CN102847553A

CN102847553A - Transition metal-containing zeolite

Info

Publication number: CN102847553A
Application number: CN2012102170351A
Authority: CN
Inventors: 陈海军; 武脇隆彦; 松尾武士
Original assignee: Mitsubishi Plastics Inc
Current assignee: Mitsubishi Plastics Inc
Priority date: 2011-06-27
Filing date: 2012-06-27
Publication date: 2013-01-02

Abstract

To easily and efficiently produce a transition metal-containing silicoaluminophosphate zeolite which has high high-temperature hydrothermal durability. A method for producing a transition metal-containing zeolite that is obtained by having a zeolite, which contains a silicon atom, a phosphorus atom and an aluminum atom in at least the skeleton structure, contain a transition metal, said method for producing a transition metal-containing zeolite being characterized by performing hydrothermal synthesis of an aqueous gel that contains a silicon atom source material, an aluminum atom source material, a phosphorus atom source material, a transition metal source material and a polyamine (excluding a diamine). The transition metal-containing silicoaluminophosphate zeolite, which is produced by hydrothermal synthesis of an aqueous gel that contains a transition metal source material and a polyamine together with a zeolite source material, exhibits high high-temperature hydrothermal durability, while having high catalytic activity.

Description

The zeolite that contains transition metal

Technical field

The pump-down process catalyst and the water vapor adsorption material that the present invention relates to comprise SAPO zeolite, its manufacture method of transition metal and comprise this zeolite that contains transition metal.

Background technology

Make the zeolite that comprises transition metal, need to make transition metal be supported on operation in the zeolite by being immersed in the transition metal salt solution with containing through synthetic zeolite or carrying out ion-exchange, support in the operation at this, following problem is arranged.Namely, as the transition metal salt solution that is used for the impregnation zeolite, the aqueous solution of normal operation transition metal salt, but transition metal salt is easy to form hydroxide, appearing at the transition metal hydroxide that generates in the maceration extract is not to be attached in a large number in the pore of Zeolite support, but be attached in a large number phenomenon such on the particle surface, be difficult to make transition metal to be supported on equably in the pore of zeolite.In addition, also exist from this transition metal and support many and so on the problems of the process number of filtration, cleaning etc. of processing problem, the zeolite dipping sizing agent of a large amount of waste liquids of discharging the operation.

To this, in patent documentation 1 and non-patent literature 1, proposed by will being directed in the gel of zeolite synthesis procedure as transition metal oxide, the transition metal salt of transition metal raw material, thus in an operation a synthetic process for one-pot synthesis that comprises the SAPO zeolite of transition metal.Yet, with regard to the SAPO zeolite that comprises transition metal that is synthesized by the method, transition metal imports by replacing with the part of zeolitic frameworks element, therefore the performance as catalyst, sorbing material the time is insufficient, if carry out high-temperature water heat treatment, then exist the deteriorated problem of zeolite occurs.In addition, in the synthetic zeolite that comprises transition metal of the method, comprise the impurity such as noncrystalline thing, therefore exist catalytic performance to hang down such problem.

In patent documentation 2, also proposed Cu is added the synthetic initial gel of zeolite and the synthetic method that comprises the SAPO zeolite of Cu.The zeolite that comprise transition metal synthetic with the method also exists hydrothermal stability to hang down such problem.

In patent documentation 3, proposed to utilize after the synthesized silicon-aluminum phosphate zeolite, to support Cu and the synthetic method that comprises the SAPO zeolite of Cu.The zeolite that comprise transition metal synthetic with the method has high catalytic activity and hydrothermal stability.And then, record the high-durability that has for the adsorption and de-adsorption of water.Yet, although that even the zeolite that obtains in this patent documentation 3 also can be kept after the adsorption and desorption adhesion test repeatedly at steam is zeolite structured, exists and the reduction of the catalytic performance low temperature (for example 200 ℃) under occurs, particularly in the steam insufficient such shortcoming of low temperature catalyst activity after the adsorption and desorption adhesion test repeatedly.When the SAPO zeolite that will comprise transition metal is used as catalyst, sorbing material, sometimes on zeolite, carry out continually the adsorption and de-adsorption of water.For example, when zeolite catalyst is used to automobile, when automobile parking, the moisture in the zeolite catalyst air amount.On the other hand, when running car, when the temperature of automobile emission gas rose, zeolite catalyst was expelled to the moisture that sucks in the air.Like this, carry out the adsorption and de-adsorption of water at zeolite catalyst.In addition, with regard to regard to the zeolite that contains transition metal that proposes in the patent documentation 3, think and cause the bond angle of backbone element key Si-O-Al, bond distance to change by the adsorption and de-adsorption of water, thereby cause being fixed in the transition metal cohesion of Si-O-Al key mapping point, reduce in high dispersive transition-metal catalyst activated centre, causes catalyst activity to reduce.

With regard to the SAPO zeolite in the non-patent literature 2, the adsorption and de-adsorption of water causes backbone element key Si-O-Al, P-O-Al bond angle, bond distance to change.If it is attached that the Adsorption and desorption of water occurs repeatedly, then backbone element key Si-O-Al, P-O-Al are decomposed, zeolitic frameworks destructurized.If zeolitic frameworks is destructurized, then cause the further reduction by the catalyst activity due to the reduction of catalyst surface area.

In addition, open in patent documentation 4, water absorption or desorb invest the SAPO zeolite, thereby the lattice paprmeter of zeolite changes and contraction or expansion, thus, in the honeycomb structured body with the cellular unit that comprises the SAPO zeolite, exist the adsorption and de-adsorption by water to cause easily damaged such problem of cellular unit.Therefore, make the SAPO that the amount of Si is adjusted to specified quantitative with respect to ratio and the acid site of the amount sum of Al and P although disclose, if but only adopt this adjustment, then the high-temperature water heat durability, and as steam catalyst activity, the water vapor adsorption performance used of the pump-down process after the adsorption and desorption adhesion test is insufficient repeatedly.

The prior art document

Non-patent literature 1:Journal of Catalysis, 217(2003) 100-106

Non-patent literature 2:Microporous and Mesoporous Materials 57(2003) 157-168.

Patent documentation 1: U.S. publication 2010/0310440A1 specification

Patent documentation 2: Chinese publication 102259892A specification

Patent documentation 3: international the 2010/084930th communique that discloses

Patent documentation 4: international the 2012/029159th communique that discloses

Summary of the invention

Problem of the present invention is to provide the Heteroatom-aluminophosphate Zeolites that contains transition metal that has for high stability and the high catalytic performance of water adsorption and de-adsorption.

And then, problem of the present invention is to provide can be easy and make expeditiously the method for the zeolite that contains transition metal, this zeolite that contains transition metal is the SAPO zeolite that comprises transition metal, and is high as excellent performance and the high-temperature water heat durability of catalyst, sorbing material.

The invention provides a kind of zeolite that contains transition metal, it is transition metal to be contained in the zeolite that comprises at least silicon atom, phosphorus atoms and aluminium atom in skeleton structure form, in the water vapor adsorption isotherms of 25 ℃ of mensuration, adsorbance during relative vapour pressure 0.01 is more than the 1.3mol/molSi, and the adsorbance during relative vapour pressure 0.7 is 150mg/g ~ 300mg/g.

Described zeolite can be Heteroatom-aluminophosphate Zeolites.

In addition, the described zeolite that contains transition metal can comprise the above transition metal of 3 % by weight.

And then, with regard to the described zeolite that contains transition metal, distributing when marking and drawing at the element that carries out the transition metal M in this zeolite with probe-microanalyser, the variation coefficient of transition metal intensity can be below 33%.

In addition, with regard to the described zeolite that contains transition metal, the aluminium atom can be more than 0.9 with respect to the mol ratio of the total of silicon atom and phosphorus atoms.

In addition, described Heteroatom-aluminophosphate Zeolites is preferably the Heteroatom-aluminophosphate Zeolites that has 8 ring structures in the skeleton structure.

In addition, the invention provides a kind of zeolite that contains transition metal, it is the Heteroatom-aluminophosphate Zeolites that comprises the above transition metal M of 3 % by weight, when carrying out the element distribution plotting of the transition metal M in this zeolite with probe-microanalyser, the Strength Changes coefficient of transition metal M is below 33%, and the aluminium atom is more than 0.9 with respect to the mol ratio of the total of silicon atom and phosphorus atoms.

In the present invention, with regard to the described zeolite that contains transition metal, in the water vapor adsorption isotherms of 25 ℃ of mensuration, the adsorbance during relative vapour pressure 0.01 can be more than the 1.3mol/molSi.

In addition, in the present invention, with regard to the described zeolite that contains transition metal, the adsorbance during relative vapour pressure 0.7 can be 150mg/g ~ 300mg/g.

And then in the present invention, the described zeolite that contains transition metal can be to make transition metal contain the zeolite that contains transition metal that forms in the zeolite that comprises at least silicon atom, phosphorus atoms and aluminium atom in skeleton structure.

In addition, in the present invention, the described zeolite that contains transition metal can be the Heteroatom-aluminophosphate Zeolites that has 8 ring structures in the skeleton structure.

The described zeolite that contains transition metal of the present invention, preferred described transition metal M is iron and/or copper.

The above-mentioned zeolite that respectively contains transition metal of the present invention, preferred BET specific area is 500m ²More than/the g.

The above-mentioned zeolite that respectively contains transition metal of the present invention, preferred zeolite in the zeolite structured middle skeletal density of International Zeolite Association IZA regulation is

In addition, the above-mentioned zeolite that respectively contains transition metal of the present invention, preferred zeolite is CHA in International Zeolite Association IZA regulation zeolite structured.

The invention provides a kind of manufacture method that contains the zeolite of transition metal, it is characterized in that, for making transition metal, manufacturing contains the method for the zeolite that contains transition metal that in the zeolite that in skeleton structure, comprises at least silicon atom, phosphorus atoms and aluminium atom, forms, carry out Hydrothermal Synthesis by aqueous gel, described aqueous gel comprises silicon atom raw material, aluminium atomic raw material, phosphorus atoms raw material, transition metal atoms raw material and polyamines (still, except the diamines), and at least a combination of selecting respectively at least 2 groups from the group of following (1) ~ (3) respectively:

(1) comprises at least nitrogen-atoms as heteroatomic ester ring type heterocyclic compound;

(2) alkylamine;

(3) Cycloalkyl amine.

In above-mentioned manufacture method, described zeolite can be Heteroatom-aluminophosphate Zeolites.

And then, with regard to the described zeolite that contains transition metal, distributing when marking and drawing at the element that adopts probe-microanalyser to carry out the transition metal in this zeolite, the variation coefficient of transition metal intensity can be below 33%.

In the manufacture method of the zeolite that contains transition metal of the invention described above, described transition metal is preferably iron and/or copper.

In addition, the invention provides a kind of manufacture method that contains the zeolite of transition metal, it is characterized in that, for making transition metal, manufacturing contains the method for the zeolite that contains transition metal that in the zeolite that in skeleton structure, comprises at least silicon atom, phosphorus atoms and aluminium atom, forms, wherein, to be pre-mixed phosphorus atoms raw material and water as cupric oxide (II) or the copper acetate of transition metal raw material, then mix silicon atom raw material, aluminium atomic raw material, reach polyamines (still, except the diamines), the modulation aqueous gel carries out Hydrothermal Synthesis.

At this, should of the present inventionly contain the manufacture method of the zeolite of transition metal, preferably in aqueous gel, further comprise at least a kind the combination of selecting respectively at least 2 groups that are selected from respectively from the group of following (1) ~ (3):

(2) alkylamine;

(3) Cycloalkyl amine.

At this, described zeolite can be Heteroatom-aluminophosphate Zeolites.

In addition, with regard to the described zeolite that contains transition metal, in the water vapor adsorption isotherms of 25 ℃ of mensuration, the adsorbance during relative vapour pressure 0.01 can be more than the 1.3mol/molSi.

In addition, with regard to the described zeolite that contains transition metal, the adsorbance during relative vapour pressure 0.7 can be 150mg/g ~ 300mg/g.

In addition, the described zeolite that contains transition metal can be the Heteroatom-aluminophosphate Zeolites that has 8 ring structures in the skeleton structure.

In addition, the above-mentioned manufacture method that contains the zeolite of transition metal of the present invention can be the manufacture method of the zeolite that respectively contains transition metal of the invention described above.

In addition, in each manufacture method of the above-mentioned zeolite that contains transition metal of the present invention, described polyamines is preferably uses general formula H ₂N-(C _nH _2nNH) _xIn-H(the formula, n is 2 ~ 6 integer, and x is 2 ~ 10 integer) expression polyamines.

In addition, in the manufacture method of the above-mentioned zeolite that contains transition metal of the present invention, the mol ratio when the aluminium atomic raw material in the composition of described aqueous gel, silicon atom raw material, phosphorus atoms raw material and transition metal (M) atomic raw material are represented with oxide is:

SiO ₂/ Al ₂O ₃Value be 0.1 ~ 0.8;

P ₂O ₅/ Al ₂O ₃Value be 0.6 ~ 1.2;

M _aO _b/ Al ₂O ₃Value be 0.05 ~ 1(wherein, a and b represent respectively the atomic ratio of M and O).

The invention provides the manufacture method of the zeolite that respectively contains transition metal of the invention described above.

In addition, the present invention also provides the pump-down process catalyst of the zeolite that respectively contains transition metal of the invention described above.

In addition, the present invention also provides the water vapor adsorption material of the zeolite that respectively contains transition metal of the invention described above.

According to the present invention, carry out Hydrothermal Synthesis by the aqueous gel that will comprise transition metal atoms raw material and polyamines with the zeolite raw material, thereby in the Hydrothermal Synthesis operation of zeolite, in synthetic zeolite, carry out the enhancement of dispersion of transition metal in the zeolite pore, can make easy and expeditiously the SAPO zeolite that contains transition metal that the high-temperature water heat durability is high and catalyst activity is excellent.

In addition, according to the present invention, in the water vapor adsorption isotherms of 25 ℃ of mensuration, adsorbance during relative vapour pressure 0.01 is more than the 1.3mol/molSi, adsorbance during relative vapour pressure 0.7 is 150mg/g ~ 300mg/g, can obtain making transition metal to contain the zeolite that contains transition metal that forms in the zeolite that comprises at least silicon atom, phosphorus atoms and aluminium atom in skeleton structure.With the zeolite facies ratio that contains transition metal in the past, catalyst activity and the hydrothermal durability of the zeolite that contains transition metal of the present invention are high, even and then at steam repeatedly after the adsorption and desorption adhesion test, catalyst activity is also high, has excellent stability for the adsorption and de-adsorption of water.

Description of drawings

Fig. 1 is the chart that is illustrated in the measurement result of the XRD of the zeolite 1 of manufacturing among the embodiment 1.

Fig. 2 is the Si of the EPMA of the zeolite 1 of manufacturing in embodiment 1 and the distribution diagram of element of Cu.

Fig. 3 is the figure that is illustrated in the water vapor adsorption isotherms of the zeolite 1 of making among the embodiment 1.

Fig. 4 is the Si of the EPMA of the zeolite 3 of manufacturing in embodiment 3 and the distribution diagram of element of Cu.

Fig. 5 is the figure that is illustrated in the water vapor adsorption isotherms of the zeolite 3 of making among the embodiment 3.

Fig. 6 is the chart that is illustrated in the measurement result of the XRD of the zeolite 5 of manufacturing among the embodiment 5.

Fig. 7 is the figure that is illustrated in the water vapor adsorption isotherms of the zeolite 6 of making among the embodiment 6.

Fig. 8 is the chart that is illustrated in the measurement result of the XRD of the zeolite 8 of manufacturing among the embodiment 8.

Fig. 9 is the figure that is illustrated in the water vapor adsorption isotherms of the zeolite 8 of making among the embodiment 8.

Figure 10 is the figure that is illustrated in the water vapor adsorption isotherms of the zeolite 10 of making among the embodiment 10.

Figure 11 is adsorption and desorption adhesion test-2(90 ℃-60 ℃-5 ℃ repeatedly of the steam that are used for using in an embodiment) the schematic diagram of formation of experimental rig.

Figure 12 is the Si of the EPMA of the zeolite C of manufacturing in comparative example 3 and the distribution diagram of element of Cu.

Figure 13 is the figure of the water vapor adsorption isotherms of the zeolite C of manufacturing in comparative example 3.

Figure 14 is the figure of the water vapor adsorption isotherms of the zeolite E of manufacturing in comparative example 5.

Figure 15 is the Si of the EPMA of the zeolite F of manufacturing in comparative example 6 and the distribution diagram of element of Cu.

Figure 16 is the figure of the water vapor adsorption isotherms of the zeolite F of manufacturing in comparative example 6.

Figure 17 is the figure of the water vapor adsorption isotherms of the zeolite G of manufacturing in comparative example 7.

Figure 18 is the Si of the EPMA of the zeolite H of manufacturing in comparative example 8 and the distribution diagram of element of Cu.

Figure 19 is the Si of the EPMA of the zeolite I of manufacturing in comparative example 9 and the distribution diagram of element of Cu.

Symbol description

1,2,3 thermostatic chambers

4,5,6 containers

A, b pump

The specific embodiment

Below, be elaborated for embodiments of the present invention, but below be illustrated as the example (typical example) of embodiment of the present invention, the present invention is not limited to these contents.

[Heteroatom-aluminophosphate Zeolites that contains transition metal]

The 1st main idea of the present invention relates to a kind of zeolite that contains transition metal, transition metal to be contained in the zeolite that comprises at least silicon atom, phosphorus atoms and aluminium atom in skeleton structure form, in the water vapor adsorption isotherms of 25 ℃ of mensuration, adsorbance during relative vapour pressure 0.01 is more than the 1.3mol/molSi, and the adsorbance during relative vapour pressure 0.7 is 150mg/g ~ 300mg/g.

The of the present invention the 2nd will be intended to a kind of zeolite that contains transition metal, it is characterized in that, it is the Heteroatom-aluminophosphate Zeolites that comprises the above transition metal M of 3 % by weight, when the element that adopts probe-microanalyser to carry out the transition metal M in this zeolite distributes plotting, the Strength Changes coefficient of transition metal M is below 33%, the aluminium atom is more than 0.9 with respect to the mol ratio of the total of silicon atom and phosphorus atoms

The 3rd main idea of the present invention is present in a kind of zeolite that contains transition metal, it is characterized in that, to comprise the Heteroatom-aluminophosphate Zeolites that has 8 ring structures in the above transition metal M of 3 % by weight and the skeleton structure, the element that adopts probe-microanalyser to carry out the transition metal M in this zeolite distributes when marking and drawing, the Strength Changes coefficient of transition metal M is below 33%, and the aluminium atom is more than 0.9 with respect to the mol ratio of the total of silicon atom and phosphorus atoms.

For so of the present invention the 1st, the 2nd, and manufacture method of the zeolite that contains transition metal of the 3rd main idea, as described later, but the aftermentioned manufacture method is the typical example of the manufacture method of the zeolite that contains transition metal of the present invention, and the manufacture method that contains the zeolite of transition metal of the present invention is not subject to any restriction of aftermentioned manufacture method.

At first, describe for the zeolite that contains transition metal as the specific water absorption energy of having of the 1st main idea of the present invention.

For example, when the zeolite that will comprise transition metal was used catalyst as pump-down process, the exhaust of the diesel engine of automobile etc. comprised the water of 5 ~ 15 volume % in exhaust.In running car, exhaust becomes the high temperature more than 200 ℃, and relative humidity is reduced to below 5%, and catalyst becomes the state of desorption moisture.Yet, also existing when stopping, the relative humidity of air becomes more than 30%, particularly becomes situation more than 50%, the water in the catalyst absorbed air because weather conditions cause the relative humidity of air.Because the water adsorption and de-adsorption of zeolite is carried out in travelling and parking of automobile at the zeolite that comprises transition metal.Relative therewith, the water adsorption amount during low humidity (below 5%) is many, the fewer zeolite of water adsorption amount during high humility (more than 50%), even the humidity of environment for use is changed to high humility from low humidity, the amount of the water of adsorption and de-adsorption is also fewer.Therefore, tailed off by the bond angle of the backbone element key Si-O-Al due to the adsorption and de-adsorption of water and Al-O-P, bond distance's variation.Thus, the stability of zeolite uprises, and can suppress by the variation of the lattice paprmeter of the zeolite due to the adsorption and de-adsorption of water, the Volume Changes of zeolite.The cellular unit that comprises the SAPO zeolite also can solve the damaging problem by the cellular unit due to the adsorption and de-adsorption of water.

In the water vapor adsorption isotherms of 25 ℃ of mensuration, be that relative vapour pressure is 0.01(relative humidity 1% with respect to the dividing potential drop of the steam of Saturated water vapor pressure) time the adsorbance of water to be subject to the impact of amount of the Si in the zeolite large.If usually Si increases, then the absorption quantitative change of the water during relative vapour pressure 0.01 is many.The absorption of water when thinking relative vapour pressure 0.01 is by the Si-O(H from the Si in the zeolite)-H in the Al key adsorbs with the water that the hydrogen bond of hydrone produces.Therefore, the water adsorption amount of zeolite when relative vapour pressure 0.01 that comprises transition metal of the present invention uses the molal quantity (mol/molSi) that is adsorbed on the water in the zeolite with respect to the 1molSi in the zeolite to stipulate.That is more than the preferred 1.3mol/molSi of adsorbance of the water in the time of, relative vapour pressure 0.01(relative humidity 1%), more than the further preferred 1.4mol/molSi.The upper limit of the adsorbance of the water during relative vapour pressure 0.01 is not particularly limited.If lack than above-mentioned lower limit, the hydrolysis absorption of zeolite under low humidity is fierce, so zeolitic frameworks element bond stability step-down.

The water absorption constant of the zeolite in the time of in addition, in the water vapor adsorption isotherms of 25 ℃ of mensuration, relative vapour pressure 0.7(relative humidity 70%) reaches the saturation state of water absorption.The water adsorption amount of the zeolite under this saturation state and the amount of the Si in the zeolite have nothing to do and are determined by the pore volume of zeolite, the hydrophily on surface etc.The water adsorption amount of zeolite when relative vapour pressure 0.7 that contains transition metal of the present invention is preferably 150mg/g ~ 300mg/g with respect to the 1g zeolite, more preferably more than the 200mg/g, and further preferred 260mg/g ~ 290mg/g.Relative vapour pressure 0.7(relative humidity 70%) if the time the adsorbance of water of zeolite more than the above-mentioned upper limit, then when environment for use was converted to low humidity from high humility, the hydrolysis absorption on the zeolite was fierce, zeolitic frameworks element bond stability step-down.

In addition, by the lattice paprmeter of the zeolite due to the adsorption and de-adsorption of water change, the Volume Changes cellular unit that comprises the SAPO zeolite greatly of zeolite is easily damaged because of the adsorption and de-adsorption of water.On the other hand, when forming mesoporous the grade in crystallization of zeolites, the water adsorption amount of the zeolite when having relative vapour pressure 0.7 becomes the situation of Duoing than the above-mentioned upper limit, but the hydrothermal stability of zeolite may step-down in this case.Relative vapour pressure 0.7(relative humidity 70%) if the time the water adsorption amount of zeolite lack than above-mentioned lower limit, mean that then the crystallinity of zeolite is low, according to circumstances, catalytic performance might be insufficient.

The skeleton structure of＜zeolite 〉

The zeolite that contains transition metal of the present invention is transition metal to be contained in the Heteroatom-aluminophosphate Zeolites that comprises phosphorus atoms and aluminium atom in the skeleton structure at zeolite at least form, and preferably further also comprises silicon atom in the skeleton structure of zeolite.

It is the SAPO zeolite that contains transition metal that comprises transition metal in the following zeolite that has a ratio with following ratio that the zeolite that contains transition metal of the present invention is preferably mol ratio at aluminium atom, phosphorus atoms and the silicon atom of skeleton structure of zeolite.

The ratio that exists of contained aluminium atom, phosphorus atoms and silicon atom preferably satisfies following formula (I), (II) and (III) in the skeleton structure of the zeolite that contains transition metal of the present invention.

0.001≦x≦0.3 …（I）

(in the formula, x represents that silicon atom is with respect to the mol ratio of the total of the silicon atom in the skeleton structure, aluminium atom and phosphorus atoms)

0.3≦y≦0.6 …（II）

(in the formula, y represents that the aluminium atom is with respect to the mol ratio of the total of the silicon atom in the skeleton structure, aluminium atom and phosphorus atoms)

0.3≦z≦0.6 …（III）

(in the formula, z represents that phosphorus atoms is with respect to the mol ratio of the total of the silicon atom in the skeleton structure, aluminium atom and phosphorus atoms)

As the x value, be generally more than 0.001, be preferably more than 0.01, more preferably more than 0.03, and be generally below 0.3, be preferably below 0.2, more preferably below 0.18.If the x value is less than above-mentioned lower limit, the modulation condition of the zeolite of the reaction temperature during then sometimes because of Hydrothermal Synthesis etc. causes being difficult to carrying out crystallization of zeolites.If the x value is greater than above-mentioned higher limit, the modulation condition of the zeolite of the reaction temperature during then because of Hydrothermal Synthesis etc. causes existing becoming when synthesizing easily sneaks into the tendency of impurity in zeolite.About the modulation condition of zeolite, those skilled in the art can easily solve above-mentioned zeolite and be difficult to the problem of crystallization, become in zeolite and easily sneak into the problem of impurity by carry out the experiment of limited number of time based on the instruction of present specification.About also being same in the situation less than the lower limit of following each number range, the situation larger than higher limit.

And then y is generally more than 0.3, is preferably more than 0.35, more preferably more than 0.4, and is generally below 0.6, is preferably below 0.55.If less than above-mentioned lower limit or greater than above-mentioned higher limit, then existing to become when synthesizing, the y value easily in zeolite, sneaks into the tendency of impurity.

And then z is generally more than 0.3, is preferably more than 0.35, more preferably more than 0.4, and is generally below 0.6, is preferably below 0.55, more preferably below 0.50.If the z value is less than above-mentioned lower limit, then existing becomes when synthetic easily sneaks into the tendency of impurity in zeolite, if the z value greater than above-mentioned higher limit, then zeolite is difficult to crystallization sometimes.

As transition metal M, be not particularly limited, but the characteristic aspect from sorbing material purposes, catalyst applications is considered, usually can enumerate the transition metal of the 3-12 family of iron, cobalt, magnesium, zinc, copper, palladium, iridium, platinum, silver, gold, cerium, lanthanum, praseodymium, titanium, zirconium etc., be preferably iron, cobalt, copper grade in an

imperial examination

8,9,11 families, more preferably the 8th, 11 families.The transition metal that contains in zeolite can be a kind in these, and the transition metal combination more than 2 kinds is contained in zeolite.Be particularly preferably iron and/or copper in these transition metal, especially be preferably copper.

In addition, the ratio that exists of the transition metal atoms M in the zeolite that contains transition metal of the present invention preferably satisfies following formula (IV).

0.001≦m≦0.3 …（IV）

(in the formula, m is the mol ratio of transition metal of the total of silicon atom, aluminium atom and phosphorus atoms with respect to skeleton structure of zeolite)

As the m value, be preferably more than 0.01, more preferably more than 0.05, more preferably more than 0.08, be particularly preferably more than 0.1, and be generally below 0.3, be preferably below 0.25, more preferably below 0.2, be particularly preferably below 0.1.If the m value is less than above-mentioned lower limit, the tendency that then exists the activated centre to tail off causes insufficient catalytic performance that manifests because of the requirement difference for catalytic performance in the various uses of catalyst sometimes.If the m value is greater than the above-mentioned upper limit, then exist because of zeolite synthetic in modulation conditions such as temperature conditions during interpolation order, stirring, the hydro-thermal reaction of transition metal raw material and other raw material cause the cohesion of transition metal to become being inclined to significantly, compare for the situation in the scope of above-mentioned formula (IV) with the m value, catalytic performance reduces sometimes.

Particularly with regard to the content of the transition metal M of the zeolite that contains transition metal of the of the present invention the 1st and the 2nd main idea, in the weight of the transition metal M ratio with respect to the weight of the zeolite that contains transition metal under the anhydrous state, need to be for more than 3%, be preferably more than 3.5%, more preferably more than 4%, and be generally below 10%, be preferably below 8%, more preferably below 6%.If the content of transition metal M lacks than above-mentioned lower limit, then the high dispersive transition metal active centres is insufficient, if more than above-mentioned higher limit, then zeolite is difficult to crystallization sometimes.

Should illustrate, with regard to the atomic ratio in the skeleton structure of above-mentioned zeolite, utilize elementary analysis and determine, elementary analysis among the present invention is after making the sample heating for dissolving in aqueous hydrochloric acid solution, utilizes inductively coupled plasma (ICP:Inductively Coupled Plasma) ICP Atomic Emission Spectrophotometer to obtain; Perhaps with behind the zeolite powder compression molding, utilize fluorescent x-ary analysis (XRF) to obtain.

Should illustrate, atom in the above-mentioned skeleton structure of zeolite, the content of transition metal M are determined by elementary analysis, with regard to the elementary analysis among the present invention, to make sample in aqueous hydrochloric acid solution after the heating for dissolving, utilize inductively coupled plasma (ICP:Inductively Coupled Plasma) ICP Atomic Emission Spectrophotometer, perhaps utilize fluorescent x-ary analysis (XRF) after with the sample compression molding, wherein particularly utilize energy dispersion type optical spectroscopy (EDX), thereby obtain the atom in the skeleton structure of zeolite, the content W of transition metal M ₁(% by weight) on the other hand, utilizes thermogravimetric analysis (TG) to obtain moisture W in the sample _H2O(% by weight) calculates the atom of the skeleton structure in the zeolite that contains transition metal under the anhydrous state, the content W(% by weight of transition metal M with following formula (V)).

W=W ₁/（1-W _H2O） …（V）

The Strength Changes coefficient of＜transition metal M 〉

The zeolite that contains transition metal of the of the present invention the 1st and the 2nd main idea is characterised in that, when the element that carries out transition metal M with probe-microanalyser (EPMA) distributes plotting, the variation coefficient of the intensity of metallic element M is generally below 33%, this variation coefficient is preferably below 31%, more preferably below 29%.

The lower limit of the Strength Changes coefficient of the transition metal M in the zeolite that contains transition metal of the of the present invention the 1st and the 2nd main idea is not particularly limited.The Strength Changes coefficient of transition metal M is less, shows that more transition metal M in the zeolite more is evenly dispersed in the exchange site from Si.If the Strength Changes coefficient of transition metal M surpasses above-mentioned higher limit, then produce following problem: the dispersed variation of the transition metal M in the zeolite, the catalyst activity of zeolite that contains transition metal is insufficient, and perhaps zeolite is stable low.

Should illustrate, in the present invention, variation coefficient is the mean value of the variation coefficient of the intensity measured in a plurality of visuals field more than 3 o'clock.Particularly, the element distribution plotting according to EPMA utilizes the method for putting down in writing in the project of aftermentioned embodiment to implement.

In addition, when the zeolite that contains transition metal of the present invention is used as purification catalyst for automobile exhaust, water vapor adsorption material, in the zeolite of being made by the present invention, the zeolite that preferably has following structure and skeletal density.

The structure of zeolite is utilized the XRD(X ray diffraction method: X-ray diffraction) determine, when the coding with International Zeolite Association (IZA) regulation represents, be AEI, AFR, AFS, AFT, AFX, AFY, AHT, CHA, DFO, ERI, FAU, GIS, LEV, LTA, VFI, preferred AEI, AFX, GIS, CHA, VFI, AFS, LTA, FAU, AFY, in the present invention, the zeolite that wherein more preferably has 8 ring structures, the zeolite that most preferably has the CHA structure.

In addition, skeletal density for the reflection crystalline texture parameter, for IZA at the numerical value shown in the ATLAS OF ZEOLITE FRAMEWORK TYPES Fifth Revised Edition 2001, be preferably 10.0T/

Above, be generally 16.0T/

Below, be preferably 15.0T/

Below.

Skeletal density should be described

Refer to the unit volume with zeolite

The number of the T atom that meter exists (consisting of the oxygen atom atom (T atom) in addition of the skeleton structure of zeolite), this value is determined by the structure of zeolite.

During less than above-mentioned lower limit, structure becomes unstable sometimes in the skeletal density of zeolite, the tendency that exists durability to reduce, and on the other hand, if surpass above-mentioned higher limit, then adsorbance, catalyst activity diminish sometimes, or sometimes are not suitable as the use of catalyst.

Be not particularly limited for the particle diameter that contains the zeolite of transition metal of the present invention, but be generally more than the 0.1 μ m, more preferably more than the 1 μ m, more preferably more than the 3 μ m, and be generally below the 30 μ m, be preferably below the 20 μ m, more preferably below the 15 μ m.

The mean value of the one-level particle diameter of any 10 ~ 30 zeolite particles when particle diameter of the zeolite that contains transition metal among the present invention refers to contain the zeolite of transition metal with electron microscope observation should be described.

＜BET specific area 〉

The upper limit of the BET specific area of the zeolite that contains transition metal of the present invention is not particularly limited, but for lower limit, is preferably 500m ²More than/the g, 550m more preferably ²More than/the g, be particularly preferably 600m ²More than/the g.If the BET specific area less than above-mentioned lower limit, then exists the crystallinity of zeolite low, the performances such as the catalyst activity inadequate tendency that becomes.

[manufacture method that contains the zeolite of transition metal]

Manufacture method as the zeolite that contains transition metal of the 4th main idea of the present invention is a kind of manufacture method that contains the zeolite of transition metal, as making expeditiously the 1st of the invention described above, the method of the zeolite that contains transition metal that the 2nd and the 3rd main idea is related is effective, it is characterized in that, come Hydrothermal Synthesis that transition metal is contained by aqueous gel and in skeleton structure, comprising at least silicon atom, the zeolite that contains transition metal that forms in the zeolite of phosphorus atoms and aluminium atom, described aqueous gel comprises the silicon atom raw material, the aluminium atomic raw material, the phosphorus atoms raw material, transition metal atoms raw material and polyamines are (still, except the diamines.Below, when in the present invention, only being called " polyamines ", except as otherwise noted, be " polyamines except diamines ") and at least 2 groups from the group of following (1) ~ (3) at least a kind combination selecting respectively.

(1) comprises at least nitrogen-atoms as heteroatomic ester ring type heterocyclic compound

(2) alkylamine

(3) Cycloalkyl amine

Usually, adopt conventional method to carry out Hydrothermal Synthesis by this aqueous gel, then utilize calcining to wait to remove polyamines, other template and obtain containing the zeolite of transition metal.

The reason details that the method according to this invention can be made the high SAPO zeolite that contains transition metal of high-temperature water heat durability it be unclear that, but is speculated as following reason.

Namely, in the method for the invention, in aqueous gel, when comprising the transition metal atoms raw material, comprise specific polyamines, therefore when synthetic zeolite, transition metal in the aqueous gel and polyamines interact consumingly and carry out stabilisation, and are difficult to react with the zeolitic frameworks element.Therefore, from different such as the synthetic method of the SAPO zeolite that contains transition metal in the past of record in patent documentation 1 and the non-patent literature 1, transition metal is difficult to enter the skeleton (the zeolitic frameworks element is difficult to be replaced by transition metal) of zeolite, transition metal is present in outside the skeleton of zeolite, and be present in the pore of zeolite main the dispersion.

And then, in the present invention, by so specific known form assembly is used, can make the Heteroatom-aluminophosphate Zeolites that contains transition metal of high-temperature water heat durability excellence.

Think thus, according to the present invention, can synthesize the SAPO zeolite that contains transition metal with high catalytic performance and absorption property and high high-temperature water heat durability.

Below, an example of the manufacture method of the zeolite that contains transition metal of the present invention is described.

{ raw material }

For describing for each raw material of modulating aqueous gel involved in the present invention.

＜aluminium atomic raw material 〉

The aluminium atomic raw material of the zeolite among the present invention is not particularly limited, and usually can enumerate the aluminium alkoxide of boehmite, aluminium isopropoxide, aluminium ethoxide etc.; Aluminium hydroxide; Alumina sol; Sodium aluminate etc.These can use separately a kind, also can be mixed with two or more.Consider from the aspect of processing ease and reactive high aspect, as the aluminium atomic raw material, preferred boehmite.

＜silicon atom raw material 〉

The silicon atom raw material of the zeolite among the present invention is not particularly limited, and usually can enumerate gas phase (fumed) silica, silicon dioxide gel, cataloid, waterglass, silester, methyl silicate.These can use separately a kind, also can be mixed with two or more.Consider from high-purity and reactive high aspect, as the silicon atom raw material, preferred aerosil.

＜phosphorus atoms raw material 〉

The phosphorus atoms raw material of zeolite in the present invention is generally phosphoric acid, but also can use aluminum phosphate.The phosphorus atoms raw material can use separately a kind, also can be mixed with two or more.

＜transition metal atoms raw material 〉

In the present invention, the transition metal atoms raw material that contains in the zeolite is not particularly limited, and usually uses the inorganic acid salt such as sulfate, nitrate, phosphate, chloride, bromide of transition metal; The acylates such as acetate, oxalates, citrate; The organo-metallic compound of pentacarbonyl-iron, ferrocene etc. etc.Wherein, consider preferred inorganic acid salt, acylate from the deliquescent viewpoint to water.According to circumstances also can use colloidal oxide or micronized oxide.

As transition metal, be not particularly limited, but aspect the characteristic sorbing material purposes, catalyst applications, consider, can enumerate the transition metal of iron, cobalt, magnesium, zinc, copper, palladium, iridium, platinum, silver, gold, cerium, lanthanum, praseodymium, titanium, zirconium grade in an imperial examination 3-12 family, be preferably iron, cobalt, copper grade in an

imperial examination

8,9,11 families, more preferably the 8th, 11 families.The transition metal that contains in the zeolite can be a kind in these, also can make the transition metal combination more than 2 kinds and contains in zeolite.In these transition metal, be particularly preferably iron and/or copper, especially be preferably copper.

In the present invention, preferential oxidation copper (II) or copper acetate (II), more preferably cupric oxide (II).

As the transition metal atoms raw material, can and with in the different transition metal atoms raw material of kinds of transition metals or classes of compounds more than 2 kinds.

＜polyamines 〉

As the polyamines that uses in the present invention, preferably use general formula H ₂N-(C _nH _2nNH) _xIn-H(the formula, n is 2 ~ 6 integer, and x is 2 ~ 10 integer) expression polyamines.

In above-mentioned formula, the integer of n preferred 2 ~ 5, more preferably 2 ~ 4 integer, further preferred 2 or 3, particularly preferably 2.The integer of x preferred 2 ~ 6, more preferably 2 ~ 5 integer, further preferred 3 or 4, particularly preferably 4.

As such polyamines, wherein, diethylenetriamine, triethylene tetramine, TEPA is inexpensive and preferred, wherein particularly preferably triethylene tetramine, TEPA.These polyamines can use separately a kind, also can be mixed with two or more.The polyamines that can also contain in addition, a chain.

＜template 〉

In aqueous gel of the present invention, the template during as the manufacturing zeolite comprises at least a kind the combination of selecting respectively at least 2 groups from the group of following (1) ~ (4).

(1) comprises nitrogen-atoms as heteroatomic ester ring type heterocyclic compound;

(2) has the amine (alkylamine) of alkyl;

(3) has the amine (Cycloalkyl amine) of cycloalkyl; And

(4) tetra-alkyl ammonium hydroxide.

These are from easily obtaining and the processing ease of inexpensive and then the SAPO zeolite made and also be difficult to the aspect that recurring structure destroys and consider to suit.Wherein, from (1) comprise nitrogen-atoms as heteroatomic ester ring type heterocyclic compound, (2) alkylamine, and these 3 groups of (3) Cycloalkyl amines at least 2 groups in each group respectively during the compound of choice for use more than a kind, can easily make zeolite of the present invention, therefore preferred.

(1) comprises nitrogen-atoms as heteroatomic ester ring type heterocyclic compound

Comprise nitrogen-atoms and be generally 5 ~ 7 yuan of rings as the heterocycle of heteroatomic ester ring type heterocyclic compound, be preferably 6 yuan of rings.The heteroatomic number that contains in heterocycle is generally below 3, is preferably below 2.Hetero atom beyond the nitrogen-atoms is arbitrarily, but preferably not only comprises nitrogen-atoms, and comprises oxygen atom.Heteroatomic position is not particularly limited, but preferred hetero atom is not adjacent to each other.

In addition, comprise nitrogen-atoms and be generally below 250 as the molecular weight of heteroatomic ester ring type heterocyclic compound, be preferably below 200, more preferably below 150, and be generally more than 30, be preferably more than 40, more preferably more than 50.

Comprise nitrogen-atoms as heteroatomic ester ring type heterocyclic compound as such, can enumerate morpholine, N-methylmorpholine, piperidines, piperazine, N, N '-lupetazin, Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane, N-methyl piperidine, 3-methyl piperidine, quinuclidine, pyrrolidines, 1-METHYLPYRROLIDONE, hexamethylene imine etc.These can use separately a kind, also can be mixed with two or more.Wherein, preferred morpholine, hexamethylene imine, piperidines, particularly preferably morpholine.

(2) alkylamine

The alkyl of alkylamine is generally chain-like alkyl, and contained alkyl number is not particularly limited in 1 molecule of alkylamine, but preferred 3.

In addition, the part in the alkyl of alkylamine can have the substituting groups such as hydroxyl.

The carbon number of the alkyl of alkylamine is preferred below 4, and more preferably the carbon number of the whole alkyl in 1 molecule adds up to 5 ~ 30.

In addition, the molecular weight of alkylamine is generally below 250, is preferably below 200, more preferably below 150.

As such alkylamine, can enumerate di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, triethylamine, triethanolamine, N, N-diethyl ethylene diamine, N, N-dimethylethanolamine, N methyldiethanol amine, N-methylethanolamine, di-n-butyl amine, neopentyl amine, two n-amylamines, isopropylamine, tert-butylamine, ethylenediamine, diisopropylethylamine, N-methyl-n-butylamine etc.These can use separately a kind, also can be mixed with two or more.Wherein, preferred di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, triethylamine, di-n-butyl amine, isopropylamine, tert-butylamine, ethylenediamine, diisopropylethylamine, N-methyl-n-butylamine, particularly preferably triethylamine.

(3) Cycloalkyl amine

As Cycloalkyl amine, the carbon number of preferred alkyl is 4 ~ 10 Cycloalkyl amine, wherein preferred cyclohexylamine.Cycloalkyl amine can use separately a kind, also can be mixed with two or more.

(4) tetraalkylammonium hydroxide

As tetraalkylammonium hydroxide, preferred 4 alkyl are that carbon number is the tetraalkylammonium hydroxide of 4 following alkyl.Tetraalkylammonium hydroxide can be used separately a kind, also can be mixed with two or more.

As template, when being used in combination more than 2 kinds, its combination is arbitrarily, but preferred and with in morpholine, triethylamine and the cyclohexylamine more than 2 kinds, wherein preferred and with morpholine and triethylamine.

The blending ratio of each group of these templates need to be selected according to condition.When 2 kinds of templates were mixed, usually, the mol ratio of 2 kinds of templates of mixing was 1:20 ~ 20:1, is preferably 1:10 ~ 10:1, more preferably 1:5 ~ 5:1.When 3 kinds of templates were mixed, the mol ratio of common the 3rd kind of template was preferably 1:10 ~ 10:1, more preferably 1:5 ~ 5:1 with respect to take 2 kinds of templates of above-mentioned mixed in molar ratio as 1:20 ~ 20:1.

{ modulation of aqueous gel }

Aqueous gel for above-mentioned silicon atom raw material, aluminium atomic raw material, phosphorus atoms raw material, transition metal atoms raw material, and polyamines, other template mix with water and modulate.

With with silicon atom raw material, aluminium atomic raw material, phosphorus atoms raw material, and the molar ratio computing of transition metal atoms raw material when representing as oxide, the composition of the aqueous gel that uses among the present invention preferably is made as following composition.

SiO ₂/ Al ₂O ₃Value be generally greater than 0, be preferably more than 0.1, and be preferably below 0.8, more preferably below 0.6, and more preferably below 0.4, be particularly preferably below 0.3.

In addition, P ₂O ₅/ Al ₂O ₃Value be generally more than 0.6, be preferably more than 0.7, more preferably more than 0.8, and be generally below 1.3, be preferably below 1.2, more preferably below 1.1.

M _aO _b/ Al ₂O ₃The value of (wherein, a and b represent respectively the atomic ratio of M and O) is generally more than 0.01, is preferably more than 0.03, more preferably more than 0.05, and is generally below 1, is preferably below 0.8, more preferably below 0.4, more preferably below 0.3.

If SiO ₂/ Al ₂O ₃Greater than the above-mentioned upper limit, then be difficult to crystallization, perhaps hydrothermal durability is insufficient.

If P ₂O ₅/ Al ₂O ₃Less than above-mentioned lower limit, then be difficult to crystallization, perhaps hydrothermal durability is insufficient, and is difficult to equally crystallization greater than the above-mentioned upper limit, and perhaps hydrothermal durability is insufficient.

By having correlation forming with forming of aqueous gel of the resulting zeolite of Hydrothermal Synthesis, therefore, in order to obtain the zeolite of required composition, the composition of aqueous gel suitably set in the above range get final product.

In addition, if M _aO _b/ Al ₂O ₃Less than above-mentioned lower limit, then the import volume of transition metal is insufficient in the zeolite, if greater than the above-mentioned upper limit, then is difficult to crystallization, and perhaps hydrothermal durability is insufficient.

The amount of the polyamines in the aqueous gel is when using template, and being set as is enough to make the amount of transition metal atoms raw material stabilisation to get final product, but when not using template, polyamines has the effect of template concurrently, therefore need to be set as for the amount that works as template.

Particularly, preferably be made as following use amount.

＜template 〉

With regard to template, the Al that the polyamines in the aqueous gel and the total amount of template convert with respect to the oxide of the aluminium atomic raw material in the aqueous gel with the total of polyamines and template ₂O ₃Molar ratio computing, be generally more than 0.2, be preferably more than 0.5, more preferably more than 1, and be generally below 4, be preferably below 3, more preferably below 2.5.

If polyamines lacks than above-mentioned lower limit with the total amount of template, then might be because of the difference of the modulation condition of zeolite, zeolite may be difficult to crystallization, perhaps because of the difference for the requirement of catalytic performance, hydrothermal durability may be insufficient, if more than the above-mentioned upper limit, then the yield of zeolite might become insufficient.

In addition, polyamines preferably uses with following amount: with the M of polyamines with respect to the oxide conversion of transition metal atoms raw material _aO _bMolar ratio computing, be generally more than 0.1, be preferably more than 0.5, more preferably more than 0.8, and be generally below 10, be preferably below 5, more preferably below 4.

If the amount of the polyamines in the aqueous gel is lacked than above-mentioned lower limit, then can't obtain fully the effect of the present invention because using polyamines to produce, the effect of the cooperation materialization of the transition metal atoms raw material that is namely caused by polyamines and the stabilisation that produces, high-temperature water heat durability etc., if more than the above-mentioned upper limit, then the yield of zeolite is insufficient.

Should illustrate, as previously mentioned, template need to be according to condition and suitably select, for example, and with morpholine and triethylamine during as template, preferably become 0.05 ~ 20, particularly 0.1 ~ 10, especially 0.2 ~ 9 mode with the mol ratio of morpholine/triethylamine and use.

To from above-mentioned group more than 2, respectively organize the order of selecting respectively the template more than a kind to mix and be not particularly limited, mix with other material after template can being mixed with each other, also each template can be mixed with other material respectively.

In addition, for the ratio of the water in the aqueous gel, consider from the viewpoint that easily synthetic and generation rate is high, when the aluminium atomic raw material is represented with oxide, with water for Al ₂O ₃Molar ratio computing, be generally more than 3, be preferably more than 5, more preferably more than 10, and be generally below 200, be preferably below 150, more preferably below 120.

The pH of aqueous gel is generally more than 5, is preferably more than 6, more preferably more than 6.5, and is generally below 11, is preferably below 10, more preferably below 9.

Should illustrate, in aqueous gel, according to required, can contain above-mentioned composition in addition.As such composition, can enumerate the hydrophilic organic solvent such as hydroxide, salt, alcohol of alkali metal or alkaline-earth metal.As the content of these other compositions in the aqueous gel, for hydroxide, the salt of alkali metal or alkaline-earth metal, when the aluminium atomic raw material is represented with oxide, with respect to Al ₂O ₃Molar ratio computing, be generally below 0.2, be preferably below 0.1, alcohol waits hydrophilic organic solvent to be generally below 0.5 with molar ratio computing with respect to the water in the aqueous gel, is preferably below 0.3.

Not restriction of the order by merging of each raw material during the modulation aqueous gel is suitably selected to get final product according to used condition, but usually at first phosphorus atoms raw material, aluminium atomic raw material is mixed in water, mixes therein silicon source and template.Transition metal atoms raw material, polyamines can add any opportunity when they are mixed, if but be pre-mixed transition metal atoms raw material and polyamines, then have the stabilization effect that the cooperation materialization of effectively bringing into play the transition metal atoms raw material that is caused by polyamines produces.

On the other hand, the transition metal raw material is dissolved in the aqueous gel.When synthesizing under the state that does not fully dissolve, transition metal fully disperses on zeolite, and purifying property reduces.When making the dissolving of transition metal raw material, the transition metal raw material is dissolved in the water mixes with aqueous gel afterwards.But, in this case owing to considering the solubility of transition metal raw material in water, with aqueous gel in the use the relationship between quantities of water on, sometimes be difficult to finally increase the transition metal amount of dissolving in the aqueous gel.Therefore, when synthesize increasing the transition metal amount, preferably in water, be dissolved with at least in the phosphorus atoms material solution of phosphorus atoms raw material the method for other raw material of interpolation behind the mixed dissolution transition metal raw material.Because the phosphorus atoms material solution is acid, therefore not only can dissolve with comparalive ease transition metal salt, but also can be than the oxide that is easier to dissolve transition metal, available more a small amount of water carries out Hydrothermal Synthesis.

{ Hydrothermal Synthesis }

Hydrothermal Synthesis is by putting into pressure vessel according to the aqueous gel of above-mentioned modulation, under the pressure that self produces, perhaps under the gas pressurized of the degree that does not hinder crystallization, keeps set point of temperature to carry out under stirring or static condition.

Reaction temperature during Hydrothermal Synthesis is generally more than 100 ℃, is preferably more than 120 ℃, more preferably more than 150 ℃, and is generally below 300 ℃, is preferably below 250 ℃, more preferably below 220 ℃.Reaction time was generally more than 2 hours, was preferably more than 3 hours, more preferably more than 5 hours, and was generally below 30 days, was preferably below 10 days, more preferably below 4 days.Reaction temperature can be constant in reaction, also can make it interim ground or continuously variation.

{ containing the zeolite of template etc. }

Behind the Hydrothermal Synthesis, will from hydrothermal synthesis reaction liquid, separate as the zeolite that contains polyamines and the template of using as required (below, polyamines or polyamines are called " template etc. " with template) of product.The separation method of zeolite from hydrothermal synthesis reaction liquid that contains template etc. is not particularly limited.Usually, can utilize and filter or decant etc. separates, after the washing, obtain the zeolite that contains template etc. as product under the temperature of room temperature to 150 ℃, carrying out drying.

Then, usually from the zeolite that contains template etc. that from hydrothermal synthesis reaction liquid, separates, remove template etc.The method of removing of template etc. is not particularly limited.Usually, can air or contain the non-active gas of aerobic or the atmosphere of non-active gas under calcine the method that the extraction solvent that perhaps utilize ethanol water, contains the ether etc. of HCl extracts etc. and remove contained organic matter (template etc.) in 300 ℃ ~ 1000 ℃ temperature.

Aspect property easy to manufacture, template etc. is removed in preferred utilization calcining.In this case, about calcining heat, be preferably 400 ℃ ~ 900 ℃, more preferably 450 ℃ ~ 850 ℃, more preferably 500 ℃ ~ 800 ℃.

[purposes that contains the zeolite of transition metal]

As the purposes that contains the zeolite of transition metal of the present invention, be not particularly limited, but, catalyst activity high from resistance to water and high-temperature water heat durability also excellent, steam repeatedly the stability of the attached catalyst activity of adsorption and desorption also consider excellent aspect, be especially suitable for use as exhaust gas purification catalyst and or the water vapor adsorption material of automobile etc.

＜exhaust emission control catalyst 〉

The zeolite that contains transition metal of the present invention can be used as exhaust emission control catalyst, preferably can be used as automobile exhaust gas purifying catalyst.When the zeolite that contains transition metal of the present invention is used as automobile exhaust gas purifying catalyst, can be directly with the Powdered use zeolite that contains transition metal of the present invention, in addition, also can mix with adhesives such as silica, aluminium oxide, clay minerals, carry out granulation, moulding and use.In addition, when the purification catalyst for automobile exhaust, also available rubbing method, the method for forming and the fixed shape of moulding established practice and use, preferred plastic one-tenth is cellular and use.

When the formed body of the catalyst that utilizes rubbing method to obtain to comprise the zeolite that contains transition metal of the present invention, usually zeolite and the silica by containing transition metal, the inorganic bonds such as aluminium oxide mix, make slurry, surface at the formed body of making of inorganic matters such as cordierites is coated with, calcine and make, can obtain cellular catalyst preferred this moment by the formed body coating in honeycomb shape.

When moulding comprises the formed body of catalyst of the zeolite that contains transition metal of the present invention, usually, the inorganic bonds such as the zeolite by will containing transition metal and silica, aluminium oxide; The inorfil of alumina fibre, glass fibre etc. is mediated, and carries out the moulding of extrusion molding, compression method etc., then calcines and makes, and can obtain honeycombed catalyst preferred this moment by being molded into honeycomb shape.

The catalyst that comprises the zeolite that contains transition metal of the present invention is as contacting with the exhaust that comprises nitrogen oxide and the purification catalyst for automobile exhaust of purifying nitrogen oxide is effective.Nitrogen oxide composition in addition can be comprised in this exhaust, for example hydrocarbon, carbon monoxide, carbon dioxide, hydrogen, nitrogen, oxygen, oxysulfide, water can be comprised.In addition, also can use the known reducing agent of nitrogen-containing compounds such as hydrocarbon, ammonia, urea etc.Particularly, utilize purification catalyst for automobile exhaust of the present invention, can purify contained nitrogen oxide in the multiple exhaust of discharging the various diesel engines used from diesel car, gasoline automobile, stationary power generation boats and ships agricultural machinery building machinery motorcycle aircraft, boiler, the fuel oil turbine etc.

Catalyst when comprising the catalyst of the zeolite that contains transition metal of the present invention as use and the contact conditions of exhaust, be not particularly limited, but can use under the following conditions: the air speed of exhaust (extraction flow hourly/catalyst loading) is generally more than the 100/h, be preferably more than the 1000/h, and be generally below the 500000/h, be preferably below the 100000/h, temperature is generally more than 100 ℃, be preferably more than 150 ℃, and be generally below 700 ℃, be preferably below 500 ℃.

Above, be treated to prerequisite and describe to be applied to automobile exhaust, as long as but satisfy above-mentioned characteristic, certainly also can fully be applied to the exhaust of factory, from fixed, the purification of the nitrogen oxide that comprises in the diversified exhaust of namely discharging in the various diesel engines used of stationary power generation, boats and ships, agricultural machinery, building machinery, cart, aircraft, boiler, the fuel oil turbine etc.

In addition, as the applicable exhaust that contains the zeolite of transition metal of the present invention, preferably contain the NOx(nitrogen oxide) exhaust, in this exhaust, can comprise the composition beyond the nitrogen oxide, for example hydrocarbon, carbon monoxide, carbon dioxide, hydrogen, nitrogen, oxygen, oxysulfide, water.In addition, purify the NOx(nitrogen oxide at the known reducing agents such as nitrogenate with hydrocarbon, ammonia, urea etc.) time, the known reducing agents such as nitrogen-containing compound of hydrocarbon, ammonia, urea etc. also can be comprised.

[water vapor adsorption material]

The zeolite that contains transition metal of the present invention demonstrates the adsorption-desorption characteristic of excellent steam.

The degree of this adsorption-desorption characteristic is different different because of condition, but generally speaking, all adsorbable to the high-temperature area that usually is difficult to the adsorbed water steam from low temperature, all adsorbable to the low humidity zone that usually is difficult to the adsorbed water steam from the high humility state in addition, and can be in lower temperature carry out desorption below 100 ℃.

As the purposes of such water vapor adsorption material, can enumerate adsorption heat pump, heat exchanger, dehumidification air conditioner etc.

With regard to the zeolite that contains transition metal of the present invention, as the water vapor adsorption material, demonstrate especially excellent performance, but when the zeolite that will of the present inventionly contain transition metal is used as the water vapor adsorption material, can with the metal oxides such as silica, aluminium oxide, titanium dioxide; The adhesive ingredients such as clay; The composition that heat conductivity is high uses together.When the zeolite that contains transition metal of the present invention is used with these other compositions, the content that contains the zeolite of transition metal of the present invention in the water vapor adsorption material is preferably more than 60 % by weight, more preferably more than 70 % by weight, more preferably more than 80 % by weight.

Embodiment

Below, utilize embodiment to specify the present invention, but the present invention is not subject to any restriction of following examples in the scope that does not exceed its main idea.

Analysis and the performance evaluation of the zeolite that contains transition metal that obtains in following examples and comparative example (below, only be recited as " zeolite ") utilize following methods to carry out.

[mensuration of XRD]

Use is measured under the following conditions with the sample of following methods modulation.

The modulation of＜sample 〉

Will with agate mortar manually pulverize and the zeolite sample approximately 100mg make sample size certain with the specimen holder of same shape.

＜condition determination 〉

X-ray source: Cu-K alpha ray

Output is set: 40kV, 30mA

Optical condition during mensuration:

Divergent slit=1 °

Scatter slit=1 °

Be subjected to optical slits=0.2mm

The position of diffraction maximum: 2 θ (angle of diffraction)

Measurement range: 2 θ=3 ~ 50 degree

Sweep speed: 3.0 ° (2 θ/sec), continuous sweep

[analysis that Cu content and zeolite form]

With regard to the elementary analysis in silicon, aluminium, phosphorus atoms and the transition metal copper atom of skeleton structure of zeolite, make sample in aqueous hydrochloric acid solution, after the heating for dissolving, utilize inductively coupled plasma (ICP:Inductively Coupled Plasma) ICP Atomic Emission Spectrophotometer to obtain the content W of silicon, aluminium, phosphorus atoms and the Cu of skeleton structure of zeolite ₁(% by weight).Perhaps, behind the sample compression molding, utilize fluorescent x-ary analysis (XRF), wherein utilize especially energy dispersion type optical spectroscopy (EDX) and obtain the content W of silicon, aluminium, phosphorus atoms and the Cu of skeleton structure of zeolite ₁(% by weight).

On the other hand, utilize thermogravimetric analysis (TG) to obtain moisture W in the sample _H2O(% by weight) according to following formula (V), calculates the content W(% by weight of each atom and the Cu of the skeleton structure in the zeolite that contains transition metal under anhydrous state).

W=W ₁/（1-W _H2O） …（V）

＜BET specific area 〉

Use large storehouse reason to grind company's automatic powder specific area measuring processed device (AMS1000), utilize the flow type one point method to measure.

[water vapor adsorption isotherms]

With the zeolite sample of modulation in 120 ℃ carry out vacuum exhaust in 5 hours after, utilize water vapor adsorption amount determining device (Bellsorp18: the Japanese Bell Co., Ltd. system) water vapor adsorption isotherms when measuring 25 ℃ according to following condition.

Air thermostat temperature: 50 ℃

Adsorption temp: 25 ℃

Initial stage imports pressure: 3.0torr

The importing pressure setting is counted: 0

Saturated vapour pressure: 23.755torr

Equilibration time: 500 seconds

[evaluation of catalyst activity (initial activity)]

After the zeolite sample of modulation is compressing, carry out fragmentation, sieve, whole grain becomes 0.6 ~ 1mm.To under normal pressure, be filled in the fixed bed flow type reaction tube through the zeolite sample 1ml of whole grain.The gas of the composition of following table 1 is circulated on one side in zeolite layer with air speed SV=100000/h, Yi Bian heat zeolite layer.150 ℃, 175 ℃, 200 ℃ at each temperature, become when constant in outlet NO concentration, utilize

NO purifying rate (%)

The value of={ (entrance NO concentration)-(outlet NO concentration) }/(entrance NO concentration) * 100, the activity of removing nitrogen oxide of evaluation zeolite sample.

Table 1

Gas componant	Concentration
		NO	350ppm
NH ₃	385ppm
		O ₂	15 volume %
H ₂O	5 volume %
		N ₂	The surplus of mentioned component

[evaluation of catalyst activity (after the hydro-thermal long duration test)]

After the zeolite sample of modulation is compressing, carry out fragmentation, sieve, after whole grain becomes 0.6 ~ 1mm, utilize the hydro-thermal long duration test of following steam treatment.For the zeolite sample that has carried out the hydro-thermal long duration test, with above-mentioned same, carry out the evaluation of catalyst activity (after hydro-thermal is durable).

[hydro-thermal long duration test]

With zeolite in 800 ℃, the steam of 10 volume %, under the atmosphere of air speed SV=3000/h by 5 hours, carry out hydrothermal treatment consists.For the sample that reclaims after the test, estimate the NO purifying rate with the evaluation method of above-mentioned catalyst activity.

[evaluation of catalyst activity (steam is adsorption and desorption adhesion test-1(90 ℃-80 ℃-5 ℃ repeatedly adsorption and desorption adhesion test of steam repeatedly))]

The zeolite sample 0.5g of modulation is remained in the collar plate shape vacuum tank that remains in 90 ℃, in 5 ℃ saturated steam atmosphere and 80 ℃ of saturated steam atmosphere, expose respectively 90 seconds, repeat aforesaid operations.When the saturated steam atmosphere that is exposed to 80 ℃, be adsorbed on water in the sample this moment 5 ℃ saturated steam atmosphere next part desorption, move in the catch pit that remains on 5 ℃.From the m time be adsorbed to the n time the desorption, by the total amount (Qn that moves to the water in 5 ℃ the catch pit; M(g)) with the dry weight (W(g) of sample) followingly obtain each average adsorbance (Cn; M(g/g)).

[Cn；m]=[Qn；m]/（n-m+1）/W

At above-mentioned steam repeatedly in the adsorption and desorption adhesion test, obtain from the 1001st time to the 2000th time average adsorbance with respect to the ratio from the 1st time to the 1000th time average adsorbance with percentage, be made as the sustainment rate of adsorption and desorption adhesion test.(below, be expressed as " 90-80-5 is durable ")

[evaluation of catalyst activity (steam is adsorption and de-adsorption endurancing-2(90 ℃-60 ℃-5 ℃ repeatedly adsorption and desorption adhesion test of steam repeatedly))]

As the repeatedly adsorption and de-adsorption experimental condition close to the actual installation condition, use the experimental rig shown in Figure 11, implement " 90 ℃-60 ℃-5 ℃ repeatedly adsorption and desorption adhesion tests of steam " (following table is shown as " 90-60-5 is durable ") of catalyst.

In Figure 11,1 for remaining on 60 ℃ thermostatic chamber, and 2 for remaining on 90 ℃ thermostatic chamber, and 3 for remaining on 5 ℃ thermostatic chamber.In thermostatic chamber 1, be provided with the container 4 of saturated steam, in thermostatic chamber 2, be provided with the vacuum tank 5 that keeps sample, in thermostatic chamber 3, be provided with the container 6 that becomes catch pit.Container 4 is situated between with vacuum tank 5 and is connected by the pipe arrangement with pump a, and container 6 is situated between with vacuum tank 5 and is connected by the pipe arrangement with pump 6.

Sample is remained in the vacuum tank 5 that remains in 90 ℃, under 5 ℃ saturated steam atmosphere (90 ℃ relative humidity 1%) and 60 ℃ saturated steam atmosphere (90 ℃ relative humidity 28%), expose respectively 90 seconds, repeat aforesaid operations.That is, be exposed to 60 ℃ being operating as of saturated steam atmosphere, in Figure 11, open pump a(pump b and keep closing).After keeping 90 seconds under this state, when being closed, pump a opens pump b.At this moment, when the saturated steam atmosphere that is exposed to 60 ℃, be adsorbed on water in the sample 15 ℃ saturated steam atmosphere next part desorption, move in the container 6 of the catch pit that remains in 5 ℃.Under this state, kept 90 seconds.

Repeatedly carry out 2000 times above Adsorption and desorption is attached.

For the sample that reclaims after the test, based on the condition of the evaluation method of above-mentioned catalyst activity, estimate the NO purifying rate.The diesel engine exhaust of car etc. comprises the water of 5 ~ 15 volume % in exhaust.In car travelled, exhaust became the high temperature more than 200 ℃, and relative humidity is reduced to below 5%, and catalyst becomes the state with water decomposition absorption.Yet, become more than 15% the catalyst adsorbed water when stopping 90 ℃ of left and right sides relative humidity.Relative humidity becomes 28% when this condition of utilization, 90 ℃ absorption.Important near the repeatedly durability under the state of this physical condition during in actual installation.

[mensuration of probe-microanalyser (EPMA)]

The zeolite sample of preparation is embedded in resin, after cutting with cross-sectional slice machine (diamond sword), carries out the Au evaporation and make sample, for the sample of making, measure under the following conditions.

Device: JEOL shaseiJXA-8100

Electron gun: W transmitter, accelerating potential 15kV, irradiation electric current 20nA

Element is marked and drawed: the visual field that is equivalent to analyze 3000 times of areas or 4000 times

Acquisition time: 100 milliseconds/point

Object elements (analyzing crystal): Si (PET), Cu (LIFH)

[variation coefficient]

In the Heteroatom-aluminophosphate Zeolites of the transition metal M more than containing 3 % by weight, choose zeolite particles by the Si intensity scale drawing of the sample that adopts probe-microanalyser (EPMA) to observe in any 3 visuals field.Image is processed and is used ImageProPlus (Media Cybernetics company system).

Adopt this process software, the Si plot lift-launch median filter that obtains adopting EPMA to analyze carries out noise processed, then chooses the high part of intensity as the sample particle.Then, calculate mean value and the standard deviation of the CuK alpha ray intensity of the sample inside particles of selecting, obtain its variation coefficient.Process the copper of removing the isolated state that is not scattered in zeolite by this image, can check the distribution of the copper that is scattered in zeolite.For example, in the same visual field, be present in intensity scale that particle that the intensity scale of Cu draws the is not present in Si situation in drawing and remove as the copper of isolated state.

[embodiment 1]

Phosphoric acid 8.1g and the cupric oxide 0.5g of adding 85% in water 20g are stirred to fully dissolving with cupric oxide.Then, slowly add boehmite (water that contains 25 % by weight, Condea company system) 5.4g, stirred 1 hour.And then, add aerosil (Aerosil200) 0.6g and water 13.4g, stirred 1 hour.Then, slowly add morpholine 3.4g, triethylamine 4.0g, stirred 1 hour.And then, behind interpolation TEPA (the Kishida Chemical company) 1.1g, stirred 1 hour.Obtain having the aqueous gel of following composition.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.25

Al ₂O ₃:1

P ₂O ₅:0.875

CuO:0.15

TEPA: 0.15

Morpholine: 1

Triethylamine: 1

Water: 50

The aqueous gel that obtains is like this packed in the stainless steel autoclave of 100ml that is placed with the fluororesin inner core, with 15rpm stir on one side, on one side in 190 ℃ of reactions 24 hours.Behind the Hydrothermal Synthesis, cool off, utilize decant to remove cleer and peaceful copper powder, reclaim sediment.Filter after the sediment water cleaned 3 times, carry out drying in 100 ℃.Then calcine under air draught in 550 ℃, remove organic matter, obtain zeolite 1.

Measure the XRD of zeolite 1, the result is the CHA structure

(measurement result of XRD is shown among Fig. 1).The average one-level particle diameter of this zeolite is 14 μ m.Utilizing the loading of the Cu of EDX analysis is 4.3%.In addition, utilize the composition analysis of the zeolite of EDX, each composition with respect to the composition (mol ratio) of the total of silicon, aluminium and the phosphorus of skeleton structure is as a result: silicon is 0.097, and aluminium is 0.49, and phosphorus is 0.41(Al/(Si+P)=0.97).

In addition, the measurement result (distribution diagram of element of Si and Cu) with EPMA is shown among Fig. 2.In zeolite 1, the mean change coefficient of the intensity of Cu is 27.9%.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 3.52mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 267mg/g.The water vapor adsorption isotherms measurement result is shown among Fig. 3.

For this zeolite 1, carry out the evaluation of catalyst activity.Evaluation result is shown in Table 3.In addition, for this zeolite 1, carry out the mensuration of BET specific area, the result is 647m ²/ g.

[embodiment 2]

Carry out similarly to Example 1 Hydrothermal Synthesis, calcine under air draught in 800 ℃, remove organic matter, obtain zeolite 2.Measure the XRD of the zeolite 2 that obtains like this, the result is the CHA structure

Utilizing the loading of the Cu of EDX analysis is 4.3%.In addition, utilize the composition analysis of the zeolite of EDX, each composition with respect to the composition (mol ratio) of the total of silicon, aluminium and the phosphorus of skeleton structure is as a result: silicon is 0.097, and aluminium is 0.49, and phosphorus is 0.41.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 3.52mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 267mg/g.

[embodiment 3]

Phosphatase 79 5g and the cupric oxide 7.2g of adding 75% in water 217g are stirred to fully dissolving with cupric oxide.Then, slowly add boehmite (water that contains 25 % by weight, Condea system) 61.8g, stirred 2 hours.And then, add aerosil (Aerosil200) 16.4g and water 153.2g, stirred 10 minutes.Then, slowly add morpholine 39.6g, triethylamine 46g, stirred 1 hour.And then, behind interpolation TEPA (the Kishida Chemical company) 17.2g, stirred 0.5 hour.Obtain having the aqueous gel of following composition.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.6

Al ₂O ₃:1

P ₂O ₅:0.8

CuO:0.2

TEPA: 0.2

Morpholine: 1

Triethylamine: 1

Water: 50

The aqueous gel that obtains is like this packed in the stainless steel autoclave of 1L that is placed with the fluororesin inner core, with 200rpm stir on one side, on one side in 190 ℃ of reactions 24 hours.Behind the Hydrothermal Synthesis, cool off, filter, after the gained product is cleaned with ion exchange water, carry out drying in 100 ℃.Then calcine under air draught in 550 ℃, remove organic matter, obtain zeolite 3.The average one-level particle diameter of this zeolite is 13 μ m.

Measure the XRD of the zeolite 3 that obtains like this, the result is the CHA structure

Utilizing the loading of the Cu of EDX analysis is 5.1%.In addition, utilize the composition analysis of EDX zeolite, each composition with respect to the composition (mol ratio) of the total of silicon, aluminium and the phosphorus of skeleton structure is as a result: silicon is 0.16, and aluminium is 0.50, and phosphorus is 0.34.

In addition, the loading that utilizes the Cu of XRF analysis is 5.1 % by weight, each atom with respect to the composition (mol ratio) of the total of silicon atom, aluminium atom and the phosphorus atoms of skeleton structure of zeolite is: silicon atom is 0.16, and the aluminium atom is 0.50, and phosphorus atoms is 0.34(Al/(Si+P)=1).

The measurement result (distribution diagram of element of Si and Cu) of the EPMA of this zeolite 3 is shown among Fig. 4.In zeolite 3, the mean change coefficient of the intensity of Cu is 28.4%.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 1.68mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 275mg/g.Water vapor adsorption isotherms is shown among Fig. 5.

For this zeolite 3, carry out the evaluation of catalyst activity.Evaluation result is shown in Table 3.

In addition, for this zeolite 3, carry out the mensuration of BET specific area, the result is 590m ²/ g.

[embodiment 4]

Carry out similarly to Example 3 Hydrothermal Synthesis, calcine under air draught in 800 ℃, remove organic matter, obtain zeolite 4.

Measure the XRD of the zeolite 4 that obtains like this, the result is the CHA structure

Utilizing the loading of the Cu of EDX analysis is 5.5%.In addition, utilize the composition analysis of the zeolite of EDX, each composition with respect to the composition (mol ratio) of the total of silicon, aluminium and the phosphorus of skeleton structure is as a result: silicon is 0.16, and aluminium is 0.50, and phosphorus is 0.34.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 2.09mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 275mg/g.

For this zeolite 4, carry out the evaluation of catalyst activity.Evaluation result is shown in Table 3.

[embodiment 5]

In water 10g, slowly add phosphoric acid 8.1g and boehmite (water that contains 25 % by weight, the Condea company system) 5.4g of 85 % by weight, stirred 1 hour.And then, add aerosil (Aerosil200, Japanese Aerosil company system) 0.6g and water 10g, stirred for 1 time.Then, slowly add morpholine 3.4g, triethylamine 4.0g, stirred 1 hour.This is made as A liquid.

Different from A liquid, with CuSO ₄5H ₂O(KISHIDA CHEMICAL company system) after 1.0g is dissolved in the 13.4g water, adds 0.8g TEPA (KISHIDA CHEMICAL company system), mix, modulation B liquid.

B liquid is added in the A liquid lentamente.It was stirred 1 hour, obtain having the aqueous gel of following composition.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.25

Al ₂O ₃:1

P ₂O ₅:0.875

CuO:0.1

TEPA: 1

Morpholine: 1

Triethylamine: 1

Water: 50

The aqueous gel that obtains is like this packed in the stainless steel autoclave of the 100ml that is placed with the fluororesin inner core, with 15rpm stir on one side, on one side in 190 ℃ of 24 times of reaction.Behind the Hydrothermal Synthesis, cool off, utilize decant to remove supernatant, reclaim sediment.After sediment water cleaning 3 times, filter, carry out drying in 100 ℃.Then, calcine under air draught in 550 ℃, remove organic matter, obtain zeolite 5.

Measure the XRD of the zeolite 5 that obtains like this, the result is the CHA structure

Measure SEM, average grain diameter is 10 μ m as a result.

The measurement result of XRD is shown among Fig. 6.

In addition, for this zeolite 5, carry out the evaluation of the catalyst activity of steam treatment front and back.Evaluation result is shown in Table 2.

[embodiment 6]

Similarly to Example 5 operation, modulation A liquid.

Different from A liquid, with CuSO ₄5H ₂O(KISHIDA CHEMICAL company system) after 1.0g is dissolved in the 13.4g water, adds triethylene tetramine (KISHIDA CHEMICAL company system) 0.6g, mix, modulation B liquid.

B liquid is slowly added in the A liquid.It was stirred 1 hour, obtain having the aqueous gel of following composition.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.25

Al ₂O ₃:1

P ₂O ₅:0.875

CuO:0.1

Triethylene tetramine: 1

Morpholine: 1

Triethylamine: 1

Water: 50

The aqueous gel that use obtains, separation, drying and the calcining of Hydrothermal Synthesis, product are carried out in similarly to Example 5 operation, obtain zeolite 6.

Measure the XRD of the zeolite 6 that obtains like this, the zeolite 5 of result and embodiment 5 is similarly the CHA structure.Measure SEM, average grain diameter is 12 μ m as a result.

The water vapor adsorption isotherms measurement result of the zeolite 6 that obtains is shown among Fig. 7.

For the zeolite 6 that obtains, carry out the evaluation of the catalyst activity of steam treatment front and back.Evaluation result is shown in Table 2.

In addition, for this zeolite 6, adsorption and desorption adhesion test-1(90-80-5 is durable repeatedly to carry out steam), the sustainment rate of as a result adsorption and desorption adhesion test is 100%.

[embodiment 7]

In water 10g, slowly add phosphoric acid 6.5g and boehmite (water that contains 25 % by weight, the Condea company system) 5.4g of 85 % by weight, stirred 1 hour.And then, add aerosil (Aerosil200, Japanese Aerosil company system) 1.4g and water 10g, stirred 1 hour.Then, slowly add morpholine 3.4g, triethylamine 4.0g, stirred 1 hour.This is made as A liquid.

Different from A liquid, with CuSO ₄5H ₂O(KISHIDA CHEMICAL company system) after 1.0g is dissolved in the 13.7g water, adds triethylene tetramine (KISHIDA CHEMICAL company system) 0.6g, mix, modulation B liquid.

B liquid is slowly added in the A liquid.This was stirred 1 hour, obtain having the aqueous gel of following composition.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.6

Al ₂O ₃:1

P ₂O ₅:0.7

CuO:0.1

Triethylene tetramine: 0.1

Morpholine: 1

Triethylamine: 1

Water: 50

The aqueous gel that use obtains, separation, drying and the calcining of Hydrothermal Synthesis, product are carried out in similarly to Example 5 operation, obtain zeolite 7.

Measure the XRD of the zeolite 7 that obtains like this, the zeolite 5 of result and embodiment 5 is similarly the CHA structure.

For the zeolite 7 that obtains, carry out the evaluation of the front catalyst activity of steam treatment.Evaluation result is shown in Table 2.

[embodiment 8]

Similarly to Example 5 operation, modulation A liquid.

Different from A liquid, with Cu(CH ₃COO) ₂5H ₂O(KISHIDA CHEMICAL company system) after 0.8g is dissolved in the 13.4g water, adds triethylene tetramine (KISHIDA CHEMICAL company system) 0.6g, mix, modulation B liquid.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.25

Al ₂O ₃:1

P ₂O ₅:0.875

CuO:0.1

Triethylene tetramine: 0.1

Morpholine: 1

Triethylamine: 1

Water: 50

The aqueous gel that use obtains, separation, drying and the calcining of Hydrothermal Synthesis, product are carried out in similarly to Example 5 operation, obtain zeolite 8.

Measure the XRD of the zeolite 8 that obtains like this, the result is the CHA structure

The measurement result of XRD is shown among Fig. 8.Utilizing the loading of the Cu of EDX analysis is 5.1%.In addition, utilize the composition analysis of the zeolite of EDX, each composition with respect to the composition (mol ratio) of the total of silicon, aluminium and the phosphorus of skeleton structure is: silicon is 0.09, and aluminium is 0.50, and phosphorus is 0.41.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 1.93mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 283mg/g.The water vapor adsorption isotherms measurement result is shown among Fig. 9.

In addition, the zeolite 8 for obtaining carries out the evaluation of catalyst activity.Evaluation result is shown in table 2 and the table 3.

[embodiment 9]

In water 10g, slowly add phosphoric acid 8.1g and boehmite (water that contains 25 % by weight, the Condea company system) 5.4g of 85 % by weight, stirred 1 hour.And then, add aerosil (Aerosil200, Japanese Aerosil company system) 0.6g and water 10g, stirred 1 hour.This is made as A liquid.

Different from A liquid, with CuSO ₄5H ₂O(KISHIDA CHEMICAL company system) after 1.0g is dissolved in the 13.4g water, adds 7.6g TEPA (KISHIDA CHEMICAL company system), mix, modulation B liquid.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.25

Al ₂O ₃:1

P ₂O ₅:0.875

CuO:0.1

TEPA: 1

Water: 50

The aqueous gel that use obtains, separation, drying and the calcining of Hydrothermal Synthesis, product are carried out in similarly to Example 5 operation, obtain zeolite 9.

Measure the XRD of the zeolite 9 that obtains like this, the zeolite 5 of result and embodiment 5 is similarly the CHA structure.Measure SEM, average grain diameter is 12 μ m as a result.

For the zeolite 9 that obtains, carry out the evaluation of the front catalyst activity of steam treatment.Evaluation result is shown in Table 2.

[embodiment 10]

Similarly to Example 5 operation, modulation A liquid.

Different from A liquid, with CuSO ₄5H ₂O(KISHIDA CHEMICAL company system) after 0.3g is dissolved among the water 13.4g, adds triethylene tetramine (KISHIDA CHEMICAL company system) 0.6g, mix, modulation B liquid.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.25

Al ₂O ₃:1

P ₂O ₅:0.875

CuO:0.03

Triethylene tetramine: 0.1

Morpholine: 1

Triethylamine: 1

Water: 50

The aqueous gel that use obtains, separation, drying and the calcining of Hydrothermal Synthesis, product are carried out in similarly to Example 5 operation, obtain zeolite 10.

Measure the XRD of the zeolite 10 obtain like this, be similarly the CHA structure with the zeolite 5 of embodiment 5.

In addition, the water vapor adsorption isotherms when measuring 25 ℃ of this zeolite 10, the result adsorbance variable quantity in relative vapour pressure 0.04 ~ 0.09 o'clock is 0.15g-H ₂O/g.In addition, the water vapor adsorption isotherms when measuring 25 ℃, relative vapour pressure is that 0.2 o'clock water adsorption amount is 0.26g-H as a result ₂O/g.

The water vapor adsorption isotherms of zeolite 10 is shown among Figure 10.

[embodiment 11]

Similarly to Example 5 operation, modulation A liquid.

Different from A liquid, with FeSO ₄7H ₂O(KISHIDA CHEMICAL company system) after 1.1g is dissolved in the 13.4g water, adds TEPA (KISHIDA CHEMICAL company system) 2.4g, mix, modulation B liquid.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.25

Al ₂O ₃:1

P ₂O ₅:0.875

FeO:0.1

TEPA: 0.3

Morpholine: 1

Triethylamine: 1

Water: 50

The aqueous gel that use obtains, separation, drying and the calcining of Hydrothermal Synthesis, product are carried out in similarly to Example 5 operation, obtain zeolite 11.

Measure the XRD of the zeolite 11 that obtains like this, the zeolite 5 of result and embodiment 5 is similarly the CHA structure.

[embodiment 12]

Similarly to Example 5 operation, modulation A liquid.

Different from A liquid, with FeSO ₄7H ₂O(KISHIDA CHEMICAL company system) after 1.1g is dissolved among the water 13.4g, adds 7.7g TEPA (KISHIDA CHEMICAL company system), mix, modulation B liquid.

＜aqueous gel forms (mol ratio)

SiO ₂:0.25

Al ₂O ₃:1

P ₂O ₅:0.875

FeO:0.1

TEPA: 1

Morpholine: 1

Triethylamine: 1

Water: 50

The aqueous gel that use obtains, separation, drying and the calcining of Hydrothermal Synthesis, product are carried out in similarly to Example 5 operation, obtain zeolite 12.

Measure the XRD of the zeolite 12 that obtains like this, the zeolite 5 of result and embodiment 5 is similarly the CHA structure.

[table 2]

By above result as can be known, according to the present invention, can make the zeolite that contains transition metal easy and efficiently, with regard to the zeolite that contains transition metal that makes, the adsorption-desorption excellent performance of catalyst activity and steam, in addition, the high-temperature water heat durability is also excellent.

[comparative example 1]

Utilization is disclosed method in the embodiment 2 of JP 2003-183020 communique, synthetic zeolite X.The dry X zeolite of gained is crushed to particle diameter 3 ~ 5 μ m with airflow milling, then calcines under air draught in 700 ℃, remove template (Wessalith CS).Measure the XRD of gained Wessalith CS, the result is the CHA structure

In addition, utilize the composition analysis of the zeolite of icp analysis, each composition with respect to the composition (mol ratio) of the total of silicon atom, aluminium atom and the phosphorus atoms of skeleton structure is as a result: silicon atom is 0.092, and the aluminium atom is 0.50, and phosphorus atoms is 0.40.Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 0.42mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 314mg/g.

[comparative example 2]

With water 1484kg, 75% phosphoric acid 592kg, and boehmite (water that contains 25 % by weight, Sasol company system) 440kg mix, stirred 3 hours.In this mixed liquor, add aerosil (Aerosil200, Japanese Aerosil company system) 117kg and water 1607kg, stirred 10 minutes.In this mixed liquor, add morpholine 285kg and triethylamine 331kg, stirred 1.5 hours, obtain having the aqueous gel of following composition.

＜aqueous gel forms (mol ratio) 〉

SiO ₂:0.6

Al ₂O ₃:1

P ₂O ₅:0.7

Morpholine: 1

Triethylamine: 1

Water: 60

With this aqueous gel 5m that packs into ³Stainless steel autoclave in, on one side stir, be warming up to heating-up time of 10 hours on one side and be up to 190 ℃ of Da Wendu, kept 24 hours in 190 ℃.After the reaction, cool off, filter, carry out drying under reduced pressure in 90 ℃ after the washing.Gained xeraphium body and function airflow milling is crushed to 3 ~ 5 μ m, then calcines under air draught in 750 ℃, remove template after, obtain zeolite B.

Measure the XRD of zeolite B, the result is the CHA structure

In addition, utilize icp analysis to carry out elementary analysis, each composition with respect to the composition (mol ratio) of the total of silicon atom, aluminium atom and the phosphorus atoms of skeleton structure is as a result: silicon atom is x=0.17, and the aluminium atom is y=0.52, and phosphorus atoms is z=0.31.Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 0.69mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 262mg/g.

[comparative example 3]

For the Wessalith CS that in comparative example 1, obtains, utilize in the world and disclose disclosed method among the embodiment 2A of No. 2010/084930 communique, support copper, calcined 2 hours in 800 ℃, obtain zeolite C.Utilize the composition analysis of the zeolite of icp analysis, each atom with respect to the composition (mol ratio) of the total of silicon atom, aluminium atom and the phosphorus atoms of skeleton structure is as a result: silicon atom is 0.09, and the aluminium atom is 0.50, and phosphorus atoms is 0.41.The loading of the Cu that utilizes XRF analysis of this zeolite C is 3 % by weight.

The measurement result (distribution diagram of element of Si and Cu) of the EPMA of this zeolite C is shown among Figure 12.In zeolite C, the mean change coefficient of the intensity of Cu is 34.1%.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 1.22mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 246mg/g.Water vapor adsorption isotherms is shown among Figure 13.

In addition, for this zeolite C, carry out the evaluation of catalyst activity.Evaluation result is shown in Table 3.

In addition, carry out the mensuration of the BET specific area of this zeolite C, the result is 414m ²/ g.

[comparative example 4]

For the Wessalith CS that in comparative example 1, obtains, utilize in the world and disclose disclosed method among the embodiment 2A of No. 2010/084930 communique, support the copper of 4 % by weight, calcined 2 hours in 800 ℃, obtain zeolite D.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 29mg/g(1.22mol/molSi as a result), the adsorbance during relative vapour pressure 0.7 is 217mg/g.In addition, for this zeolite D, carry out the evaluation of catalyst activity.Evaluation result is shown in Table 3.

[comparative example 5]

For the zeolite B that in comparative example 2, obtains, utilize in the world and disclose disclosed method among the embodiment 2A of No. 2010/084930 communique, support the copper of 3.8 % by weight, calcined 2 hours in 800 ℃, obtain zeolite E.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 0.94mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 225mg/g.Water vapor adsorption isotherms is shown among Figure 14.

In addition, for this zeolite E, carry out the evaluation of catalyst activity.Evaluation result is shown in Table 3.

[comparative example 6]

Utilization is disclosed method in the embodiment 1 of Chinese publication 102259892A specification, synthetic zeolite F.Utilize EDX to analyze (XRF) and carry out elementary analysis, the loading of Cu is 5.8% as a result.Each composition with respect to the composition (mol ratio) of the total of silicon atom, aluminium atom and phosphorus atoms is: silicon atom is x=0.17, and the aluminium atom is y=0.46, and phosphorus atoms is z=0.37.

The measurement result (distribution diagram of element of Si and Cu) of the EPMA of this zeolite F is shown among Figure 15.In zeolite F, the mean change coefficient of the intensity of Cu is 28.2%.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 3.16mol/molSi as a result, the adsorbance during relative vapour pressure 0.7 is 341mg/g.Water vapor adsorption isotherms is shown among Figure 16.In addition, for this zeolite F, carry out the evaluation of catalyst activity.Evaluation result is shown in Table 3.

In addition, carry out the mensuration of the BET specific area of this zeolite F, the result is 610m ²/ g.

[comparative example 7]

Utilization is disclosed method in the embodiment 4 of U.S. publication 2010/0310440A1 specification, synthetic zeolite G.

Water vapor adsorption isotherms when measuring 25 ℃, the adsorbance during relative vapour pressure 0.01 is 0.98mol/molSi as a result), the adsorbance during relative vapour pressure 0.7 is 139mg/g.The steam adsorption isotherm is shown among Figure 17.In addition, for this zeolite G, carry out the evaluation of catalyst activity.Evaluation result is shown in Table 3.

[comparative example 8]

Utilization is disclosed method in the embodiment 6 of U.S. publication US2010/0310440A1 specification, synthetic zeolite H.

Utilize XRF analysis to carry out elementary analysis, each atom with respect to the composition (mol ratio) of the total of silicon atom, aluminium atom and phosphorus atoms is as a result: silicon atom is 0.12, and the aluminium atom is 0.51, and phosphorus atoms is 0.37.

In addition, utilizing the loading of the Cu of XRF analysis is 3.4 % by weight.

With the EPMA(Si of this zeolite H and the distribution diagram of element of Cu) measurement result be shown among Figure 18.In zeolite H, the mean change coefficient of the intensity of Cu is 43.1%.

In addition, in this zeolite H, the evaluation result of catalyst activity is shown among the table 3-2.

In addition, carry out the mensuration of the BET specific area of this zeolite F, the result is 570m ²/ g.

[comparative example 9]

Utilization is disclosed method in the comparative example 5 of WO2010/084930A1 specification, synthetic zeolite I.

It is 2.8 % by weight that this zeolite I utilizes the loading of the Cu of XRF analysis.

In addition, the measurement result (distribution diagram of element of Si and Cu) with EPMA is shown among Figure 19.In zeolite I, the variation coefficient of the intensity of Cu is 15%.

In addition, for this zeolite I, carry out the evaluation of catalyst activity.Show the result among the table 3-2.

Table 3

The evaluation result of catalyst activity

Table 3-2

By above result as can be known, the variation coefficient of the Cu of the zeolite of comparative example 9 is little, but the content of Cu is few, and catalytic performance is low.The Cu of the zeolite of comparative example 3 and comparative example 8 contains quantitative change when many, and variation coefficient uprises, and catalyst activity is low, the repeatedly reduction of the catalyst activity after the adsorption and de-adsorption endurancing of steam occurs.In the zeolite of comparative example 6, the content of Cu is many, and the variation coefficient of Cu is little, but the aluminium atom is below 0.9 with respect to the mol ratio of the total of silicon atom and phosphorus atoms, thereby the catalyst activity after the hydro-thermal long duration test significantly reduces.

Low catalytic performance with respect to these comparative examples 3,6,8,9 zeolite, according to the present invention, the following Heteroatom-aluminophosphate Zeolites that contains transition metal can be provided: it is high levels of transition metals, low variation coefficient (high transition metal dispersion), and the aluminium atom is more than 0.9 with respect to the mol ratio of the total of silicon atom and phosphorus atoms, thereby zeolite structured excellent in stability.This zeolite that contains transition metal has high catalyst activity and stability.

In addition, by above result as can be known, in the water vapor adsorption isotherms of 25 ℃ of mensuration, adsorbance during relative vapour pressure 0.01 is that the catalyst activity of the following SAPO zeolite that contains transition metal of 1.3mol/molSi is low, and perhaps the catalyst low-temperature activity after the adsorption and desorption adhesion test is low repeatedly for steam.Adsorbance during relative vapour pressure 0.7 is that the catalyst activity of the following SAPO zeolite that contains transition metal of 150mg/g is low.Adsorbance during relative vapour pressure 0.7 is that the hydrothermal durability of the above SAPO zeolite that contains transition metal of 300mg/g is low.According to the present invention, in the water vapor adsorption isotherms of 25 ℃ of mensuration, adsorbance during relative vapour pressure 0.01 is that 1.3mol/molSi is above, the adsorbance during relative vapour pressure 0.7 is 150mg/g ~ 300mg/g and transition metal is contained is comprising the zeolite that contains transition metal that forms in the zeolite of silicon atom, phosphorus atoms and aluminium atom in the skeleton structure at least, catalyst activity and hydrothermal durability are high, and then steam the catalyst activity after the adsorption and desorption adhesion test is high repeatedly, also high for the stability of the adsorption and de-adsorption of water.

Utilizability on the industry

The manufacture method that contains the zeolite of transition metal of the present invention is to make easy and efficiently the SAPO zeolite that contains transition metal with high high-temperature water heat durability.

If use the zeolite that contains transition metal by the manufacture method manufacturing of the zeolite that contains transition metal of the present invention, then the nitrogen oxide that comprises in the exhaust of discharging from internal combustion engine etc. can be purified expeditiously, can be not deteriorated in this external high-temperature exhaust air yet, therefore can reduce catalytic amount.

In addition, if use the zeolite that contains transition metal by the manufacture method manufacturing of the zeolite that contains transition metal of the present invention, then as zeolite water steam adsorption material, the adsorption heat pump that can provide the thermal source with the lower temperature below 100 ℃ to drive.

Claims

1. zeolite that contains transition metal, transition metal to be contained in the zeolite that comprises at least silicon atom, phosphorus atoms and aluminium atom in skeleton structure form, in the water vapor adsorption isotherms of 25 ℃ of mensuration, adsorbance during relative vapour pressure 0.01 is more than the 1.3mol/molSi, and the adsorbance during relative vapour pressure 0.7 is 150mg/g ~ 300mg/g.

2. zeolite that contains transition metal, it is characterized in that, it is the Heteroatom-aluminophosphate Zeolites that comprises the above transition metal M of 3 % by weight, the element that adopts probe-microanalyser to carry out the transition metal M in this zeolite distributes when marking and drawing, the Strength Changes coefficient of transition metal M is below 33%, and the aluminium atom is more than 0.9 with respect to the mol ratio of the total of silicon atom and phosphorus atoms.

3. zeolite that contains transition metal, it is characterized in that, to comprise the Heteroatom-aluminophosphate Zeolites that has 8 ring structures in the above transition metal M of 3 % by weight and the skeleton structure, the element that adopts probe-microanalyser to carry out the transition metal M in this zeolite distributes when marking and drawing, the Strength Changes coefficient of transition metal M is below 33%, and the aluminium atom is more than 0.9 with respect to the mol ratio of the total of silicon atom and phosphorus atoms.

4. each described zeolite that contains transition metal according to claim 1 ~ 3, wherein, described transition metal M is iron and/or copper.

5. each described zeolite that contains transition metal is characterized in that according to claim 1 ~ 3, and the BET specific area is 500m ²More than/the g.

6. each described zeolite that contains transition metal according to claim 1 ~ 3, wherein, the skeletal density of zeolite in International Zeolite Association IZA regulation zeolite structured is 10.0T/

~ 16.0T

7. each described zeolite that contains transition metal according to claim 1 ~ 3, wherein, zeolite is CHA in International Zeolite Association IZA regulation zeolite structured.

8. manufacture method that contains the zeolite of transition metal, it is characterized in that, to make to make transition metal contain the method for the zeolite that contains transition metal that in the zeolite that in skeleton structure, comprises at least silicon atom, phosphorus atoms and aluminium atom, forms, carry out Hydrothermal Synthesis by aqueous gel, described aqueous gel comprises at least a combination of selecting respectively in silicon atom raw material, aluminium atomic raw material, phosphorus atoms raw material, transition metal atoms raw material and the polyamines except diamines and at least 2 groups from the group of following (1) ~ (3):

(2) alkylamine;

(3) Cycloalkyl amine.

9. the manufacture method that contains the zeolite of transition metal according to claim 8, wherein, described transition metal is iron and/or copper.

10. manufacture method that contains the zeolite of transition metal, it is characterized in that, to make to make transition metal contain the method for the zeolite that contains transition metal that in the zeolite that in skeleton structure, comprises at least silicon atom, phosphorus atoms and aluminium atom, forms, wherein, to be pre-mixed phosphorus atoms raw material and water as cupric oxide (II) or the copper acetate of transition metal raw material, then mix silicon atom raw material, aluminium atomic raw material, reach the polyamines except diamines, the modulation aqueous gel carries out Hydrothermal Synthesis.

11. the manufacture method that contains the zeolite of transition metal according to claim 10 is characterized in that, in aqueous gel, further comprises at least a kind the combination of selecting respectively at least 2 groups from the group of following (1) ~ (3):

(2) alkylamine;

(3) Cycloalkyl amine.

12. each described manufacture method that contains the zeolite of transition metal according to claim 8 ~ 11, wherein, described polyamines is for using general formula H ₂N-(C _nH _2nNH) _xThe polyamines that-H represents, in the formula, n is 2 ~ 6 integer, x is 2 ~ 10 integer.

13. according to claim 8 or the 9 described manufacture methods that contain the zeolite of transition metal, wherein, the mol ratio when the aluminium atomic raw material in the composition of described aqueous gel, silicon atom raw material, phosphorus atoms raw material and transition metal M atomic raw material are represented with oxide is:

SiO ₂/ Al ₂O ₃Value be 0.1 ~ 0.8;

P ₂O ₅/ Al ₂O ₃Value be 0.6 ~ 1.2;

M _aO _b/ Al ₂O ₃Value be 0.05 ~ 1, wherein, a and b represent respectively the atomic ratio of M and O.

14. each described manufacture method that contains the zeolite of transition metal in the claim 1 ~ 7.

15. a pump-down process catalyst comprises each described zeolite that contains transition metal in the claim 1 ~ 7.

16. a water vapor adsorption material comprises each described zeolite that contains transition metal in the claim 1 ~ 7.