CN1069555C - Denitrogen oxides catalyst containing ZSM-5 zeolite and method for preparation thereof - Google Patents

Abstract

A denitrification oxide catalyst containing ZSM-5 zeolite contains a porous metal carrier, ZSM-5 zeolite directly crystallized on the carrier and a metal ion selected from Group IB, Group VIII or a mixture thereof, so that The porous metal carrier contains at least one kind of porous nickel-aluminum, iron-aluminum or copper-aluminum alloy. The preparation method of the catalyst includes contacting the carrier with a zeolite synthesis liquid, making the zeolite synthesis liquid crystallization, and introducing IB group, VIII group metal ions or their mixture into the obtained ZSM-5 zeolite and porous metal composite material.

Description

Contain denitrifying oxide catalyst of ZSM-5 zeolite and preparation method thereof

The invention relates to a kind of denitrifying oxide catalyst that contains crystal silicon-aluminate zeolite and preparation method thereof, the denitrifying oxide catalyst about a kind of ZSM-5 of containing zeolite and preparation method thereof of more specifically saying so.

The CuZSM-5 zeolite has the active and carbon monoxide of good decompose nitrogen oxides, OXIDATION OF HYDROCARBONS activity, yet its heat, hydrothermal stability and activity stability are relatively poor, make the deficiency that also there is difficult forming in practical environmental protection catalyst.

Among the Catalysis Today 26,99～128,1995, the CuZSM-5 zeolite is contained NO300ppm, CO 300ppm, C as in the nitrogen ₃H ₆800ppm, O ₂5%, H ₂O10%, CO ₂13% atmosphere take off the nitric oxide catalyst, under the condition of 120 liters/hour of weight (hourly) space velocity (WHSV)s/gram, the nitric oxide conversion ratio reaches maximum (about 40%) at about about 425 ℃.Yet with the rising of reaction temperature, the nitric oxide conversion ratio descends gradually.This explanation CuZSM-5 zeolite exists hydrothermal stability difference and active steady electrically poor shortcoming.

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 catalysqt deactivation.

The Canadian Journal of Chemical Engineering, volume 73, pp 119～128, February 1995 with the ZSM-5 zeolite crystallization on stainless (steel) wire, obtain the composite of a kind of ZSM-5 zeolite and stainless (steel) wire, with the composite that obtains 500 ℃ of roastings after 10 hours, exchange with the Schweinfurt green aqueous solution, at last 100 ℃ of dryings, the catalyst that must contain Cu ZSM-5 zeolite fails to solve CuZSM-5 zeolite heat, hydrothermal stability and the not high problem of activity stability though this catalyst has solved the problem of shaping of catalyst.

The objective of the invention is to overcome and existing contain Cu ZSM-5 zeolite catalyst heat, hydrothermal stability and the not high shortcoming of activity stability, a kind of have higher heat, hydrothermal stability and higher denitrifying oxide catalyst activity stability, that contain the ZSM-5 zeolite and preparation method thereof are provided.

Catalyst provided by the invention contains a kind of Lacunaris metal carrier and the ZSM-5 zeolite of direct crystallization on this Lacunaris metal carrier, described Lacunaris metal carrier contains a kind of nickel porous-aluminium at least, iron-aluminium or copper-aluminium alloy, this catalyst also contains a kind of metal ion that is selected from I B family metal, VIII family metal or its mixture, and this metal ion exists with the form of oxide.

Preparation of catalysts method provided by the invention comprises the synthetic liquid of a kind of Lacunaris metal carrier and a kind of zeolite is contacted, make the synthetic liquid of zeolite crystallization under the conventional crystallization condition of synthetic ZSM-5 zeolite, and in the composite of ZSM-5 zeolite that obtains and Lacunaris metal carrier, introduce I B family metal ion, VIII family metal ion or its mixture, described Lacunaris metal carrier contains a kind of nickel porous-aluminium at least, iron-aluminium or copper-aluminium alloy.

According to catalyst provided by the invention, described Lacunaris metal carrier can be nickel porous-aluminium, iron-aluminium or copper-aluminium alloy itself, also can be the Lacunaris metal carrier that outer surface and/or inner surface contain one deck nickel porous-aluminium, iron-aluminium or copper-aluminium alloy.

When described Lacunaris metal carrier is nickel porous-aluminium, iron-aluminium or copper-aluminium alloy itself, contain the diffraction maximum of typical ZSM-5 zeolite diffraction maximum and skeleton nickel, iron or copper in the x-ray diffraction spectra of composite.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 that outer surface and/or inner surface are when containing the Lacunaris metal carrier of one deck nickel porous-aluminium, iron-aluminium or copper-aluminium alloy, 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 can be a different shape, as graininess, Powdered, netted, bar-shaped, spherical, sheet, bulk, tubulose, cellular, strip etc.Utilize the XRD spectra of the composite that this Lacunaris metal carrier is prepared into, look nickel porous-aluminium, iron-aluminium or copper-aluminium alloy and the ZSM-5 zeolite content in composite is different and change, when nickel porous-aluminium, when iron-aluminium or copper-aluminium alloy and the content of ZSM-5 zeolite in composite are big, it can have respectively as table 1, main X-ray diffract spectral line shown in table 2 or the table 3, otherwise, when nickel porous-aluminium, iron-aluminium or copper-aluminium alloy and ZSM-5 zeolite content are too hour, the X-ray diffractometer will detect the diffraction maximum less than the ZSM-5 zeolite, only occur metallic nickel in its x-ray diffraction spectra, the diffract spectral line of iron and/or copper.

According to catalyst provided by the invention, be benchmark with nickel porous-aluminium, iron-aluminium or copper-aluminium alloy, the Lacunaris metal carrier specific surface is greater than 5 meters ²/ gram is preferably greater than 10 meters ²/ gram, pore volume are preferably greater than 0.7 milliliter/gram greater than 0.5 milliliter/gram.

According to catalyst provided by the invention, gross weight with nickel porous-aluminium, iron-aluminium or copper-aluminium alloy, zeolite and metal oxide is a benchmark, the content of nickel, iron or copper preferred 25～95 heavy % in the catalyst, more preferred 35～85 heavy %, aluminium content preferred 0.1～10 heavy %, more preferred 0.1～5.0 heavy %, silicone content preferred 3.0～40 heavy %, more preferred 5.0～30 heavy %, the content of I B family, VIII family metal ion or its mixture preferred 0.1～10 heavy %, more preferred 0.1～5 heavy %.

Described I B family metal ion can be selected from copper or silver ion, the preferably copper ion.Described VIII family metal ion can be selected from iron ion, cobalt ions, nickel ion, ruthenium ion, rhodium ion, palladium ion, osmium ion, iridium ion or platinum ion, more preferred iron ion or nickel ion.

Catalyst provided by the invention also can contain the metal ion of III B family, IV B family, V B family, VI B family, VII B family, and its content can be 0～5 heavy % of total catalyst weight.

Also can contain 1 heavy %, the following Na of preferred 0.5 heavy % in the catalyst provided by the invention ₂O.

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.Weight in nickel-aluminium, iron-aluminium or copper-aluminium alloy, aluminum content can be 10～70 heavy % in the described precursor, aluminium content should drop to 0.1～20 heavy % in the Lacunaris metal carrier that forms behind the dealuminzation, and 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.

Wherein the concentration of sodium hydroxide solution can change in a big way, as can be at the range changing of 0.5～10 mol, and the scope of more preferred 1～8 mol.With naoh 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 temperature can be lower, otherwise, can be higher, treatment temperature 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, and in general, the consumption of NaOH 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 temperature, give the amount that removes aluminium changes, in general, the time of handling can 0.5 hour to hundreds of hour, preferred 1～70 hour, also available other solubility highly basic of described NaOH replaced.

Described porous alloy carrier 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 the copper metallic face of arbitrary shape, under inert gas atmosphere,, its surface gone up form thin layer nickel-aluminium, iron-aluminium or copper-aluminium alloy, handle this surface with sodium hydroxide solution as stated above again more than 0.5 hour in heating more than 800 ℃.

(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 the synthetic liquid of quantitative zeolite, crystallization in confined conditions heats up, spend the deionised water solid product to neutral, drying, roasting must contain the composite of ZSM-5 zeolite.

Wherein, the compositing range of the synthetic liquid of described zeolite is identical with the compositing range of the synthetic liquid of zeolite of conventional synthetic ZSM-5 zeolite, and for example, the synthetic liquid of described zeolite can have following mol ratio and form: SiO ₂/ Al ₂O ₃＞20, Na ₂O/SiO ₂=0.03～2, template agent/SiO ₂=0.03～1.5, H ₂O/SiO ₂=3～200.The synthetic preferred mol ratio of liquid of described zeolite consists of: SiO ₂/ Al ₂O ₃＞50, Na ₂O/SiO ₂=0.03～0.5, template agent/SiO ₂=0.03～0.5, H ₂O/SiO ₂=15～200.Described template agent can be selected from the ZSM-5 zeolite synthetic in template agent commonly used, can be selected from various water-soluble amines, ammonium salt, quarternary ammonium salt or alkali as it, preferred tetraethyl ammonium hydroxide (TEA), TPAOH (TPA), n-propylamine or n-butylamine, more preferred tetraethyl ammonium hydroxide (TEA) or TPAOH (TPA).The weight ratio of synthetic liquid of zeolite and Lacunaris metal carrier can in very large range change this weight ratio preferred 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 ℃, and preferred 140～200 ℃, crystallization time can be several hours to several days, preferred 10～120 hours, and more preferred 30～100 hours.

Described drying and roasting can be adopted conventional method, and wherein the purpose of roasting is for removing the template agent in the composite, and sintering temperature be as can being 450～650 ℃, roasting time 2～20 hours.

Na in the synthetic liquid of described zeolite ₂O also can replace with other alkali metal ion or alkaline-earth metal ions.Described other alkali metal ion can be lithium, potassium, rubidium, caesium, and alkaline-earth metal ions can be beryllium, magnesium, calcium, strontium, barium etc.

(3) introducing of metal ion

The introducing of I B family metal ion, VIII family metal ion can be adopted conventional method, as adopting ion-exchange or infusion process.When adopting ion-exchange, can will contain the composite of ZSM-5 zeolite earlier with containing NH ₄ ⁺The ion solution exchange makes Na wherein once to for several times ₂O content is reduced to 1.0 and is weighed below the %, with the solution exchange that contains I B family metal cation, VIII family metal cation once extremely for several times, makes the content of I B family's metal ion or VIII family metal ion reach predetermined value, then drying, roasting or not roasting again.Also can make the content of I B family's metal ion or VIII family metal ion reach predetermined value, then drying, roasting or not roasting directly once extremely for several times with the solution exchange that contains I B family's metal cation or VIII family metal cation.When using infusion process, can will contain the composite of ZSM-5 zeolite earlier with containing NH ₄ ⁺The ion solution exchange makes wherein Na once to for several times ₂O content drops to below the 1.0 heavy %, again with contain I B family's metal ion or VIII family metal ion solution impregnation.

When catalyst provided by the invention contained III B family, IV B family, V B family, VI B family, VII B family metal ion, the introducing of these metal ions also can be carried out with reference to said method.

Catalyst provided by the invention has the heat higher than prior art, hydrothermal stability and activity stability.

(1) in the catalyst provided by the invention, the ZSM-5 zeolite is more firm with combining of Lacunaris metal carrier.For example, the catalyst of nickeliferous or iron 40.3～92.7 heavy %, silicon 3.1～27.0 heavy %, nickel, iron or copper ion 0.4～3.0 heavy % provided by the invention was handled 10 hours with the argon gas that contains 3 heavy % water or roasting 10 hours or handled 1000 hours with argon gas at 400 ℃ in 900 ℃ of air at 600 ℃ respectively, and the weight loss of the catalyst after the processing has only 0.1～0.7 heavy %.And, handled the existing CuZSM-5/ stainless steel catalyst that contains stainless steel 94.5 heavy %, silicon 2.4 heavy %, copper ion 0.3 heavy % 10 hours with the argon gas that contains 3 heavy % water at 600 ℃, the weight loss of the CuZSM-5/ stainless steel catalyst after the processing reaches 4.1 heavy %.It should be noted that silicone content (zeolite content) in the catalyst provided by the invention far above CuZSM-5/ stainless steel catalyst, if when CuZSM-5/ stainless steel catalyst contains so high zeolite, its firm degree will be lower.

(2) framework aluminum of ZSM-5 zeolite is highly stable in the catalyst provided by the invention, and this is that prior art is incomparable.For example, the catalyst with nickeliferous 78.5 heavy % provided by the invention, aluminium 1.0 heavy %, silicon 9.1 heavy %, copper ion 1.1 heavy % weighs %H at 600 ℃ with containing 3 ₂The argon gas of O was handled after 10 hours, the ratio of catalyst mesolite framework aluminum and non-framework aluminum does not change before and after handling, and under the same conditions, the CuZSM-5 zeolite being carried out hydrothermal treatment consists, the ratio of framework aluminum and non-framework aluminum reduces significantly in the CuZSM-5 zeolite after the processing.

(3) catalyst provided by the invention has higher heat, hydrothermal stability and activity stability and also shows, catalyst provided by the invention has higher catalytic activity after heat treatment or hydrothermal treatment consists, and existing CuZSM-5 zeolite catalyst its catalytic activity after heat or hydrothermal treatment consists descends significantly.For example, with provided by the invention nickeliferous 78.5 heavy %, aluminium 1.0 heavy %, silicon 9.1 heavy %, the roasting 10 hours under 900 ℃ of air atmospheres respectively of the catalyst of copper 1.1 heavy %, or at 600 ℃ with the argon gas hydrothermal treatment consists that contains 3 heavy % water after 10 hours, be used separately as together with fresh catalyst and take off nitric oxide production catalyst under the different temperatures, the result shows, catalyst after the hydrothermal treatment consists is compared with fresh catalyst, when being higher than 550 ℃, reaction temperature has higher catalytic activity, catalyst is after heat treatment compared with fresh catalyst, all has higher catalytic activity under each reaction temperature.This has very important significance for the denitrifying oxide catalyst that uses under high temperature or high temperature moisture vapor atmosphere.

Catalyst provided by the invention has higher activity stability and shows that also it has the long-life.For example, with copper ions 0.4 heavy % provided by the invention, iron 92.7 heavy %, aluminium 0.4 heavy %, silicon 3.1 heavy %, oxygen 3.4 heavy %, with porous iron-aluminium alloy/iron net is that catalyst that carrier contains the ZSM-5 zeolite is when being used to take off the nitric oxide reaction, have only 100 milligrams in the catalyst loading amount, 300 ℃ of reaction temperatures, gas (consists of NO5000ppm, NH ₃5000ppm, O ₂0.9 heavy %, all the other are argon gas) under the condition of flow 120 ml/min, react 1000 hours rear catalyst activity and do not fall as follows.

Above-mentioned statement of facts catalyst provided by the invention has wide prospect in industrial application.

Catalyst provided by the invention is except that being particularly suitable for as also being particularly suitable for the denitrifying oxide catalyst as carbon monoxide, hydrocarbon oxidation catalyst.The process conditions that catalyst uses are the common process conditions of each reaction.

Fig. 1 be before the hydrothermal treatment consists provided by the invention copper ions be the Al2P XPS spectrum figure of the catalyst that contains the ZSM-5 zeolite of carrier with nickel porous-aluminium alloy;

Fig. 2 be after the hydrothermal treatment consists provided by the invention copper ions be the Al2P XPS spectrum figure of the catalyst that contains the ZSM-5 zeolite of carrier with nickel porous-aluminium alloy;

Fig. 3 is the Al2PXPS spectrogram of CuZSM-5 zeolite catalyst before the hydrothermal treatment consists;

Fig. 4 is the Al2PXPS spectrogram of CuZSM-5 zeolite catalyst after the hydrothermal treatment consists;

Fig. 5 be provided by the invention fresh, through the copper ions of 900 ℃ of heat treatments and 600 ℃ of hydrothermal treatment consists with nickel porous-aluminium alloy be the catalyst that contains the ZSM-5 zeolite of carrier when being used to take off the nitric oxide reaction nitric oxide conversion ratio with the variation diagram of reaction temperature;

Fig. 6 be fresh, when the CuZSM-5 zeolite catalyst of 900 ℃ of heat treatments and 600 ℃ of hydrothermal treatment consists is used to take off the nitric oxide reaction nitric oxide conversion ratio with the variation diagram of reaction temperature;

Fig. 7 be copper ions provided by the invention with porous iron-aluminium alloy/iron net be the catalyst that contains the ZSM-5 zeolite of carrier when being used to take off the nitric oxide reaction nitric oxide conversion ratio with the variation diagram in reaction time.

The following examples will the present invention will be further described.

Example 1～4

Following example illustrates the preparation of Lacunaris metal carrier in the catalyst provided by the invention.

Take by weighing 2.0 kilograms of iron (iron content 99.99 heavy % respectively, Shoudu Iron and Steel Co. produces) or copper (cupric 99.99 heavy %, produce in the copper work, Luoyang), fusion in intermediate frequency furnace, add 2.0 kilograms of aluminium (contain the heavy % of aluminium 99.99, Zhengzhou Aluminium Plant produces) respectively, in 1200 ℃ of constant temperature 10 minutes, naturally cool to room temperature, obtain bulk iron-aluminium or copper-aluminium alloy.Respectively iron-aluminium, the copper-Al alloy powder that obtains is broken into the particle of about 0.01 centimetre of diameter.

Take by weighing nickel-aluminum alloy granule (nickeliferous and each 50 heavy % of aluminium respectively; about 0.01 centimetre of particle diameter; Shanghai chemical reagents corporation produces); iron-aluminium, each 200 gram of copper-aluminum alloy granule; at room temperature add the sodium hydrate aqueous solution that quantitative concentration is 6 mol respectively; heat temperature raising to 90 or 180 ℃; constant temperature is taken out the aluminium regular hour; filter; spend the deionised water solid particle to neutral, get the used Lacunaris metal carrier nickel porous-aluminium alloy of the present invention, porous iron-aluminium alloy and porous copper-aluminium alloy.

Table 4 has provided used alloy, sodium hydroxide solution consumption, has taken out the numbering of aluminium temperature and time and gained Lacunaris metal carrier, aluminum 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.

Table 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	Nickel-aluminium	6	1000	180	48	RNA	1.20									12.5	1.2
2	Iron-aluminium									6	1000	90	3	RFA1	7.15	90.6	1.4
		3	Iron-aluminium	3	1500	180	48	RFA2	1.75									15.5	1.1
4	Copper-aluminium									6	1000	180	48	RCA	0.96	17.5	1.0

Example 5～8

Following example illustrates Preparation of catalysts provided by the invention.

Take by weighing Lacunaris metal carrier RNA, RFA1, RFA2, and each 50 gram of RCA of example 1～4 preparation, join respectively in the withstand voltage still, (contain SiO with NaOH, waterglass 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 of O synthesizes liquid.The synthetic liquid of 1500 milliliters of zeolites is joined respectively in the withstand voltage still, and in confined conditions, 180 ℃ of crystallization 48 hours are filtered, the washing solid product to neutral, dry, 550 ℃ of roastings 10 hours to remove template agent TPA wherein.

Taking by weighing 50 grams through the sample of 550 ℃ of roastings after 10 hours, is that the ammonia spirit of 0.1 mol mixes with 500 ml concns, stirring at room temperature, carried out ion-exchange 8 hours, and filtered, under similarity condition, exchange twice again, filter 110 ℃ of dryings 12 hours, 550 ℃ of roastings 2 hours.The solid product that obtains is used quantitative Schweinfurt green (chemical pure, Beijing lean reagent company produces), ferric nitrate (chemical pure respectively, Beijing lean reagent company produces) solution or nickel nitrate (chemical pure, Beijing lean chemical reagents corporation produces) mix, at room temperature stir, carry out ion-exchange hour, filter, under similarity condition, exchange twice again, filter, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 12 hours, the catalyst provided by the invention of cupric, iron or nickel ion.

Table 5 has been listed used Lacunaris metal carrier, Schweinfurt green solution usage, iron nitrate solution consumption, nickel nitrate solution consumption, and table 6 is listed catalyst and formed.Wherein catalyst A has main X-ray diffract spectral line as shown in table 1, and catalyst B and C have main X-ray diffract spectral line as shown in table 2.Catalyst D has main X-ray diffract spectral line as shown in table 3.

Wherein, the X-ray diffract spectral line is measured with CuK α target on Simens D5000 type X-ray diffractometer.The content of the nickel in the catalyst, iron, copper, aluminium, sodium and nickel ion, iron ion and copper ion 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 gravimetric method to calculate and get, that is: oxygen content=100%-nickel (or iron or copper) content-aluminium content-sodium content-nickel (or iron or copper) ion concentration-

Silicone content.

Table 5

Example number	Lacunaris metal carrier	The solution kind	Solution concentration, mole rises	Solution usage, milliliter
					5	RNA	Schweinfurt green solution	0.01	1500
6	RFA1	Iron nitrate solution	0.01	3000
					7	RFA2	Iron nitrate solution	0.02	2000
8	RCA	Nickel nitrate solution	0.01	3000

Table 6

Example number	Catalyst
												Numbering	Form heavy %
	Nickel	Iron	Copper	Aluminium	Sodium	Silicon	Oxygen	Nickel ion	Copper ion	Iron ion
											5		A	78.5	-	-	1.0	0.1	9.1	10.2	-	1.1	-
6	B	-	40.3	-	3.1	0.2	24.8	28.6	-	-		3.0
											7		C	-	67.9	-	1.1	0.1	13.8	15.9	-	-	1.2
8	D	-	-	74.3	0.7	0.1	11.2	11.7	2.0	-		-

Example 9～13

The following examples illustrate Preparation of catalysts provided by the invention.

Method by example 5～8 prepares catalyst, the consumption difference of the different synthetic liquid of just zeolite, and the concentration of Schweinfurt green solution, iron nitrate solution and nickel nitrate solution is also different with consumption.

Table 7 has provided the concentration and the consumption of used Lacunaris metal carrier, the synthetic liquid consumption of zeolite, Schweinfurt green solution, iron nitrate solution or nickel nitrate solution.Table 8 has provided the catalyst composition.Wherein catalyst E, F have main X-ray diffract spectral line as shown in table 1.G has main X-ray diffract spectral line as shown in table 2.H, I have main X-ray diffract spectral line as shown in table 3.

Table 7

Example number	Lacunaris metal carrier	Zeolite synthesizes the liquid consumption, milliliter	The solution kind	Solution concentration, mole rises	Solution usage, milliliter
						9	RNA	3000	Schweinfurt green solution	0.005	5000
10	RNA	3600	Schweinfurt green solution	0.01	2000
						11	RFA2	3000	Nickel nitrate solution	0.05	3000
12	RCA	3000	Schweinfurt green solution	0.01	3000
						13	RCA	3600	Iron nitrate solution	0.02	2000

Table 8

Example number	Catalyst
												Numbering	Form heavy %
	Nickel	Iron	Copper	Aluminium	Sodium	Silicon	Oxygen	Nickel ion	Copper ion	Iron ion
											9		E	50.3	-	-	0.6	0	22.4	25.6	-	1.1	-
10	F	39.3	-	-	0.4	0	28.5	31.2	-	0.6		-
											11		G	-	40.3	-	0.6	0.1	27.0	31.0	1.0	-	-
12	H	-	-	42.4	0.5	0	26.2	30.0	-	0.9		-
											13		I	-	-	37.4	0.4	0	28.9	32.7	-	-	0.6

Example 14～16

Following example illustrates Preparation of catalysts provided by the invention.

Method by example 5～8 prepares catalyst, and the different synthetic liquid of just zeolite are to consist of 8Na by the mole that NaOH, waterglass, TPAOH (TPA), aluminum sulfate and deionized water are made into ₂O15TPAAl ₂O ₃100SiO ₂7000H ₂The zeolite of O synthesizes liquid, and the concentration of Schweinfurt green solution, iron nitrate solution and nickel nitrate solution is also different with consumption.

Table 9 has provided the concentration and the consumption of used Lacunaris metal carrier, Schweinfurt green solution, iron nitrate solution and nickel nitrate solution, and table 10 has provided the catalyst composition.

Wherein catalyst J, K, L have the main X-ray diffract spectral line shown in table 1,2,3 successively.

Table 9

Example number	Lacunaris metal carrier	The solution kind	Solution concentration, mole rises	Solution usage, milliliter
					14	RNA	Ferric nitrate	0.01	3000
15	RFA2	Schweinfurt green	0.005	5000
					16	RCA	Nickel nitrate	0.02	2000

Table 10

Example number	Catalyst
												Numbering	Form heavy %
	Nickel	Iron	Copper	Aluminium	Sodium	Silicon	Oxygen	Nickel ion	Copper ion	Iron ion
											14		J	51.7	-	-	2.1	0.1	20.5	23.5	-	-	2.1
15	K	-	47.4	-	2.5	0.1	22.0	25.6	-	2.4		-
											16		L	-	-	47.0	3.0	0.1	22.5	25.4	2.0	-	-

Example 17

This example illustrates Preparation of catalysts provided by the invention.

Method by example 5 prepares catalyst, and the mole of the different synthetic liquid of just zeolite consists of 5Na ₂O5TPA100SiO ₂7000H ₂O, the catalyst that obtains are M.M has main X-ray diffract spectral line as shown in table 1, and has following composition: nickel 78.1 heavy %, aluminium 1.0 heavy %, sodium 0.1 heavy %, silicon 9.2 heavy %, oxygen 10.5 heavy %, copper ion 1.1 heavy %.

Example 18～21

Following example illustrates Preparation of catalysts provided by the invention.

Method by example 5～8 prepares catalyst, different is template used dose is tetraethyl ammonium hydroxide (TEA, chemical pure, the Beijing Chemical Plant produces), the composition of the synthetic liquid of zeolite and the concentration of Schweinfurt green solution, iron nitrate solution and nickel nitrate solution are also different with consumption.

Table 11 has provided the synthetic liquid of used Lacunaris metal carrier, zeolite forms, and table 12 has provided the concentration and the consumption of Schweinfurt green, ferric nitrate, nickel nitrate solution, and table 13 has provided the composition of catalyst.Wherein catalyst n has main X-ray diffract spectral line as shown in table 1, and O has main X-ray diffract spectral line as shown in table 2, and P and Q have main X-ray diffract spectral line as shown in table 3.

Table 11

Example number	Lacunaris metal carrier	The synthetic liquid mole of zeolite is formed
			18	RNA	5Na 2O·10TEA·100SiO 2·7000H 2O
19	RFA2	5Na 2O·5TEA·100SiO 2·7000H 2O
			20	RCA	5Na 2O·8TEA·100SiO 2·7000H 2O
21	RCA	5Na 2O·10TEA·100SiO 2·7000H 2O

Table 12

Example number	The solution kind	Solution concentration, mole rises	Solution usage, milliliter
				18	Schweinfurt green solution	0.01	1500
19	Schweinfurt green solution	0.01	1500
				20	Nickel nitrate solution	0.05	3000
21	Iron nitrate solution	0.02	2000

Table 13

Example number	Catalyst
												Numbering	Form heavy %
	Nickel	Iron	Copper	Aluminium	Sodium	Silicon	Oxygen	Nickel ion	Copper ion	Iron ion
											18		N	71.8	-	-	0.9	0	12.2	14.1	-	1.0	-
19	O	-	79.0	-	1.0	0.1	9.1	9.8	-	1.0
											20		P	-	-	80.0	0.8	0	8.7	9.7	0.8	-	-
21	Q	-	-	80.0	0.8	0	8.7	9.7	-	-		0.8

Example 22～24

Following example illustrates Preparation of catalysts provided by the invention.

Method by example 5～8 prepares catalyst, the composition difference of the different synthetic liquid of just zeolite, and the concentration of Schweinfurt green solution, iron nitrate solution and nickel nitrate solution is also different with consumption.

Table 14 provided the composition of the synthetic liquid of used Lacunaris metal carrier, zeolite, and table 15 has provided the concentration and the consumption of Schweinfurt green, nickel nitrate, iron nitrate solution, and table 16 has provided the catalyst composition.Wherein catalyst R, S, T have the main X-ray diffract spectral line shown in table 1,2,3 successively.

Table 14

Example number	Lacunaris metal carrier	The synthetic liquid mole of zeolite is formed
			22	RNA	5Na 2O·10TPA·100SiO 2·5000H 2O
23	RFA2	5Na 2O·10TPA·100SiO 2·10000H 2O
			24	RCA	5Na 2O·10TPA·100SiO 2·15000H 2O

Table 15

Example number	The solution kind	Solution concentration, mole rises	Solution usage, milliliter
				22	Schweinfurt green solution	0.01	3000
23	Iron nitrate solution	0.02	2000
				24	Nickel nitrate solution	0.05	3000

Table 16

Example number	Catalyst
												Numbering	Form heavy %
	Nickel	Iron	Copper	Aluminium	Sodium	Silicon	Oxygen	Nickel ion	Copper ion	Iron ion
											22		R	60.4	-	-	1.0	0.1	17.2	19.8	-	1.5	-
23	S	-	82.0	-	1.0	0.1	7.4	8.4	-	-		0.9
											24		T	-	-	84.2	1.0	0.1	6.3	7.3	1.1	-	-

Example 25～27

Following example illustrates Preparation of catalysts provided by the invention.

Method by example 5 and 7 prepares catalyst, and different is that crystallization temperature is different with crystallization time, and the concentration of Schweinfurt green solution, iron nitrate solution, nickel nitrate solution is also different with consumption.

Table 17 has provided used Lacunaris metal carrier, crystallization temperature and time, and table 18 has provided the concentration and the consumption of Schweinfurt green solution, iron nitrate solution, nickel nitrate solution, and table 19 provided the catalyst composition.Wherein catalyst U has main X-ray diffract spectral line as shown in table 1, and V and W have main X-ray diffract spectral line as shown in table 2.

Table 17

Example number	Lacunaris metal carrier	Crystallization temperature, ℃	Crystallization time, hour
				25	RNA	160	70
26	RFA2	150	82
				27	RFA2	170	40

Table 18

Example number	The solution kind	Solution concentration, mole rises	Solution usage, milliliter
				25	Schweinfurt green solution	0.01	1500
26	Iron nitrate solution	0.02	3000
				27	Nickel nitrate solution	0.05	3000

Table 19

Example number	Catalyst
												Numbering	Form heavy %
	Nickel	Iron	Copper	Aluminium	Sodium	Silicon	Oxygen	Nickel ion	Copper ion	Iron ion
											25		U	78.0	-	-	1.0	0.1	9.2	10.6	-	1.1	-
26	V	-	79.0	-	1.0	0.1	9.1	9.8	-	-		1.0
											27		W	-	-	84.2	1.0	0.1	6.3	7.3	1.1	-	-

Example 28～29

Following example illustrates Preparation of catalysts provided by the invention.

Take by weighing 100 gram iron net (0.04 centimetre of iron wire diameter respectively, voidage is 50%, Shoudu Iron and Steel Co. produces) and copper mesh (0.02 centimetre of brass wire diameter, voidage are 80%, copper work, Luoyang product) place middle frequency furnace, put into 50 gram aluminium bits in the middle frequency furnace bottom, feed argon gas after 1 hour, be warming up to 650 ℃, kept 1 hour, heated again 2 hours in 900 ℃, make on the iron net surface and the copper mesh surface on contain the sample of one deck iron-aluminium and copper-aluminium alloy.

Take by weighing each 50 gram of sample of iron content-aluminium and copper-aluminium alloy on the surface that obtains, add 1250 milliliters in the NaOH that concentration is the 6M mol 90 ℃ and 180 ℃ respectively, constant temperature was taken out aluminium 1.5 hours, contain the Lacunaris metal carrier of one deck porous iron-aluminium, copper-aluminium alloy, porous iron-aluminium alloy/iron net and porous copper-aluminium alloy/copper mesh on surperficial.

Take by weighing each 20 gram of porous iron-aluminium alloy/iron net and porous copper-aluminium alloy/copper mesh and join respectively in the withstand voltage still, and in withstand voltage still, add 1000 milliliters of moles respectively and consist of 5Na ₂O10TPAAl ₃O ₃100SiO ₂7000H ₂The zeolite of O synthesizes liquid, is closing under the close condition 180 ℃ of crystallization 48 hours, filters, the washing solid product is to neutral, drying, 550 ℃ of roastings were made the composite of ZSM-5 and porous iron-aluminium alloy/iron net and ZSM-5 and porous copper-aluminium alloy/copper mesh to remove template agent TPA wherein in 10 hours.

Take by weighing 10 gram ZSM-5 zeolite and porous iron-aluminium alloy/iron net and ZSM-5 zeolite and porous copper-aluminium alloy/copper mesh composites respectively, be that 0.1 mol ammonia spirit mixes with 250 ml concns respectively, at room temperature carry out ion-exchange 8 hours, filter, under similarity condition, exchange twice again, filter 110 ℃ of dryings 12 hours, 550 ℃ of roastings 2 hours.The solid product that obtains mixes with Schweinfurt green solution and iron nitrate solution respectively, at room temperature carried out ion-exchange 8 hours, filters, again twice of similarity condition exchange, filter, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 12 hours, catalyst X provided by the invention and Y.

Table 20 has been listed the concentration and the consumption of used Lacunaris metal carrier and Schweinfurt green solution and iron nitrate solution, and table 21 has been listed the composition of catalyst X and Y.

Table 20

Example number	Used Lacunaris metal carrier	The solution kind	Solution concentration, mol	Solution usage, milliliter
					28	Porous iron-aluminium alloy/iron net	Schweinfurt green solution	0.01	1500
29	Porous copper-aluminium alloy/copper mesh	Iron nitrate solution	0.01	5000

Table 21

Example number	Catalyst
										Numbering	Form heavy %
	Copper	Iron	Aluminium	Sodium	Silicon	Oxygen	Copper ion	Iron ion
									28		X	-	92.7	0.4	0	3.1	3.4	0.4	-
29	Y	89.4	-	0.7	0	3.9	4.3	-		1.7

Example 30～37

Following example illustrates the firmness that the ZSM-5 zeolite combines with Lacunaris metal carrier in the catalyst provided by the invention.

Accurately take by weighing each 5.00 gram of composite A, B, C, E, G, J, K and X of quantitative example 5,6,7,9,11,14,15 and 28 preparations, put into U type pipe respectively, at 600 ℃ is that the argon gas of 100 ml/min was handled 10 hours with containing 3 heavy % water, flow velocity down, or 900 ℃ of roastings 10 hours in air, or be that the argon gas of 100 ml/min was handled 1000 hours with flow velocity at 400 ℃, cooling is isolated the particle that has magnetic with magnet, weighs.Because of ZSM-5 zeolite and nickel porous-aluminium (or iron-aluminium) alloy composite materials have magnetic, after under different condition, handling, the zeolite that splits away off from composite does not have magnetic, thereby can find out the firmness that the ZSM-5 zeolite combines with Lacunaris metal carrier according to its weightlessness.Treatment conditions and the results are shown in Table 22.

Comparative Examples 1

ZSM-5 zeolite and carrier-bound firmness in the existing CuZSM-5 zeolite of this Comparative Examples explanation/stainless steel catalyst.

With reference to the method for The Canadian Journal of Chemical Engineering 73,120,1995, take by weighing stainless (steel) wire (voidage is 80%, and Shoudu Iron and Steel Co. produces) 50 grams of 0.02 centimetre of diameter, put into withstand voltage still.Use NaOH, waterglass (contains SiO ₂23.5 heavy %, Chang Ling oil-refining chemical head factory is produced), TPAOH (Beijing Chemical Plant produces for TPA, chemical pure) and deionized water are made into mole and consist of 5Na ₂O10TPA100SiO ₂7000H ₂The zeolite of O synthesizes liquid, and the synthetic liquid of 1500 milliliters of zeolites is joined in the withstand voltage still, in confined conditions, 180 ℃ of crystallization 48 hours, filter, the washing solid product is to neutral, dry, 550 ℃ of roastings were made ZSM-5/ stainless (steel) wire composite to remove template agent TPA wherein in 10 hours.

With the above-mentioned ZSM-5/ stainless (steel) wire composite that obtains 10 grams and 250 milliliters, concentration is that the ammonia spirit of 0.1 mol mixes, and at room temperature carries out ion-exchange 8 hours, filtration, under similarity condition, exchange twice again, filter, drying was in 550 ℃ of roastings 2 hours.The solid product that obtains and 300 milliliters, concentration are that the Schweinfurt green solution of 0.01 mol mixes, and at room temperature carry out ion-exchange 8 hours, filter, and exchange twice again under similarity condition, filter, drying, in 550 ℃ of roastings 12 hours, reference catalyst Z.Z has following composition: stainless steel 94.5 heavy %, aluminium 0.2 heavy %, silicon 2.4 heavy %, oxygen 2.6 heavy %, copper ion 0.3 heavy %.

The reference catalyst Z5.00 gram that obtains above-mentioned is put into U type pipe, handles zeolite under the condition identical with example 30,36 and 37, weighs, calculates the loss in weight of composite, treatment conditions and the results are shown in Table 22.

Table 22

Example number	Composite	Treatment conditions	Handle the rear catalyst weight loss, heavy %
				30	A	600 ℃ contain 3 heavy % water, and the argon gas of flow velocity 100 ml/min was handled 10 hours	0.1
31	B	Roasting is 10 hours in 900 ℃ of air	0.7
				32	C	The argon gas that 400 ℃ of flow velocitys are 100 ml/min was handled 1000 hours	0.1
33	E	Roasting is 10 hours in 900 ℃ of air	0.5
				34	G	Roasting is 10 hours in 900 ℃ of air	0.5
35	J	The argon gas that 400 ℃ of flow velocitys are 100 ml/min was handled 1000 hours	0.2
				36	K	600 ℃ contain 3 heavy % water, and the argon gas of flow velocity 100 ml/min was handled 10 hours	0.2
37	X	600 ℃ contain 3 heavy % water, and the argon gas of flow velocity 100 ml/min was handled 10 hours	0.1
				Comparative Examples 1	Z	600 ℃ contain 3 heavy % water, and the argon gas of flow velocity 100 ml/min was handled 10 hours	4.1

The presentation of results of table 22, catalyst provided by the invention is under the condition of zeolite content far above reference catalyst, the weight loss of catalyst after treatment is far below reference catalyst, this illustrates that in the catalyst provided by the invention, the firmness that zeolite combines with Lacunaris metal carrier is far above prior art.

Example 38

Following example illustrates the hydrothermal stability of catalyst provided by the invention.

Take by weighing preceding catalyst A and each 0.1 gram of the catalyst after example 30 hydrothermal treatment consists of hydrothermal treatment consists of example 5 preparations, on legbold LHS 12 MCD associating spectrometer, with Mg source (MgK, 1253.6 electron-volts, 240 watts), in vacuum 1 * 10 ^-10Under the condition of millibar, measure Al2PX X-ray photoelectron spectroscopy X (XPS) in the composite.

Before and after the hydrothermal treatment consists Al2P XPS spectrum figure of catalyst respectively as among Fig. 11 and Fig. 2 in shown in 5.Known binding energy is that the peak about 77.4 electron-volts is the peak of non-framework aluminum, the peak that binding energy is 74.4 electron-volts is the peak of zeolitic frameworks aluminium, the ratio of two peak areas is represented the ratio of framework aluminum and non-framework aluminum quantity, thereby can measure the ratio of framework aluminum and non-framework aluminum according to the ratio of two peak areas.2 smoothed curves for the curve 1 of computer simulation among Fig. 1 wherein, 3 and 4 are respectively the framework aluminum of computer simulation and the peak of non-framework aluminum among Fig. 1.6 is smoothed curves of the curve 5 of computer simulation among Fig. 2, and 7 and 8 is respectively the framework aluminum of computer simulation and the peak of non-framework aluminum among Fig. 2.Composite mesolite framework aluminum is listed in the table 23 with the ratio of non-framework aluminum before and after the hydrothermal treatment consists that calculates thus.

Comparative Examples 2

The hydrothermal stability of this Comparative Examples explanation CuZSM-5 zeolite.

Measure by the method for example 38 that silica alumina ratio is 40, the ratio of CuZSM-5 zeolite (Chang Ling catalyst plant products) the hydrothermal treatment consists front and back framework aluminum of content of copper ion 2.3 heavy %.Before and after the hydrothermal treatment consists Al2P XPS spectrum figure of ZSM-5 zeolite as among Fig. 39 and Fig. 4 in shown in 13.10 are smoothed curves of the curve 9 of computer simulation among Fig. 3 wherein, 11 and 12 is the framework aluminum of computer simulation and the peak of non-framework aluminum.14 is smoothed curves of the curve 13 of computer simulation among Fig. 4, and 15 and 16 is respectively the framework aluminum of computer simulation and the peak of non-framework aluminum.Framework aluminum is listed in the table 23 with the ratio of non-framework aluminum before and after the hydrothermal treatment consists.

Table 23

Example number	Sample	The ratio of framework aluminum and non-framework aluminum
				Before the hydrothermal treatment consists	After the hydrothermal treatment consists
		38	A			10∶1	10∶1
Comparative Examples 2	The CuZSM-5 zeolite			4.1∶1	1.1∶1

The result of table 23 shows that after 10 hours, CuZSM-5 zeolitic frameworks aluminium obviously reduces with the ratio of non-framework aluminum through 600 ℃ of hydrothermal treatment consists, illustrates that hydrothermal treatment consists makes a large amount of dealuminzations of CuZSM-5 zeolite.And catalyst provided by the invention is after similarity condition is handled down, and framework aluminum does not change with the ratio of non-framework aluminum, illustrates in the catalyst provided by the invention that the framework aluminum of zeolite has very high hydrothermal stability.

Example 39

Following example illustrates the denitrifying oxide performance of catalyst provided by the invention.

Take by weighing the catalyst A of example 5 preparation, the catalyst A after handling by example 30 described conditions, the catalyst B after handling by example 31 described conditions, the catalyst C after handling by example 32 described conditions, the catalyst E after handling by example 33 described conditions, the catalyst G after handling by example 34 described conditions and handle by 37 described conditions after each 100 milligrams of catalyst X, the internal diameter of packing into is in 6 millimeters the U-shaped reactor, to contain NO, NH ₃, O ₂Argon gas be raw material, under the differential responses condition, estimate it and take off nitric oxide bioactivity, the nitric oxide conversion ratio under different condition is listed in the table 24, described nitric oxide conversion ratio is the result of reaction after 2 hours.Nitrogen oxide is detected by QGS-08B type nitrogen-oxide analyzer, (Beijing analyzer factory product).

Table 24

Example number	The catalyst numbering	Preparation of Catalyst or treatment conditions	NO concentration, ppm	NH 3Concentration, ppm	O 2Concentration, heavy %	Reaction temperature, ℃	Air speed, 10 5Hour -1	The NO conversion ratio, heavy %
									39	A	Example 5	500	500	2	300	1.5	48
40	A	Example 30	100	500	2	300	1.5	91
									41	A	Example 30	1000	1000	10	200	0.5	21
42	A	Example 30	500	1000	1	400	2.0	62
									43	A	Example 30	500	500	5	350	2.5	54
44	B	Example 31	500	500	2	250	1.5	34
									45	B	Example 31	500	500	2	350	3.0	60
46	B	Example 31	750	750	5	450	1.5	57
									47	C	Example 32	500	500	2	150	1.5	11
48	C	Example 32	500	500	2	550	0.5	47
									49	C	Example 32	500	750	3	400	2.0	91
50	E	Example 33	500	500	2	300	1.0	27
									51	E	Example 33	300	500	2	500	3.5	43
52	G	Example 34	50	500	3	200	4.0	71
									53	X	Example 37	750	1000	3	450	4.0	41
54	X	Example 37	500	600	4	350	5.0	23
									55	G	Example 34	300	500	2	300	1.0	51

Example 56～58

Following example illustrates that catalyst provided by the invention takes off nitric oxide production catalytic performance.

In 100 milligrams of example 39 described reactors of packing into of catalyst A with example 5 preparations, to contain NO5000ppm, NH ₃500ppm, O ₂0.9 the argon gas of heavy % is a raw material to be estimated it and take off nitric oxide production activity, gas flow is 120 ml/min, pressure be under normal pressure, the differential responses temperature nitric oxide production conversion ratio shown among Fig. 5 17.

Catalyst A is handled by example 30 and example 31 described conditions respectively, obtain after 600 ℃ of hydrothermal treatment consists and 900 ℃ of heat treatments after catalyst.

To after 900 ℃ of heat treatments and the catalyst after 600 ℃ of hydrothermal treatment consists by condition evaluating its activity identical with catalyst A, the nitric oxide conversion ratio is successively shown among Fig. 5 18 and 19 under the differential responses temperature.

Comparative Examples 3～5

The denitrifying oxide performance of following Comparative Examples explanation Cu ZSM-5 zeolite catalyst.

Each 100 milligrams of the CuZSM-5 zeolite catalysts that takes by weighing Comparative Examples 2 described CuZSM-5 zeolite catalysts and handle with example 30 and 31 described conditions, estimate it with identical reaction raw materials and take off nitric oxide bioactivity under the condition identical with example 56～58, the nitric oxide conversion ratio is successively shown in 20 among Fig. 6,21 and 22 under the differential responses temperature.

From the result of Fig. 5 and Fig. 6 as can be seen, catalyst provided by the invention is after hydrothermal treatment consists, when being higher than 550K, reaction temperature has the higher catalytic activity of more untreated catalyst, after 900 ℃ of heat treatment, more untreated catalyst all has higher catalytic activity under each reaction temperature.And the CuZSM-5 zeolite catalyst is after hydro-thermal or heat treatment, and its activity but descends significantly.Lot of documents (as CatalysisToday, 26,99,1995; J.Catal., 161,43,1996; Zeolite, 13,602,1993) also obtain similar result, this has seriously limited this Application of Catalyst.And have rule in contrast to this with catalyst provided by the invention, this has very important significance for the denitrifying oxide catalyst that uses under high temperature moisture vapor atmosphere, for catalyst provided by the invention has been opened up wide prospect in the practical application in environmental protection field.

Example 59

Following example illustrates activity of such catalysts stability provided by the invention.

Take by weighing the catalyst X100 milligram of example 28 preparations, in the example 39 described reactors of packing into, to contain NO5000ppm, NH ₃5000ppm, O ₂0.9 the argon gas of heavy % is that reaction raw materials is estimated its activity, 300 ℃ of reaction temperatures, and the pressure normal pressure, gas flow 120 ml/min, the nitric oxide conversion ratio is over time as shown in Figure 7.

The result of Fig. 7 shows, when adopting catalyst provided by the invention to be reducing agent with ammonia, 300 ℃ of reaction temperatures, the pressure normal pressure is under the condition of gas flow 120 ml/min, during the reaction beginning, the nitric oxide conversion ratio is about 20 heavy %, prolong with the reaction time, the nitric oxide conversion ratio progressively improves and is stabilized in level near 40 heavy %, and reaction reaches 1000 hours activity and do not fall as follows.This illustrates that catalyst provided by the invention has very high activity stability.

Claims (13)

1. denitrifying oxide catalyst that contains the ZSM-5 zeolite, contain a kind of Lacunaris metal carrier and the direct crystallization ZSM-5 zeolite on this Lacunaris metal carrier, 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 catalyst also contains a kind of metal ion that is selected from I B family metal, VIII family metal or its mixture; With nickel porous-aluminium, iron-aluminium or copper-aluminium alloy is benchmark, and the specific surface of Lacunaris metal carrier is greater than 10 meters ²/ gram, pore volume is greater than 0.7 milliliter/gram; Gross weight with nickel porous-aluminium, iron-aluminium or copper-aluminium alloy, zeolite and metal oxide is a benchmark, the content of nickel, iron or copper is that the content of 25～95 heavy %, aluminium is 0.1～10 heavy % in the catalyst, silicone content is 3～40 heavy %, content 0.1～10 heavy % of I B family metal ion, VIII family metal ion or its mixture.

2. according to the described catalyst of claim 1, it is characterized in that described Lacunaris metal carrier is nickel porous-aluminium, iron-aluminium or copper-aluminium alloy, or outer surface and/or inner surface contain the Lacunaris metal carrier of one deck nickel porous-aluminium, iron-aluminium or copper-aluminium alloy.

3. according to the described catalyst of claim 1, it is characterized in that the gross weight with nickel porous-aluminium, iron-aluminium or copper-aluminium alloy, zeolite and metal oxide is a benchmark, the content of nickel, iron or copper is that the content of 35～85 heavy %, aluminium is 0.1～5.0 heavy % in the catalyst, silicone content is 5～30 heavy %, content 0.1～5 heavy % of I B family metal ion, VIII family metal ion or its mixture.

4. according to the described catalyst of claim 1, it is characterized in that described I B family metal ion refers to that copper ion, VIII family metal ion refer to nickel ion or iron ion.

5. claim 1 Preparation of catalysts method, comprise a kind of Lacunaris metal carrier and the synthetic liquid of a kind of zeolite are contacted and make the synthetic liquid of zeolite crystallization under the conventional crystallization condition that synthesizes the 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 I B family metal ion, VIII family metal ion or its mixture, it is characterized in that described Lacunaris metal carrier contains a kind of nickel porous-aluminium, iron-aluminium or copper-aluminium alloy at least.

6. according to the described method of claim 5, it is characterized in that described a kind of nickel porous-aluminium that contains at least, the preparation method of the Lacunaris metal carrier of iron-aluminium or copper-aluminium alloy is as follows: 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, iron-aluminium or copper-aluminium alloy are benchmark, aluminum content is 10～70 heavy % in the described precursor, the condition of handling precursor with sodium hydroxide solution should make aluminium content reduce to 0.1～20 heavy %, with nickel porous-aluminium, iron-aluminium or copper-aluminium alloy are benchmark, and the specific surface of Lacunaris metal carrier is greater than 5 meters ²/ gram, pore volume is greater than 0.5 milliliter/gram.

7. according to the described method of claim 6, it is characterized in that described condition with sodium hydroxide solution processing precursor should make aluminium content reduce to 0.1～10 heavy %, the specific surface of Lacunaris metal carrier is greater than 10 meters ²/ gram, pore volume is greater than 0.7 milliliter/gram.

8. according to the described method of claim 5, it is characterized in that the synthetic liquid of described zeolite has following mol ratio and forms: SiO ₂/ Al ₂O ₃＞20, Na ₂O/SiO ₂=0.03～2, template agent/SiO ₂=0.03～1.5, H ₂O/SiO ₂=3～200.

9. described according to Claim 8 method is characterized in that the synthetic liquid of described zeolite has following mol ratio and forms: SiO ₂/ Al ₂O ₃＞50, Na ₂O/SiO ₂=0.03～0.5, template agent/SiO ₂=0.03～0.5, H ₂O/SiO ₂=15～200.

10. according to Claim 8 or 9 described methods, it is characterized in that described template agent refers to tetraethyl ammonium hydroxide or TPAOH.

11., it is characterized in that described crystallization condition comprises 100～200 ℃ of crystallization temperatures, crystallization time 10～120 hours according to the described method of claim 5.

12., it is characterized in that described crystallization condition comprises 140～200 ℃ of crystallization temperatures, crystallization time 30～100 hours according to the described method of claim 11.

13., it is characterized in that ion-exchange is adopted in the introducing of described I B family metal ion, VII family metal ion according to the described method of claim 5.

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