly basic of described sodium hydroxide replaced.
Described Lacunaris metal carrier material also can be purchased and obtain, and can use existing Raney nickel (Raney Ni) as nickel porous-aluminium alloy.
When the Lacunaris metal carrier material is when containing the Lacunaris metal carrier of one deck nickel porous-aluminium, iron-aluminium or copper-aluminium alloy on the surface, this carrier can prepare with the following method: evaporation last layer aluminium on nickel, iron or copper metallic face, under inert gas atmosphere, heating more than 0.5 hour more than 800 ℃, its surface is gone up form thin layer nickel-aluminium, iron-aluminium or copper-aluminium alloy, handle this surface with sodium hydroxide solution as stated above again.Nickel, iron or copper metal can be shapes arbitrarily, as particulate state, Powdered, netted, bar-shaped, spherical, sheet, bulk, tubulose, cellular, strip etc.
(2) contain the preparation of ZSM-5 Zeolite composite materials.
The quantitative Lacunaris metal carrier that contains nickel porous-aluminium, iron-aluminium or copper-aluminium alloy is joined in the withstand voltage still, add quantitative zeolite synthesis liquid, crystallization in confined conditions heats up, extremely neutral with the deionized water wash solid product, drying, roasting must contain the matrix material of ZSM-5 zeolite.
Wherein, the compositing range of described zeolite synthesis liquid is identical with the compositing range of the zeolite synthesis liquid of the synthetic ZSM-5 zeolite of routine.For example, described zeolite synthesis liquid can have following mol ratio composition: SiO
2/ Al
2O
3＞20, Na
2O/SiO
2=0.03～2, template/SiO
2=0.03～1.5, H
2O/SiO
2=3～200.The preferred mol ratio of described zeolite synthesis liquid consists of: SiO
2/ Al
2O
3＞50, Na
2O/SiO
2=0.03～0.5, template/SiO
2=0.03～0.5, H
2O/SiO
2=15～200.Described template can be selected from template commonly used in the ZSM-5 zeolite synthesis.For example, it can be selected from various water-soluble amines, ammonium salt, quarternary ammonium salt or alkali, preferred tetraethyl ammonium hydroxide (TEA), TPAOH (TPA), Tri N-Propyl Amine or n-Butyl Amine 99, more preferred tetraethyl ammonium hydroxide (TEA) or TPAOH (TPA).The consumption of zeolite synthesis liquid at least can wetting described Lacunaris metal carrier.Under the preferable case, the weight ratio of zeolite synthesis liquid and described Lacunaris metal carrier is 5～100, more preferred 10～50.
The condition of described crystallization adopts the conventional crystallization condition of synthetic ZSM-5 zeolite.Crystallization temperature is 100～200 ℃, preferred 140～200 ℃; Crystallization time can be several hours to several days, preferred 10～120 hours, and more preferred 30～100 hours.
(3) will obtain ZSM-5 zeolite and porous metal composite material exchanges with the solution that contains ammonium ion.
Described ion-exchange can adopt conventional method to carry out, and the condition of exchange should make most of sodium ion of introducing in building-up process be replaced by ammonium ion.In general, the condition of exchange should make sodium oxide content less than 0.15 heavy %.Described ammonium ion exchange can be carried out under the following conditions: 50～100 ℃ of temperature.Be preferably 60～90 ℃; At least 0.1 hour time, be preferably 1～5 hour; Liquid-solid ratio is not less than 5, is preferably to be not less than 10.Described ammonium ion exchange can be carried out repeatedly.
(4) contain the processing of ZSM-5 Zeolite composite materials.
The matrix material that obtains is handled with at least a method as described below:
1. contain rare gas element or contain rare gas element and the atmosphere of oxygen in, handled at least 0.5 hour under greater than 650 to 1000 ℃ temperature;
2. in containing water vapor atmosphere, under 400～700 ℃ temperature, handled at least 0.5 hour.
Wherein, described rare gas element comprises one or more in nitrogen, argon gas, xenon, nitrogen, the carbonic acid gas, is preferably nitrogen and/or carbonic acid gas.The described preferred air of atmosphere that contains rare gas element and oxygen.Described contain rare gas element or contain rare gas element and the atmosphere of oxygen in handle preferred 700～900 ℃ of the temperature of matrix material, the treatment time can be very long, as can being several thousand hours even longer, but is save energy, preferred 1～10 hour of treatment time.Described containing water vapor atmosphere comprises the gas mixture of one or more and water vapour in 100% water vapour and rare gas element and the oxygen.The content of water vapour should be preferably greater than 5 body % greater than 1% in the gas mixture.Preferred 450～600 ℃ of the described temperature of handling matrix material in containing water vapor atmosphere, the treatment time can be very long, as can being several thousand hours even longer, but is save energy, preferred 1～10 hour of treatment time.
Wherein, step (3) and step (4) can be carried out in any order.
In the catalyzer of method preparation provided by the invention, when described metallic carrier is nickel porous-aluminium, iron-aluminium or copper-aluminium alloy itself, contain typical ZSM-5 zeolite diffraction peak and skeleton nickel, iron or copper diffraction peak in the x-ray diffraction spectra of the catalyzer that obtains.For example, when Lacunaris metal carrier is nickel porous-aluminium alloy, has main X-ray diffract spectral line as shown in table 1.When Lacunaris metal carrier is porous iron-aluminium alloy, has main X-ray diffract spectral line as shown in table 2.When Lacunaris metal carrier is porous copper-aluminium alloy, has main X-ray diffract spectral line as shown in table 3.
Table 1
| The d value | Relative intensity |
| 11.20 | 15～35 |
| 9.95 | 15～30 |
| 3.84 | 30～70 |
| 3.72 | 10～30 |
| 3.63 | 5～15 |
| 2.41 | 80～95 |
| 2.08 | 100 |
Table 2
| The d value | Relative intensity |
| 11.20 | 15～35 |
| 9.95 | 15～30 |
| 3.84 | 30～70 |
| 3.72 | 10～30 |
| 3.63 | 5～15 |
| 2.53 | 100 |
| 2.32 | 80～95 |
Table 3
| The d value | Relative intensity |
| 11.20 | 15～35 |
| 9.95 | 15～30 |
| 3.84 | 30～70 |
| 3.72 | 10～30 |
| 3.63 | 5～15 |
| 2.50 | 100 |
When porous carrier materials is outside surface and/or internal surface when containing the Lacunaris metal carrier of one deck nickel porous-aluminium, iron-aluminium or copper-aluminium alloy, the part beyond nickel porous-aluminium, iron-aluminium or the copper-aluminium alloy can be metallic nickel, iron, copper or wherein two or three alloy.It is different and change to utilize the XRD spectra of the catalyzer that this Lacunaris metal carrier is prepared into to look nickel porous-aluminium, iron-aluminium or copper-aluminium alloy and the content of ZSM-5 zeolite in catalyzer.When nickel porous-aluminium, iron-aluminium or copper-aluminium alloy and ZSM-5 zeolite containing in catalyzer was big, it can have the main X-ray diffract spectral line shown in table 1, table 2 or table 3 respectively.Otherwise, when the content of nickel porous-aluminium, iron-aluminium or copper two aluminium alloys and ZSM-5 zeolite too hour, the X-ray diffraction only will detect the diffraction peak less than the ZSM-5 zeolite, only occur the diffract spectral line of metallic nickel, iron and/or copper in its x-ray diffraction spectra.
The catalyzer of method provided by the invention preparation has application number, and to be that ZSM-5 zeolite that 97122091.3 described matrix materials are had combines with Lacunaris metal carrier more firm than prior art, and advantage that zeolite framework aluminium is highly stable and application number are that 97125801.5 described catalyzer have the higher denitrifying oxide activity and the advantage of activity stability.
In addition, method provided by the invention has been saved the step of carrying out ion-exchange with IB family and/or VIII family metal, directly the matrix material that Processing of Preparation becomes under high temperature or steam atmosphere.Cupric ion wherein, iron ion, nickel ion can the ion-exchange of nationality solid phase process migration to the cation-bit of zeolite, form and have highly active catalyzer.Therefore, the present invention has not only invented the method that a kind of brand-new employing solid phase ion-exchange prepares catalyzer, and this method also has simple more advantage.
Fig. 1 is the stereoscan photograph of the used porous iron-aluminium alloy of the present invention;
Fig. 2 is the stereoscan photograph of catalyzer provided by the invention.
Following example will the present invention will be further described, though used Lacunaris metal carrier is the porous carrier materials that contains porous iron-aluminium alloy in the example, but, on behalf of the used Lacunaris metal carrier of the present invention, this only limit to contain the porous carrier materials of porous iron-aluminium alloy, not thereby limiting the invention yet.
Example 1～2
The following examples illustrate the preparation of the used Lacunaris metal carrier of method provided by the invention.
Take by weighing 2.0 kilograms of iron (the heavy % of iron content 99.99, Shoudu Iron and Steel Co. produces) fusion in intermediate frequency furnace, adds 2.0 kilograms of aluminium (containing aluminium 99.99 weights, Zhengzhou Aluminium Plant's product),, naturally cool to room temperature, obtain bulk iron-aluminium alloy in 1200 ℃ of constant temperature 10 minutes.Iron-the Al alloy powder that obtains is broken into the particle of about 0.01 centimetre of diameter.
Take by weighing each 200 gram of iron-aluminum alloy granule respectively, at room temperature add the aqueous sodium hydroxide solution that quantitative concentration is 6 mol or 3 mol respectively, heat temperature raising to 90 or 180 ℃, constant temperature is taken out the aluminium regular hour, filter, to neutral, get the used Lacunaris metal carrier of the present invention, i.e. porous iron-aluminium alloy RFA1 and RFA2 with the deionized water wash solid particulate.Wherein, amplify 2600 times RFA1 stereoscan photograph as shown in Figure 1.
Table 4 has provided the concentration and the consumption of used alloy, sodium hydroxide solution, the numbering of taking out aluminium temperature and time and gained Lacunaris metal carrier, aluminium content, BET specific surface and pore volume.Wherein, aluminium content adopts plasma emission spectrometry (ICP) to measure, and BET specific surface and pore volume adopt low-temperature nitrogen adsorption method to measure.Stereoscan photograph obtains on Hittach 4000 type scanning electron microscope.Table 4
Example 3～4
| Example number | Used alloy | NaOH solution | Take out the aluminium temperature and time | Lacunaris metal carrier | |||||
| Concentration, mol | Consumption, milliliter | Temperature, ℃ | Time, hour | Numbering | Aluminium content, heavy % | Specific surface, rice 2/ gram | Pore volume, milliliter/gram | ||
| 1 | Iron-aluminium | 6 | 1000 | 90 | 3 | RFA1 | 7.15 | 90.6 | 1.4 |
| 2 | Iron-aluminium | 3 | 1500 | 180 | 48 | RFA2 | 1.75 | 15.5 | 1.1 |
Prepare catalyzer by method provided by the invention.
Take by weighing each 50 gram of Lacunaris metal carrier RFA1, RFA2 of example 1～2 preparation, join respectively in the withstand voltage still, (contain SiO with sodium hydroxide, water glass
223.5 heavy %, Chang Ling oil-refining chemical head factory is produced), TPAOH (Beijing Chemical Plant produces for TPA, chemical pure) and deionized water be made into mole and consist of 5Na
2O10TPA100SiO
27000H
2The zeolite synthesis liquid of O.1500 milliliters of zeolite synthesis liquid are joined respectively in the withstand voltage still, in confined conditions, 180 ℃ of crystallization 48 hours are filtered, the washing solid product to neutral, dry, 550 ℃ of roastings 10 hours removing template TPA wherein, ZSM-5 zeolite and porous metal composite material.With the ZSM-5 zeolite that obtains and porous metal composite material and concentration is that the aqueous ammonium chloride solution of 1 mol is 10 mixed by liquid-solid ratio, under 70 ℃ temperature, carry out ion-exchange 2 hours, with the deionized water wash solid product to there not being acid ion, 120 ℃ of oven dry, roasting is 5 hours under 700 ℃ of air atmospheres, obtains catalyst A provided by the invention and B.
Table 5 has provided used Lacunaris metal carrier, catalyzer numbering and has formed.Wherein, catalyst A and B have main X-ray diffract spectral line as shown in table 2.Amplify 2600 times catalyst A stereoscan photograph as shown in Figure 2.
Wherein, the X-ray diffract spectral line is measured with CuK α target on Simens D5000 type X-ray diffractometer.The content of the iron in the catalyzer, aluminium, sodium adopts plasma emission spectrometry (ICP) to measure, the content of silicon adopts X-ray fluorescence method to measure on the Xray fluorescence spectrometer that Japan Industrial Co., Ltd of science produces, the content of oxygen adopts weighting method to calculate and get, that is: oxygen level=100%-iron level-aluminium content-sodium content-silicone content.
Table 5
| Example number | Lacunaris metal carrier | Catalyzer | |||||
| Numbering | Form heavy % | ||||||
| Iron | Aluminium | Sodium | Silicon | Oxygen | |||
| 3 | RFA1 | A | 40.9 | 3.1 | 0.1 | 24.8 | 31.1 |
| 4 | RFA2 | B | 68.3 | 1.1 | 0.07 | 13.8 | 16.73 |
Example 5～13
Prepare catalyzer by method provided by the invention.
Method by example 4 prepares ZSM-5 zeolite and porous metal composite material, and the consumption of different is zeolite synthesis liquid is 3000 milliliters, after the ammonium ion exchange, carries out heat or hydrothermal treatment consists under the different condition respectively, catalyzer C～K provided by the invention.Treatment condition are listed in the table 6.Table 7 has provided the numbering and the composition of the catalyzer that obtains.
Wherein catalyzer C～K has main X-ray diffract spectral line as shown in table 2.
Table 6
| Example number | Used atmosphere | Treatment temp, ℃ | Treatment time, hour |
| 5 | Air | 680 | 8 |
| 6 | Air | 800 | 3 |
| 7 | Air | 850 | 2 |
| 8 | Air | 900 | 5 |
| 9 | 100% water vapour | 600 | 6 |
| 10 | Contain the air of 50 body % air and the gas mixture of water vapour | 600 | 3 |
| 11 | Contain the water vapour of 50 body % water vapour and the gas mixture of argon gas | 500 | 8 |
| 12 | Contain the water vapour of 8 body % water vapour and the gas mixture of argon gas | 600 | 1000 |
| 13 | Contain the water vapour of 8 body % water vapour and the gas mixture of nitrogen | 600 | 5 |
Table 7
Example 14
| Example number | The catalyzer numbering | Catalyzer is formed, heavy % | ||||
| Iron | Aluminium | Sodium | Silicon | Oxygen | ||
| 5 | C | 65.0 | 0.9 | 0.06 | 16.1 | 17.94 |
| 6 | D | 64.9 | 0.9 | 0.06 | 16.2 | 17.94 |
| 7 | E | 65.0 | 0.9 | 0.06 | 16.1 | 17.94 |
| 8 | F | 65.1 | 0.9 | 0.06 | 16.1 | 17.84 |
| 9 | G | 65.2 | 0.8 | 0.06 | 16.1 | 17.84 |
| 10 | H | 65.0 | 0.9 | 0.06 | 16.1 | 17.94 |
| 11 | I | 65.0 | 0.9 | 0.06 | 16.1 | 17.94 |
| 12 | J | 65.1 | 0.8 | 0.06 | 16.1 | 17.94 |
| 13 | K | 65.0 | 0.9 | 0.06 | 16.1 | 17.94 |
Prepare catalyzer by method provided by the invention.
Method by example 4 prepares catalyzer, and different is that zeolite synthesis liquid is to consist of 8Na by the mole that sodium hydroxide, water glass, TPAOH (TPA), Tai-Ace S 150 and deionized water are made into
2O15TPAAl
2O
3100SiO
27000H
2The zeolite synthesis liquid of O.Table 8 has provided the numbering and the composition of used Lacunaris metal carrier, gained catalyzer.Wherein, catalyzer L has the main X-ray diffract spectral line shown in the table 2.
Table 8
| Example number | Catalyzer | |||||
| Numbering | Form heavy % | |||||
| Iron | Aluminium | Sodium | Silicon | Oxygen | ||
| 14 | L | 47.8 | 2.5 | 0.1 | 23.0 | 26.6 |
Example 15
Prepare catalyzer by method provided by the invention.
Method by example 4 prepares catalyzer, and different is that template used dose is tetraethyl ammonium hydroxide (TEA, chemical pure, the Beijing Chemical Plant produces), the composition of zeolite synthesis liquid is also different, and the condition of ammonium ion exchange is 90 ℃ of temperature, 3 hours time, liquid-solid ratio 20.Table 9 has provided used Lacunaris metal carrier, zeolite synthesis liquid is formed, and table 10 has provided the numbering and the composition of gained catalyzer.Wherein, catalyzer M has main X-ray diffract spectral line as shown in table 2.
Table 9
| Example number | Lacunaris metal carrier | Zeolite synthesis liquid mole is formed |
| 15 | RFA2 | 5Na 2O·5TEA·100SiO 27000H 2O |
Table 10
| Example number | Catalyzer | |||||
| Numbering | Form heavy % | |||||
| Iron | Aluminium | Sodium | Silicon | Oxygen | ||
| 15 | M | 72.5 | 0.9 | 0.11 | 11.3 | 15.19 |
Example 16
Prepare catalyzer by method provided by the invention.
Method by example 4 prepares catalyzer, the different just composition differences of zeolite synthesis liquid.Table 11 has provided the composition of used Lacunaris metal carrier, zeolite synthesis liquid, and table 12 has provided the numbering and the composition of gained catalyzer.Wherein catalyst n has main X-ray diffract spectral line as shown in table 2.
Table 11
| Example number | Lacunaris metal carrier | Zeolite synthesis liquid mole is formed |
| 16 | RFA2 | 5Na 2O·10TPA·100SiO 2·10000H 2O |
Table 12
| Example number | Catalyzer | |||||
| Numbering | Form heavy % | |||||
| Iron | Aluminium | Sodium | Silicon | Oxygen | ||
| 16 | N | 82.3 | 1.0 | 0.05 | 7.4 | 9.25 |
Example 17
Prepare catalyzer by method provided by the invention.
Method by example 4 prepares catalyzer, and different is that crystallization temperature is different with crystallization time.Table 13 has provided numbering, the composition of used Lacunaris metal carrier, crystallization temperature and time and gained catalyzer.Wherein catalyzer O has main X-ray diffract spectral line as shown in table 2.
Table 13
| Example number | Lacunaris metal carrier | Crystallization process | Catalyzer | ||||||
| Temperature, ℃ | Time, hour | Numbering | Form heavy % | ||||||
| Iron | Aluminium | Sodium | Silicon | Oxygen | |||||
| 17 | RFA2 | 150 | 82 | 0 | 79.3 | 1.0 | 0.05 | 9.4 | 10.25 |
Example 18
Prepare catalyzer by method provided by the invention.
Take by weighing 50 gram iron net (0.04 centimetre of iron wire diameter respectively, voidage 50%, Shoudu Iron and Steel Co.'s product) places middle frequency furnace, put into 25 gram aluminium bits in the bottom of middle frequency furnace, feed argon gas after 1 hour, be warming up to 650 ℃, kept 1 hour, 900 ℃ of reheat 2 hours are made the sample that contains one deck iron-aluminium alloy on the iron net surface.
Take by weighing sample 20 grams that contain one deck pincers one aluminium alloy on the iron net surface that obtains, add 500 milliliters in the sodium hydroxide that concentration are 6 mol at 90 ℃, constant temperature was taken out aluminium 1.5 hours, contain the Lacunaris metal carrier of one deck porous iron-aluminium alloy, i.e. porous iron-aluminium alloy/iron net on surperficial.
Take by weighing porous iron-aluminium alloy/iron net 10 grams and join in the withstand voltage still, and in withstand voltage still, add 500 milliliters of moles respectively and consist of 5Na
2O10TPAAl
2O
3100SiO
27000H
2The zeolite synthesis liquid of O was closing under the close condition 180 ℃ of crystallization 48 hours.Filter, the washing solid product is to neutral, drying, and 550 ℃ of roastings were made ZSM-5 and porous metal composite material to remove template TPA wherein in 10 hours.Method by example 3～4 is carried out ammonium ion exchange and roasting, obtains the catalyzer of method preparation provided by the invention.Table 14 provides the numbering and the composition of catalyzer.
Table 14
| Example number | Catalyzer | |||||
| Numbering | Form heavy % | |||||
| Iron | Aluminium | Sodium | Silicon | Oxygen | ||
| 18 | P | 92.67 | 0.4 | 0.03 | 3.2 | 3.7 |
Example 19～34
Following example illustrates the catalytic performance of the catalyzer of method preparation provided by the invention.
Be in 6 millimeters the U type pipe reactor, with each 100 milligrams of internal diameter of packing into of catalyst A～P of example 1～18 preparation to contain NO, NH
3And O
2Argon gas be that reaction raw materials is estimated it and taken off nitric oxide production activity, reaction pressure is NO, NH in normal pressure, the reaction raw materials
3And O
2Content and the differential responses temperature under nitric oxide production transformation efficiency as shown in Table 15.Wherein,
Wherein, content of nitric oxide adopts QGS-08B type nitrogen-oxide analyzer, (Beijing Analytical Instrument Factory's product) analysis.
Comparative Examples 1～10 (DB1～DB10)
The catalytic performance of the following existing catalyzer of Comparative Examples explanation.
With the activity of the method evaluate catalysts of example 19～34, different is that catalyst system therefor is respectively reference catalyst Q
1, Q
2, Q
3, R
1, R
2, R
3And S
1, S
2, S
3And the porous iron-aluminium alloy RFA2 of example 2 preparations.Reaction conditions and evaluation result are listed in the table 15.
Wherein, reference catalyst Q
1, Q
2, Q
3Adopt following method preparation: HZSM-5 zeolite (Chang Ling refinery catalyst plant product) 2 grams that take by weighing silica alumina ratio 80, mix with the neutralized verdigris solution of 50 milliliters of 0.01M, stir, at room temperature carry out ion-exchange 8 hours, filter, exchange twice under the same conditions again, filter, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 12 hours, the fresh CuZSM-5 catalyzer Q1 of cupric 2.0 heavy %.Fresh CuZSM-5 catalyzer heat-treated with hydrothermal treatment consists by example 8 and 9 described conditions respectively obtain 900 ℃ of CuZSM-5 catalyzer Q after the thermal treatment respectively
2With the CuZSM-5 catalyzer Q after 600 ℃ of hydrothermal treatment consists
3
Reference catalyst R
1, R
2, R
3Adopt the preparation of following method: taking by weighing 50 gram silica alumina ratios and be 16 HZSM-5 zeolite (dying of Shanghai seven factories product) and 500 ml concns is the FeCl of 0.1 mol
2Solution mixes, and carries out ion-exchange 2 hours at 90 ℃, with the deionized water wash solid product to there not being chlorion, drying, 500 ℃ of roastings 2 hours obtain containing the fresh FeZSM-5 catalyzer R of pincers 2.52 weight %
1Fresh FeZSM-5 catalyzer heat-treated with hydrothermal treatment consists by example 8 and 9 described conditions respectively obtain 900 ℃ of FeZSM-5 catalyzer R after the thermal treatment respectively
2With the FeZSM-5 catalyzer R after 600 ℃ of hydrothermal treatment consists
3
Reference catalyst S
1, S
2, S
3Adopt the preparation of following method: silica alumina ratio is that 16 HZSM-5 zeolite (ditto) is reference catalyst S1.The HZSM-5 zeolite heat-treated with hydrothermal treatment consists by example 8 and 9 described conditions respectively obtain 900 ℃ of HZSM-5 catalyst S after the thermal treatment respectively
2With the HZSM-5 catalyst S after 600 ℃ of hydrothermal treatment consists
3
The result of table 15 shows that CuZSM-5 and FeZSM-5 are after hydro-thermal and thermal treatment, and it takes off nitric oxide production activity and all significantly descends.Simple HZSM-5 zeolite and porous iron-aluminium alloy denitrifying oxide activity is very low, does not even have the activity of denitrifying oxide.And have the activity of higher denitrifying oxide with the catalyzer of method preparation provided by the invention, and, the catalyzer of method preparation provided by the invention is the catalyzer through hydrothermal treatment consists or high-temperature heat treatment, this catalyzer that method preparation provided by the invention is described also has the stability of good heat resistanceheat resistant and hydro-thermal and good activity stability, and this is that prior art is incomparable.
Table 15
| Example number | Catalyzer | Temperature of reaction, ℃ | The reaction raw materials flow velocity, milliliters/second | NO concentration, ppm | NH3 concentration, ppm | O2 concentration, body % | The NO transformation efficiency, heavy % |
| 19 | A | 300 | 120 | 500 | 500 | 2 | 89.6 |
| 20 | B | 300 | 60 | 500 | 200 | 0.9 | 81.1 |
| 21 | C | 300 | 240 | 300 | 500 | 2 | 87.9 |
| 22 | D | 350 | 120 | 300 | 500 | 10 | 93.3 |
| 23 | E | 400 | 480 | 500 | 500 | 2 | 90.0 |
| 24 | F | 350 | 120 | 500 | 500 | 0.9 | 90.7 |
| 25 | G | 350 | 120 | 500 | 500 | 0.9 | 91.3 |
| 26 | H | 350 | 120 | 300 | 500 | 10 | 93.0 |
| 27 | I | 350 | 120 | 300 | 500 | 10 | 93.0 |
| 28 | J | 400 | 120 | 500 | 500 | 0.9 | 95.2 |
| 29 | K | 300 | 120 | 500 | 500 | 3 | 87.1 |
| 30 | L | 450 | 240 | 200 | 500 | 5 | 90.0 |
| 31 | M | 400 | 60 | 1000 | 1000 | 5 | 100 |
| 32 | N | 350 | 120 | 300 | 500 | 10 | 85.5 |
| 33 | 0 | 350 | 120 | 300 | 500 | 10 | 88.6 |
| 34 | P | 350 | 120 | 300 | 500 | 10 | 83.1 |
| DB1 | Q 1 | 350 | 120 | 300 | 500 | 10 | 40.0 |
| DB2 | Q 2 | 350 | 120 | 300 | 500 | 10 | 18.5 |
| DB3 | Q 3 | 350 | 120 | 300 | 500 | 10 | 7.4 |
| DB4 | R 1 | 350 | 120 | 300 | 500 | 10 | 56.0 |
| DB5 | R 2 | 350 | 120 | 300 | 500 | 10 | 50.3 |
| DB6 | R 3 | 350 | 120 | 300 | 500 | 10 | 32.1 |
| DB7 | S 1 | 350 | 120 | 300 | 500 | 10 | 15.0 |
| DB8 | S 2 | 350 | 120 | 300 | 500 | 10 | 8.5 |
| DB9 | S 3 | 350 | 120 | 300 | 500 | 10 | 1.1 |
| DB10 | RFA2 | 350 | 120 | 300 | 500 | 10 | 0 |
Claims (19)
1. a preparation method who contains the denitrifying oxide catalyst of ZSM-5 zeolite comprises a kind of Lacunaris metal carrier is contacted with a kind of zeolite synthesis liquid, and make zeolite synthesis liquid crystallization under the conventional crystallization condition of synthetic ZSM-5 zeolite, obtain a kind of ZSM-5 zeolite and porous metal composite material, it is characterized in that described Lacunaris metal carrier contains a kind of nickel porous-aluminium, iron-aluminium or copper-aluminium alloy at least; This method comprises that also ZSM-5 zeolite and the porous metal composite material that will obtain exchange with the solution that contains ammonium ion, and, handle with at least a method as described below:
(1) contain rare gas element or contain rare gas element and the atmosphere of oxygen in, handled at least 0.5 hour under greater than 650 to 1000 ℃ temperature;
(2) in containing water vapor atmosphere, under 400～700 ℃ temperature, handled at least 0.5 hour.
2. method according to claim 1, the preparation method who it is characterized in that described Lacunaris metal carrier comprises and will contain a kind of nickel-aluminium at least, the precursor of the Lacunaris metal carrier of iron-aluminium or copper-aluminium alloy is handled with sodium hydroxide solution, to remove part aluminium wherein, be prepared into and contain a kind of nickel porous-aluminium at least, the Lacunaris metal carrier of iron-aluminium or copper-aluminium alloy, with nickel-aluminium, the weight meter of iron-aluminium or copper-aluminium alloy, aluminum content is 10～70 heavy % in the described precursor, the condition of dealuminzation makes in the Lacunaris metal carrier that forms behind the dealuminzation aluminium content drop to 0.1～20 heavy %, with nickel porous-aluminium, iron-aluminium or copper-aluminium alloy meter, specific surface is greater than 5 meter 2/ gram, and pore volume is greater than 0.5 milliliter/gram.
3. according to the described method of claim 2, it is characterized in that should making containing aluminium 0.1～10 heavy % in the Lacunaris metal carrier that is prepared into the condition that sodium hydroxide solution is handled precursor, the specific surface of Lacunaris metal carrier is greater than 10 meters
2/ gram, pore volume are greater than 0.7 milliliter/gram.
4. according to claim 2 or 3 described methods, the concentration that it is characterized in that sodium hydroxide solution is 1～8 mol, and the temperature of handling precursor with sodium hydroxide solution is that 50～200 ℃, time are 1～70 hour.
5. method according to claim 1 and 2 is characterized in that described Lacunaris metal carrier contains a kind of porous iron-aluminium alloy.
6. according to the described method of claim 1, it is characterized in that the mol ratio of described zeolite synthesis liquid consists of: SiO
2/ Al
2O
3＞50, Na
2O/SiO
2=0.03～0.5, template/SiO
2=0.03～0.5, H
2O/SiO
2=15～200.
7. according to the described method of claim 6, it is characterized in that described template refers to tetraethyl ammonium hydroxide or TPAOH.
8. according to the described method of claim 1, it is characterized in that described crystallization condition is 100～200 ℃ of crystallization temperatures, crystallization time 10～120 hours.
9. described according to Claim 8 method is characterized in that described crystallization condition is 140～200 ℃ of crystallization temperatures, crystallization time 30～100 hours.
10. according to the described method of claim 1, it is characterized in that described ammonium ion exchange carries out under the following conditions: 50～100 ℃ of temperature, at least 0.1 hour time, liquid-solid ratio is not less than 5, and described ammonium ion exchange can be carried out repeatedly.
11. according to the described method of claim 10, it is characterized in that described ammonium ion exchange carries out under the following conditions: 60～90 ℃ of temperature, 1～5 hour time, liquid-solid ratio is not less than 10.
12., it is characterized in that described rare gas element comprises one or more in nitrogen, argon gas, xenon, nitrogen, the carbonic acid gas according to the described method of claim 1.
13., it is characterized in that described rare gas element is nitrogen and/or carbonic acid gas according to the described method of claim 12.
14., it is characterized in that the described atmosphere that contains rare gas element and oxygen refers to air according to the described method of claim 1.
15., it is characterized in that described containing water vapor atmosphere comprises the gas mixture of one or more and water vapour in 100% water vapour or rare gas element and the oxygen according to the described method of claim 1.
16. according to the described method of claim 15, the content that it is characterized in that water vapour in the described gas mixture is greater than 1 body %.
17. according to the described method of claim 16, the content that it is characterized in that water vapour in the described gas mixture is greater than 5 body %.
18. according to the described method of claim 1, it is characterized in that described contain rare gas element or contain rare gas element and the atmosphere of oxygen in handle matrix material temperature be 700～900 ℃, the treatment time is 1～10 hour.
19. according to the described method of claim 1, it is characterized in that the described temperature of handling matrix material in containing water vapor atmosphere is 450～600 ℃, the treatment time is 1～10 hour.
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| CN101257960B (en) * | 2005-09-09 | 2011-07-27 | 大阳日酸株式会社 | Molded Cu-ZSM-5 zeolite adsorbent, method of activating the same, temperature swing type adsorption apparatus, and method of purifying gas |
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| CN104843740B (en) * | 2014-02-13 | 2017-12-12 | 中国科学院过程工程研究所 | A kind of molecular sieves of ZSM 5 and preparation method thereof |
| CN112169805B (en) * | 2020-10-17 | 2022-07-29 | 重庆卡贝乐化工有限责任公司 | Cobalt-gallium catalyst for preparing low-carbon alcohol from synthesis gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578372A (en) * | 1983-12-30 | 1986-03-25 | Exxon Research & Engineering Co. | Preparation of zeolite coated substrates |
| EP0481658A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Deposition process |
| EP0481660A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Membranes |
-
1998
- 1998-11-26 CN CN98125040A patent/CN1067710C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578372A (en) * | 1983-12-30 | 1986-03-25 | Exxon Research & Engineering Co. | Preparation of zeolite coated substrates |
| EP0481658A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Deposition process |
| EP0481660A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Membranes |
Cited By (1)
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|---|---|---|---|---|
| CN101257960B (en) * | 2005-09-09 | 2011-07-27 | 大阳日酸株式会社 | Molded Cu-ZSM-5 zeolite adsorbent, method of activating the same, temperature swing type adsorption apparatus, and method of purifying gas |
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