CN100546909C - The air handling unit of zeolite and preparation method thereof, the sorbent material that comprises zeolite, heat utilization system, adsorption heat pump, cold/heat storage system and moisture control - Google Patents

Abstract

The purpose of this invention is to provide a kind of zeolite and its preparation method that in repeated use or during life-time service, has reduced performance degradation, and a kind of sorbent material of this zeolite and heat utilization system of this sorbent material of use etc. of including are provided.The present invention relates to a kind of like this zeolite, its framework density is 10T/nm ³-16T/nm ³, carbon content is 1wt%-6wt%, and satisfies following (1) or (2): (1) this zeolite is an aluminate or phosphate, its nitrogen content be 0.5wt%-12wt% and wherein aluminium can part replace by Me; (2) this zeolite is an aluminosilicophosphate, and wherein aluminium can part be replaced by Me, and when by roasting when carbon content is lower than 0.3wt%, it has kept the roasting skeleton construction that aluminosilicophosphate had before; (condition is that the Me in above (1) and (2) is at least a element that is selected from periodictable 2A, 7A, 8,1B and the 2B family element).

Description

The air handling unit of zeolite and preparation method thereof, the sorbent material that comprises zeolite, heat utilization system, adsorption heat pump, cold/heat storage system and moisture control

Technical field

The present invention relates to a kind of specific zeolite (zeolite) and preparation method thereof, comprise sorbent material, heat utilization system, adsorption heat pump (absorption heat pump), the cold/heat storage system of this zeolite and be used for the air handling unit of moisture control.

Background technology

The catalyzer, parting material, optical material that zeolite is widely used as sorbent material, acid-reaction, oxidizing reaction etc. for example quantum dot and quantum wire, as the fine semiconductor grain of magneticsubstance, be used for the material of main part (host material) of fluorescent substance, dyestuff etc.According to international zeolite federation (InternationalZeolite Associate) (being called IZA hereinafter), zeolite comprises crystalline silicate, crystalline aluminium phosphoric acid salt or the like.

Usually adopt the raw material and the structure direction agent (strcuture-directing agent) (being also referred to as organic formwork) of zeolite synthetic, remove organic formwork by the technology of for example roasting or extraction then and prepare zeolite to carry out hydro-thermal.Generally speaking, as much as possible organic formwork is used as industrial available zeolite from the zeolite of wherein removing, to be used as catalyzer, sorbent material etc.The reason of removing organic formwork why as much as possible is as follows.By hydro-thermal for example synthetic obtain and not with organic formwork from the zeolite of wherein removing (being called zeolite precursor hereinafter), gap in the hole is occupied by organic formwork, thereby has prevented the matrix of reaction or the material that is adsorbed is entered hole.Therefore this zeolite can not be used as catalyzer or sorbent material.Therefore, industrial available zeolite is normally by removing the zeolite that obtains with organic formwork as much as possible from zeolite precursor.

The method that particularly contains the aluminosilicophosphate of heteroatoms silicon in the preparation zeolite has been described in the patent documentation 1 that illustrates below.This method is as follows: when organic formwork is removed from the zeolite precursor of aluminosilicophosphate, zeolite precursor is heated in airflow to decompose and to remove organic formwork (roasting method).The document comprise to the preparation roasting before carbon content be 6.9wt% SAPO-5 (framework density (and frameworkdensity, FD): 17.3T/nm ³) the elaboration of effect.Yet resulting here SAPO-5 has high relatively framework density, and we studies show that when when the sorbent material its adsorptive capacity deficiency.

The patent documentation 2 that illustrates has below been instructed under the situation that zeolite pore structure is partly occupied by the degradation production of organic formwork or organic formwork, owing to stoped the absorption atmospheric water, so its catalytic activity is storing or can not reduce between the delivery period.The example that provides in the document comprises the example that carbon atom keeps with 8.20wt% or bigger amount.On the other hand, the document instructed when with this zeolite when the catalyzer, it is carried out roasting or burn processing as activation treatment under oxygen containing atmosphere, fully organic formwork etc. is removed from the pore texture of zeolite.

The method that particularly contains the iron aluminium phosphate of heteroatoms iron in the preparation zeolite has been described in the patent documentation 3 that illustrates below.This method is as follows: when organic formwork is removed from the zeolite precursor of iron aluminium phosphate, zeolite precursor is heated in airflow or nitrogen gas stream to decompose and to remove organic formwork (roasting method).

On the other hand, the applicant proposed to be applicable to the zeolite of heat utilization system in the past, and its framework density (FD) is 10-18T/nm ³And produced the adsorption isothermal line that shows specific absorption property.More specifically, iron aluminium phosphate, aluminosilicophosphate and the iron aluminosilicophosphate (patent documentation 4 that illustrates below) of those performances have been proposed to have separately.

In addition, in the non-patent literature 1 that illustrates below, reported that aluminosilicophosphate (SAPO-43) showed selective adsorption CO ₂, H ₂O, H ₂The ability of S etc., described aluminosilicophosphate (SAPO-43) has the GIS structure, and it contains respectively with the amount of 3.99wt%-6.09wt% and 4.83wt%-6.09wt% residual carbon atom and nitrogen-atoms.Yet, wherein pointed out fully that organic formwork is unstable in essence from the zeolite of wherein removing, and the destruction of having pointed out crystalline structure is carried out along with removing of organic formwork, and organic formwork remove the adsorptive power of almost completely having deprived zeolite fully.When this zeolite of preparation so that the organic formwork that is kept is can make zeolite keep its structure the time, under the situation of water absorption, the loading capacity of the zeolite of gained is low to moderate 8wt%.

[patent documentation 1]

United States Patent (USP) 4,440,871

[patent documentation 2]

United States Patent (USP) 6,395,674

[patent documentation 3]

United States Patent (USP) 4,554,143

[patent documentation 4]

EP?1391238

[non-patent literature 1]

R.T.Yang etc., Langmuir, 2003,19,2193-2200

Summary of the invention

Zeolite according to above-mentioned correlation technique is

(1) wherein organic formwork or by its deutero-material with a large amount of relatively zeolites that keep or with this template or the material zeolite from wherein removing as much as possible; Or

(2) zeolite that can not stable existence after organic formwork is removed fully and with organic formwork from wherein removing the zeolite that does not have complete ruined degree to crystalline structure; Perhaps

(3) has high relatively framework density, the zeolite of promptly relative fine porosity volume.Therefore, these zeolites of correlation technique, when when the sorbent material, it has insufficient loading capacity, or has competent adsorptive capacity but be repeated as a class that has insufficient weather resistance in the sorbent material.

Under those situations; the inventor has found to exist such situation: even organic formwork stable zeolite after wherein removing is fully also being suffered particle be reduced into powder or along with the destruction of carrying out crystalline structure of using and experienced the reduction of corresponding adsorptive power when organic formwork being removed fully from hole, although this zeolite has high initial adsorption capacity or high initial catalytic activity.They find that further in the zeolite with low relatively framework density (big relatively volume of voids), this problem is significant.On the other hand, the zeolite that the amount of having found wherein to remain in the organic formwork in the space is not less than given content has such problem: from the beginning, the loading capacity of these zeolites under the state etc. is inadequate like this, the reduction that atmospheric water grades although the existence of organic formwork has prevented catalytic activity between the shelf lives effectively.

Realized the present invention in order to overcome the problems referred to above.The purpose of this invention is to provide a kind of zeolite that performance degradation reduces in repeated use or during life-time service, and its preparation method.Especially, this purpose provides: a kind of zeolite, when when the sorbent material, it has sufficiently high loading capacity and can not suffer zeolite granular to be reduced into powder and along with reusable crystalline structure does not have destroyedly, and therefore can not experience the corresponding reduction of loading capacity; With a kind of method for preparing this zeolite.Another purpose provides the sorbent material that comprises this zeolite and the heat utilization system that adopts this sorbent material separately, adsorption heat pump and/or cold/heat storage system.

The result who the problems referred to above is made further investigation by the inventor is, have been found that by a kind of like this zeolite and eliminated these problems: this zeolite has the framework density and the carbon content of specified range separately, in skeleton construction, contain specific element, and it is the aluminosilicophosphate that contains the aluminate or phosphate of specified range nitrogen content or kept its structure by roasting.

More specifically, we find to have eliminated the problems referred to above by following material:

(1) such zeolite: it is an aluminate or phosphate, and it has 10T/nm ³-16T/nm ³Framework density, can contain Me (condition is that Me is at least a element that is selected from periodictable 2A, 7A, 8,1B and the 2B family element), Can Yu organic formwork or remaining wherein by its deutero-amount Be Controlled, and therefore nitrogen content in this zeolite and carbon content are controlled as specified quantitative, perhaps

(2) such zeolite: it is an aluminosilicophosphate, and it has 10T/nm ³-16T/nm ³Framework density, can contain Me (condition is that Me is at least a element that is selected from periodictable 2A, 7A, 8,1B and the 2B family element), wherein Can Yu organic formwork or remnants' is controlled by its deutero-amount of substance, and therefore the carbon content in this aluminosilicophosphate is controlled as specified quantitative.

The inventor finds that further the sorbent material that includes this zeolite has good weather resistance.In addition, the inventor has been found that this sorbent material is effective when being used for heat utilization system or cold/heat storage system.Especially, find that this sorbent material can be used as cold/heat storage system, adsorption heat pump effectively, be used to dehumidify or the sorbent material of the usefulness such as air handling unit of humidification.

Zeolite of the present invention has been eliminated the problems referred to above, and it is characterized in that it being a kind of like this zeolite: its framework density is 10T/nm ³-16T/nm ³, carbon content is 1wt%-6wt%, and below satisfying (1) or (2):

(1) this zeolite is an aluminate or phosphate, its nitrogen content be 0.5wt%-12wt% and wherein aluminium can the part replace by Me;

(2) this zeolite is an aluminosilicophosphate, and wherein aluminium can part be replaced by Me, and when by roasting when carbon content is lower than 0.3wt%, it has kept the roasting skeleton construction that aluminosilicophosphate had before;

(condition is that the Me in above (1) and (2) is at least a element that is selected from periodictable 2A, 7A, 8,1B and the 2B family element).

Zeolite of the present invention has such excellent results: when this zeolite during as sorbent material for example, it has high loading capacity and can not suffer and destroys and reduced accordingly by loading capacity by reusing the crystalline structure that is caused.

This zeolite preparation method has been eliminated the problems referred to above, it is a kind of method for preparing above-mentioned zeolite, and be characterised in that: in the presence of at least a structure direction agent, synthetic to carry out hydro-thermal as at least a metallic element compound of zeolite component, and be roasting under 20 volume % or the lower atmosphere with the zeolite precursor that obtains at oxygen concn.

According to this preparation method, can stably make the zeolite of the present invention that produces above-mentioned effect.

Sorbent material of the present invention has been eliminated the problems referred to above, it is characterized in that comprising the zeolite of the invention described above.

According to sorbent material of the present invention, make it can not suffer to destroy the such preferred properties of corresponding reduction that also can not suffer loading capacity because the zeolite of this sorbent material of formation has, so this sorbent material itself also have good weather resistance by reusing the crystalline structure that is caused.Therefore, this sorbent material can be advantageously utilised in heat utilization system, adsorption heat pump, cold/heat storage system, perhaps is used for the air handling unit of moisture control.

The present invention has eliminated the problems referred to above, the invention provides: heat utilization system, and it adopts above-mentioned sorbent material and wherein utilizes by the heat of adsorption that is adsorbed onto adsorbable material on the sorbent material to be produced and/or the vaporization heat of adsorbate; And adopt adsorption heat pump, the cold/heat storage system of above-mentioned sorbent material separately and be used for the air handling unit of moisture control.

According to the present invention, because these systems have adopted the height weather resistance sorbent material that comprises the invention described above zeolite, so these systems have good weather resistance.

Description of drawings

Fig. 1 be explanation of the present invention cold/sketch of an embodiment of heat storage system.

Fig. 2 is the sketch of an embodiment of explanation adsorption heat pump of the present invention.

Fig. 3 is the sketch of an embodiment of the explanation air handling unit that is used to dehumidify of the present invention.

Fig. 4 is the sketch of an example of explanation moisture eliminator air regulator (desiccant air-conditioner), and described moisture eliminator air regulator is the air handling unit that removes wetted perimeter.

Fig. 5 represents the thermogravimetric analysis result of the zeolite precursor that obtains among the embodiment 1-1.

Fig. 6 is the XRD figure that does not stand the roasting product that obtains among the embodiment 1-1 of durability test 1.

Fig. 7 is the water vapor adsorption isotherms of roasting product under 55 ℃ that obtains among the embodiment 1-1.

Fig. 8 is the XRD figure that has stood the roasting product that obtains among the embodiment 1-1 of durability test 1.

Fig. 9 is the XRD figure that has stood the roasting product that obtains among the embodiment 1-1 of durability test 2.

Figure 10 is the XRD figure that does not stand the roasting product that obtains among the comparative example 1-1 of durability test 1.

Figure 11 is the XRD figure that has stood the roasting product that obtains among the comparative example 1-1 of durability test 1.

Figure 12 is the XRD figure that does not stand the roasting product that obtains among the comparative example 1-2 of durability test 1.

Figure 13 is the XRD figure that has stood the roasting product that obtains among the comparative example 1-2 of durability test 1.

Figure 14 is the XRD figure that does not stand the roasting product that obtains among the comparative example 1-3 of durability test 2.

Figure 15 is the XRD figure that has stood the roasting product that obtains among the comparative example 1-3 of durability test 2.

Figure 16 is the XRD figure of the roasting product that obtains among the embodiment 2-1.

Figure 17 is the water vapor adsorption isotherms of roasting product under 25 ℃ that obtains among the embodiment 2-1.

Figure 18 is the XRD figure that has stood the roasting product that obtains among the embodiment 2-1 of durability test 3.

Figure 19 represents the thermogravimetric analysis result of the iron aluminium phosphate precursor that obtains among the embodiment 2-2.

Figure 20 is the XRD figure of the roasting product that obtains among the embodiment 2-2.

Figure 21 is the water vapor adsorption isotherms of roasting product under 55 ℃ that obtains among the embodiment 2-2.

Figure 22 is the XRD figure that has stood the roasting product that obtains among the embodiment 2-2 of durability test 3.

Figure 23 is the XRD figure of the roasting product that obtains among the embodiment 2-3.

Figure 24 is the XRD figure that has stood the roasting product that obtains among the embodiment 2-3 of durability test 3.

Figure 25 is the XRD figure that has stood the roasting product that obtains among the embodiment 2-3 of durability test 2.

Figure 26 is the XRD figure of the roasting product that obtains among the comparative example 2-1.

Figure 27 is the XRD figure that has stood the roasting product that obtains among the comparative example 2-1 of durability test 3.

Figure 28 is the XRD figure of the roasting product that obtains among the comparative example 2-2.

Figure 29 is the XRD figure that has stood the roasting product that obtains among the comparative example 2-2 of durability test 3.

Figure 30 is the XRD figure that has stood the roasting product that obtains among the comparative example 2-2 of durability test 2.

Figure 31 is the XRD figure of the hydro-thermal synthetic product that obtains among the comparative example 2-6.

Reference number in the accompanying drawing has following implication: the cold/heat storage system of 11 expressions, 12,26 and 27 is the recirculated water feeder, 13,22 and 23 are absorption/desorption apparatus, and 14 is evaporator/condenser, and 21 is adsorption heat pump, 24 is vaporizer, 25 is condenser, 28,29,30 and 31 is valve, and 61 is the air handling unit that is used to dehumidify, 62 is air, 63 is the adsorbent reactivation device, and 70 is the moisture eliminator air regulator, and 71 is the original air passage, 72 is the regeneration air passage, 73 is the moisture eliminator rotor, and 74 and 75 is the temperature-sensitive interchanger, 76 is the heat supply device, and 77 is humidifier, 78 is will be by the space of artificial atmosphere, and 79 is extraneous.

Embodiment

To explain zeolite of the present invention and preparation method thereof successively below, comprise sorbent material, heat utilization system, adsorption heat pump and the cold/heat storage system of this zeolite.

Zeolite of the present invention is the zeolite of aluminate or phosphate class, its for aluminium wherein can part (condition is that Me is at least a element that is selected from periodictable 2A, 7A, 8,1B and the 2B family element by the displaced aluminate or phosphate of Me or aluminosilicophosphate; This at least a element is known as Me hereinafter).Wherein aluminium can tend to produce big adsorptive capacity difference by displaced aluminate or phosphate of Me or aluminosilicophosphate when relative vapor pressure only changes slightly in low relatively relative vapor pressure scope.In this, aluminate or phosphate or aluminosilicophosphate are particularly suitable for as sorbent material.The particular case of this aluminate or phosphate or aluminosilicophosphate will provide in the back.

The framework density of zeolite of the present invention is 10T/nm ³-16T/nm ³Too low framework density causes unsettled zeolite structured, and too high framework density causes the adsorptive capacity that reduces.Its framework density is 12T/nm more preferably ³Or higher, even 13T/nm more preferably ³Or it is higher.On the other hand, its framework density 15T/nm more preferably ³Or it is lower.The symbol T here represents to constitute the atom of zeolite framework and is not Sauerstoffatom, T/nm ³Be the every nm of expression ³The unit (framework density) of the T atom number that exists.When the framework density of zeolite is in this scope, as will be described later, significantly produced the apodictic effect that improves zeolite performance degradation when reusing, especially by the content of control carbon atom or the content of carbon atom and nitrogen-atoms.

According to the classification of international zeolite federation (IZA) regulation, zeolite of the present invention has the structure that belongs to crystalline silicate, crystalline aluminium phosphoric acid salt etc.Yet, especially from as the required weather resistance of the sorbent material that will be described later and the viewpoint of absorption property, the skeleton construction of zeolite normally is selected from the structure by code designation AEI, AFR, AFS, AFT, AFX, ATS, CHA, ERI, LEV, LTA and the VFI of IZA definition.From the viewpoint of absorption property and structural stability, preferably be selected from the structure of AEI, CHA and LEV in the middle of these.Especially preferred CHA.

In addition, from the required weather resistance of sorbent material and the viewpoint of absorption property, zeolite of the present invention be describe below can by the displaced aluminate or phosphate of specific heteroatoms (A) or describe below can be by the displaced aluminosilicophosphate of specific heteroatoms (B).

(A) aluminate or phosphate that can be replaced by specific heteroatoms:

This aluminate or phosphate is that wherein aluminium can be partly by the displaced aluminate or phosphate of one or more heteroatomss (here being represented by Me), i.e. (Me-) aluminate or phosphate.Hereinafter, the aluminate or phosphate that can contain Me is commonly referred to as " (Me-) aluminate or phosphate ".

In (Me-) aluminate or phosphate, preferably should satisfy following formula 1-1 to 1-3 as Me, the Al of aluminate or phosphate skeleton construction component and the mol ratio of P.More preferably the molar ratio of Me should satisfy following formula 1-1 ' in this case.

0≤x≤0.3...1-1 (x represents the mol ratio of Me and Me, Al and P summation)

0.2≤y≤0.6...1-2 (y represents the mol ratio of Al and Me, Al and P summation)

0.3≤z≤0.6...1-3 (z represents the mol ratio of P and Me, Al and P summation)

0.001≤x≤0.3...1-1 ' (x represents the mol ratio of Me and Me, Al and P summation).

The x value of expression Me molar ratio is too big, can cause impurity inclusion (impurity inclusion).On the other hand, even when x is 0, also produced effect of the present invention.Yet, approaching at its lower limit under 0 the situation, this aluminate or phosphate tends to have the adsorptive capacity of reduction in low adsorbate pressure span (low-absorbate-pressure-region) when as sorbent material, perhaps can be difficult to synthesize.Therefore, the lower limit of x is preferably 0.001, as shown in expression formula 1-1 '.On the other hand, on the z of the y of expression Al molar ratio and expression P molar ratio is in shown under the situation outside the scope, this aluminate or phosphate is difficult to synthesize.

The molar ratio of Me, Al and P more preferably satisfies following formula 1-4 to 1-6.This constituting helps the synthetic of (Me-) aluminate or phosphate and prevented impurity inclusion, so that can more easily obtain desirable absorption property.

0.01≤x≤0.3...1-4 (x represents the mol ratio of Me and Me, Al and P summation)

0.3≤y≤0.5...1-5 (y represents the mol ratio of Al and Me, Al and P summation)

0.4≤z≤0.5...1-6 (z represents the mol ratio of P and Me, Al and P summation)

Me is not particularly limited, as long as it is at least a element that is selected from periodictable 2A, 7A, 8,1B and the 2B family element, and can comprise these elements two or more.The example of preferred L e is Mg, and it is the element that belongs to the period 3 in the periodictable, and Ca, Mn, Fe, Co, Ni, Cu and Zn, and it is the element that belongs to the period 4.Preferably be in divalent state separately in the middle of these, ionic radius is 0.3

-0.8

Mn, Fe, Co, Ni, Cu, Zn and Mg.More preferably be in divalence and four-coordination state separately, ionic radius is 0.4

-0.7 Fe, Co, Cu, Zn and Mg.

From the easy viewpoint of synthetic and absorption property, Me preferably is selected from one or both elements of Fe, Co, Mg and Zn in the middle of those elements.Especially preferably, Me is Fe.Incidentally, 1nm can be converted into 10

Unit.

(B) can be by the displaced aluminosilicophosphate of specific heteroatoms:

This aluminosilicophosphate is that wherein aluminium can be partly by the displaced aluminosilicophosphate of one or more heteroatomss (Me), i.e. (Me-) aluminosilicophosphate.Hereinafter, the aluminosilicophosphate that can contain Me is commonly referred to as " (Me-) aluminosilicophosphate ".

Preferably, the mol ratio as Me, Al, P and the Si of (Me-) aluminosilicophosphate skeleton construction component should satisfy following formula 2-1 to 2-4:

0≤x≤0.3...2-1 (x represents the mol ratio of Me and Me, Al, P and Si summation)

0.2≤y≤0.6...2-2 (y represents the mol ratio of Al and Me, Al, P and Si summation)

0.3≤z≤0.6...2-3 (z represents the mol ratio of P and Me, Al, P and Si summation)

0.001≤w≤0.3...2-4 (w represents the mol ratio of Si and Me, Al, P and Si summation)

About the molar ratio of these elements, the x value of expression Me molar ratio is too big, can cause being difficult to synthetic carbonaceous aluminosilicophosphate.The x value can be 0; In this case, aluminosilicophosphate does not contain Me.

Yet existing in of the Me that is comprised helps zeolite of the present invention to control absorption property (relation between relative humidity and the adsorptive capacity) as under the situation of sorbent material.Therefore preferably x should satisfy following formula.

001≤x≤0.3...2 '-1 (x represents the mol ratio of Me and Me, Al, P and Si summation)

Under the situation of y less than this scope of expression Al molar ratio, shown in above situation, it is difficult that the synthetic meeting of this aluminosilicophosphate becomes.On the other hand, its value can cause impurity inclusion greater than this scope.Under the situation of z less than this scope of expression P molar ratio, shown in above situation, it is difficult that the synthetic meeting of this aluminosilicophosphate becomes.On the other hand, its value can cause impurity inclusion greater than this scope.In addition, under the situation of w less than this scope of expression Si molar ratio, shown in above situation, it is difficult that the synthetic meeting of this aluminosilicophosphate becomes.On the other hand, its value can cause being difficult to obtain desirable absorption property greater than this scope.

The molar ratio of Me, Al, P and Si more preferably satisfies following formula 2-5 to 2-8.This constituting helps synthetic carbonaceous aluminosilicophosphate of the present invention and prevented impurity inclusion, so that can more easily obtain desirable absorption property.

0≤x≤0.3...2-5 (x represents the mol ratio of Me and Me, Al, P and Si summation)

0.3≤y≤0.5...2-6 (y represents the mol ratio of Al and Me, Al, P and Si summation)

0.4≤z≤0.5...2-7 (z represents the mol ratio of P and Me, Al, P and Si summation)

0.01≤w≤0.25...2-8 (w represents the mol ratio of Si and Me, Al, P and Si summation)

Incidentally, the preferred example of the example of Me and Me with illustrate above those are identical.

Above-mentioned (Me-) aluminate or phosphate and (Me-) aluminosilicophosphate except the composition that constitutes skeleton construction, can also contain and have cationic substance a kind of that can carry out ion-exchange with another kind of positively charged ion.The example of this cationic substance comprises proton, and alkaline element is Li, Na and K for example, and alkaline earth element is Mg and Ca for example, and rare earth element is for example Fe, Co and Ni of La and Ce and transition metal for example.Preferably proton, alkaline element and alkaline earth element in the middle of these.

Although zeolite of the present invention is above-mentioned (Me-) aluminate or phosphate or (Me-) aluminosilicophosphate, the carbon content of these aluminate or phosphates is 1wt%-6wt%.

Under the situation that does not satisfy this requirement, caused crystalline structure destruction and the loading capacity in the repeated use to reduce accordingly as for example sorbent material in zeolite.

(Me-) aluminate or phosphate and (Me-) aluminosilicophosphate will be described respectively below.

At zeolite of the present invention is under the situation of (Me-) aluminate or phosphate, and as mentioned above, it contains 0.5wt%-12wt% nitrogen and contains 1wt%-6wt% carbon.Contain the nitrogen of amount in those scopes and (Me-) aluminate or phosphate of carbon and have good effect, promptly when this aluminate or phosphate during as sorbent material for example, the crystalline structure destruction during it can not reused can not suffer the corresponding reduction of loading capacity yet.Especially, this zeolite has such effect: it is not easy to suffer crystalline structure to destroy and has improved weather resistance, and therefore, it can be advantageously used in various practical applications.The example of practical application comprises heat utilization system, adsorption heat pump and cold/heat storage system, and these will be described later.

Under the too high situation of its nitrogen content and carbon content, especially when this zeolite during as sorbent material, it has the adsorptive capacity and the insufficient absorption property of reduction.On the other hand, under the too low situation of its nitrogen content and carbon content, especially when this zeolite during as sorbent material, it has the problem of the weather resistance in the repeated use of relating to.

Its nitrogen content is preferably 0.5wt% or higher, especially is preferably 0.8wt% or higher, most preferably is 1.0wt% or higher.Nitrogen content is 5wt% or lower more preferably, especially is preferably 3wt% or lower.On the other hand, its carbon content is 1.5wt% or higher more preferably, especially is preferably 2wt% or higher.Carbon content is 6wt% or lower more preferably, especially is preferably 5wt% or lower.

The reason that the zeolite that contains the nitrogen of amount in those scopes and carbon has improved weather resistance is not also got across fully.Yet, think the state changes little of crystalline structure and lattice parameter and the key when absorption/desorption of this zeolite, and this is attributable to the improvement of weather resistance.

In (Me-) of the present invention aluminate or phosphate, the weight ratio of carbon and nitrogen (C/N weight ratio) is preferably 0.8-6.5, and 1.0-4 more preferably is especially to 3.5.In the time of in the C/N weight ratio is in this scope, this zeolite will have high weather resistance and high loading capacity.On the other hand, be lower than 0.8 C/N weight ratio and can cause the weather resistance that reduces.

Contain under the situation of Me at (Me-) aluminate or phosphate, the mol ratio of nitrogen and Me (N/Me ratio) is preferably 0.1-10.N/Me ratio more preferably 0.2 or higher especially is preferably 0.5 or higher.On the other hand, the N/Me ratio is preferably 5 or lower, especially is preferably 2 or lower.Under the situation of N/Me ratio above the upper limit of this scope, this zeolite will have the adsorptive capacity of reduction.The N/Me that is lower than the lower limit of this scope causes the weather resistance that reduces than regular meeting.

On the other hand, be under the situation of (Me-) aluminosilicophosphate at zeolite of the present invention, as mentioned above, it contains 0.8wt%-6wt% carbon.(Me-) aluminosilicophosphate that contains the carbon of amount in this scope has good effect, promptly when this aluminosilicophosphate during as sorbent material for example, its have high loading capacity and good hydrothermal stability and can not reused in crystalline structure destroy the corresponding reduction that also can not suffer loading capacity.Especially, this zeolite has such effect: it is not easy to suffer crystalline structure to destroy and has improved weather resistance, and therefore, it can be advantageously used in various practical applications.The example of practical application comprises heat utilization system, adsorption heat pump and cold/heat storage system, and these will be described later.

Under the too high situation of its carbon content, especially when this zeolite was used as sorbent material, it had the adsorptive capacity and the insufficient absorption property of reduction.On the other hand, under the too low situation of its carbon content, especially when this zeolite when the sorbent material, it has and relates to the weather resistance that is exposed in the high temperature in the presence of water vapour (this weather resistance is known as " hydrothermal stability "; Be equally applicable to hereinafter) and repeat to adsorb/problem of weather resistance in the desorption.Its carbon content is 1.8wt% or higher more preferably, especially is preferably 2wt% or higher.Carbon content is 5wt% or lower more preferably.

The reason that (Me-) aluminosilicophosphate that contains the carbon of amount in this scope has improved weather resistance is not also got across fully.Yet, think the state changes little of crystalline structure and lattice parameter and the key when absorption/desorption of this (Me-) aluminosilicophosphate, and this is attributable to the improvement of weather resistance.

Incidentally, be different from above described (Me-) aluminate or phosphate, should needn't contain nitrogen by (Me-) aluminosilicophosphate, as long as its carbon content is in the scope that illustrates above.This is to contain within it aluminate or phosphate skeleton construction because should (Me-) aluminosilicophosphate have Siliciumatom.Yet it can contain nitrogen.Although nitrogen content is slight to the influence of hydrothermal stability when containing nitrogen, too big nitrogen content has caused the adsorptive power that reduces.Because this is containing under the situation of nitrogen, its content is preferably 2wt% or lower usually, more preferably 1.5wt% or lower.

The zeolite that zeolite of the present invention is preferably following, making adsorbable material (being commonly referred to as adsorbate) can enter its neutralization in this zeolite mesoporosity structure is the zeolite (this ratio is meant by the hole utilization coefficient 1 of following expression 3 definition or by the hole utilization coefficient 2 of following expression 4 definition) of 0.6-0.99 from the ratio of those parts of wherein going out.This hole utilization coefficient more preferably 0.7 or higher especially is preferably 0.8 or higher.On the other hand, this hole utilization coefficient more preferably 0.95 or lower especially is preferably 0.93 or lower.In the present invention, the hole utilization coefficient can be defined the sort of or defined the sort of by the hole utilization coefficient 2 of expression formula 4 expressions by the hole utilization coefficient 1 of expression formula 3 expressions.Any that satisfies these conditions is just enough.

Hole utilization coefficient 1=Q1/Qs 3

In expression formula 3, Qs is the water vapor adsorption amount under the situation of the structure direction agent being removed fully, Q1 is the water vapor adsorption amount of zeolite of the present invention, and condition is the water vapor adsorption capacity that these water vapor adsorption scales are shown in the per unit weight that 0.5 relative vapor pressure and room temperature (25 ℃) measure down.

Hole utilization coefficient 2=W1/Ws 4

In expression formula 4, Ws is an effective water adsorption amount under the situation of the structure direction agent being removed fully, and W1 is effective water adsorption amount of zeolite of the present invention.The term here " effectively water adsorption amount " is meant the numerical value that obtains in the following manner: sample was placed 25 ℃ of steam-laden atmosphere following 1 day so that its be adsorbed to saturated, dry air stream with 10 ℃/minute speed under to this sample heating, and calculate in 25 ℃ of-100 ℃ of scopes by the ratio of the example weight of measuring before the weight of the water of desorption and the heating.

Zeolite of the present invention preferably is preferably 10wt% or bigger by the water vapor adsorption amount that 25 ℃ adsorption isothermal line is measured, and especially is 15wt% or bigger, more preferably 20wt% or bigger zeolite.Although its upper limit is preferably higher, it is about 40wt% usually.

At zeolite of the present invention is under the situation of (Me-) aluminosilicophosphate, when this zeolite by roasting when carbon content is lower than 0.3wt%, it has kept the skeleton construction that had before the roasting.Do not keep under the situation of its original skeleton construction by roasting at (Me-) aluminosilicophosphate, because its skeleton construction former thereby suffer the destruction of crystalline structure extremely easily, and its absorption property reduces rapidly when this zeolite repeats as sorbent material for example.

Term used herein " when zeolite by roasting when carbon content is lower than 0.3wt%, it has kept the skeleton construction that had before the roasting " be meant and kept this (Me-) aluminosilicophosphate inherent skeleton construction.Below satisfying, when (1) or (2), think to have kept the inherent skeleton construction.Preferably satisfy following (1) and (2) both situations.Explanation to (1) and (2) provides below.

(1) kept under the ideal skeleton construction in supposition, when ideal water vapor adsorption scale is shown Qi and (25 ℃ of the water vapor adsorption amount of roasting after carbon content is lower than 0.3wt%; Relative vapor pressure 0.5) when being expressed as Qc, then Qc/Qi is 0.4 or bigger, and condition is that Qi measures according to following (1-1) or (1-2).Incidentally, structural framing is meant the code that is defined by IZA at this; The skeleton construction that is represented as same code although the element of formation framework is different is counted as identical.

(1-1) by analysis in the skeleton construction situation of zeolite of hydrated state, the ratio of the water that contains and the formula weight of hydrate crystal is got and is made Qi.

(1-2) in the skeleton construction situation of the zeolite of not analyzing hydrated state, with reference to D.W.Breck, zeolite molecular sieve: structure, chemical property and application, A WILEY-INTERSCIENCEPUBLICATION, 1974,48-50 page or leaf and table 2.4, and the voidage with zeolite of this structure is got and is made Qi.

(2) in the X-ray powder is derived figure, even be attributable to crystalline structure and be in three peaks in the middle of the peak observed before roasting, that have the high strength ratio at least one after being reduced to carbon content and nitrogen content below the 0.3wt% by roasting, its peak height still is at least 50% of the peak height before the roasting.Adopting identical sample clamp and identical example weight to carry out peak strength measures.

From the viewpoint of measurement precision, (A) or (B) carry out peak strength and measure by the following method.

(A) do not use the method for internal standard substance: under identical condition, measure, and the absolute value of the peak strength of compare test sample.Preferably, when before the peak strength of specimen is measured and when checking same sample afterwards, the absolute value of peak strength is changed to 10% or littler.

(B) use the method for internal standard substance: internal standard substance is mixed with specific weight ratio, and measure the peak strength of each specimen and the ratio of the peak strength of internal standard substance (peak strength compares), with the peak strength ratio of compare test sample.

More specifically, the example of these methods comprises following technology.

(a) adopt identical device, detecting with identical sample size under the same conditions is enough to by means of the specimen of manpower with pulverizing such as mortars.In this case, require the measurement that will carry out strength ratio sample was measured under the approaching as far as possible each other separately time.In addition, the personnel that carry out common XRD analysis will be appreciated that attention keeps constant as far as possible with the state of X-ray source.Before comparing and measuring with detect identical sample afterwards, be changed to 10% or littler to guarantee diffracted intensity.

(b) but may not adopting identical device or having adopted under the situation that the state of identical device X-ray source may noticeable change, carry out following steps.With given weight ratio identical internal standard substance is joined in the specimen, and to by means of after the thorough mixing such as mortar, the mixture of various gained is carried out XRD analysis.Owing to the diffraction peak intensity of internal standard substance and on owing to the ratio basis between the intensity of the diffraction peak of zeolite, the peak strength between the comparative sample.Be selected from internal standard substance based on knowledge known in those skilled in the art, for example will be used to strength ratio do not have diffraction peak owing to place, the diffraction peak position of zeolite.

Incidentally, be the index of representing to remove the state of the organic formwork that is used for the preparation of (Me-) aluminosilicophosphate by roasting with the index that carbon content is reduced to below the 0.3wt%.It is the value definite by limit of detection.

Roasting condition in the situation that by roasting carbon content is reduced to below the 0.3wt% comprises, for example 450 ℃ or more relative superiority or inferiority roasting 2 hours in oxygen containing atmosphere.At zeolite of the present invention is under the situation of (Me-) aluminate or phosphate, preferably when with the identical mode of (Me-) aluminosilicophosphate all is reduced to 0.3wt% when following with carbon content and nitrogen content, then kept the skeleton construction before the roasting.

Zeolite of the present invention has preferably kept a kind of of its crystalline structure that was had before test when carrying out the cycling durable property testing in the mode that illustrates below.

The cycling durable property testing: zeolite is placed the vacuum vessel that remains under 90 ℃, and repeats the operation below 500 times, wherein zeolite is exposed to following 90 seconds of vacuum and 90 ℃ of steam-laden atmosphere each once.

Keep crystalline structure to be meant: when adopting identical device, identical testing conditions, identical sample clamp (sample holder) and identical example weight by XRD detection zeolite, then the highest peak value of strength after the test is at least 50% of highest peak value of strength before the test, and condition is that peak strength is meant peak height and is the numerical value that obtains by by summit reading subtracting background reading.

In addition, zeolite of the present invention preferably when it carries out the cycling durable property testing in the same manner as described above, 25 ℃ with 0.5 relative vapor pressure under when measuring the water vapor adsorption amount after the test for test before determined its water vapor adsorption amount at least 80% a kind of.

In addition, when the weight loss (g1) of zeolite of the present invention when 200 ℃ are heated to 350 ℃ is preferably 0wt%-3wt%.Less weight loss (g1) value is preferred.The upper limit of weight loss is preferably 2wt%, more preferably 1.5wt%.Too big weight loss (g1) value can cause thermostability inadequate.

On the other hand, when with zeolite of the present invention when 350 ℃ are heated to 700 ℃, corresponding weight loss (g2) is preferably 2wt%-9.5wt% under the situation of (Me-) aluminate or phosphate, and is preferably 2wt%-6wt% under the situation of (Me-) aluminosilicophosphate.(Me-) reason that the weight loss of aluminate or phosphate (g2) is different with the upper limit of this value of (Me-) aluminosilicophosphate may be the performance difference of these zeolites, and this depends on that skeleton construction contains silicon or not siliceous.

When zeolite of the present invention is (Me-) aluminate or phosphate or (Me-) during aluminosilicophosphate, weight loss (g2) is preferably 2.5wt% or bigger, more preferably 3wt% or bigger.Too little weight loss (g2) value can cause poor durability.

On the other hand, (Me-) weight loss of aluminate or phosphate (g2) is preferably 9wt% or littler, and (Me-) weight loss of aluminosilicophosphate (g2) is preferably 5.5wt% or littler.Under the too big situation of its weight loss (g2), this zeolite is when as sorbent material, and it can the adsorptive capacity deficiency.

Incidentally, the equation below adopting comes the calculated weight loss, and wherein the weight the when weight 200 ℃ time the, the weight 350 ℃ time the and 700 ℃ is expressed as w1, w2 and w3 respectively.

Weight loss (g1)=(w1-w2)/w1 * 100

Weight loss (g2)=(w2-w3)/w1 * 100

(method for preparing zeolite of the present invention)

Next will set forth a kind of method for preparing zeolite of the present invention.

The method for preparing zeolite of the present invention is the method that a kind of preparation has the zeolite of the present invention of above-mentioned The Nomenclature Composition and Structure of Complexes feature.In the method, in the presence of at least a structure direction agent, it is synthetic that at least a metallic element compound as zeolite component is carried out hydro-thermal, and be that roasting prepares the target zeolite under 20 volume % or the lower atmosphere with the zeolite precursor that obtains at oxygen concn.At zeolite is under the situation of (Me-) aluminate or phosphate, preferably by being that roasting prepares this zeolite under 0.1 volume % or the higher atmosphere at oxygen concn.

At first explanation is used to prepare constitutive material according to zeolite of the present invention.At zeolite is under the situation of (Me-) aluminate or phosphate, the constitutive material that uses is comprised aluminium source, Me source (especially being preferably source of iron), phosphorus source and as the organic formwork of structure direction agent.

At zeolite is under the situation of (Me-) aluminosilicophosphate, uses aluminium source, Me source (especially being preferably source of iron), phosphorus source, silicon source and as the organic formwork of structure direction agent.

These raw materials are mixed, carry out hydro-thermal then and synthesize, obtain zeolite precursor thus.

The aluminium source:

The aluminium source is not particularly limited.Usually use pseudobochmite (pseudoboehmite), aluminium-alcohol salt for example aluminum isopropylate or three aluminum ethylates, aluminium hydroxide, alumina sol, sodium aluminate etc.In the middle of these,, preferably use pseudobochmite from the viewpoint of operability and reactive behavior.

The Me source:

Optional Me source of using also is not particularly limited.The salt of common use mineral acid is vitriol, nitrate, phosphoric acid salt, muriate or bromide for example, and organic acid salt is acetate, oxalate or Citrate trianion for example, and organometallic compound is pentacarbonyl compound or ferrocene for example, or the like.

In the middle of these,, preferably use inorganic acid salt or organic acid salt from the deliquescent viewpoint water.Can use colloidal oxide (colloidal oxide) in some cases.Preferred L e source is divalence Me.About the kind of Me, as described in above.

The phosphorus source:

Usually phosphoric acid is used as the phosphorus source.Yet, can use aluminum phosphate.

The silicon source:

As the silicon source, can use for example tetraethyl silicate of silicon sol, pyrogenic silica or silicoorganic compound.From the viewpoint of operability, preferred silicon sol or pyrogenic silica of using in the middle of these.

Organic formwork:

Organic formwork as can be used as the structure direction agent in hydro-thermal is synthetic can use amine, imines or quaternary ammonium salt.Yet preferred the use is selected from (1) and contains the cycloaliphatic heterocycle compound of heteroatoms nitrogen, (2) and contain at least a compound in the amine of one or more cycloalkyl and the amine that (3) contain one or more alkyl.These compounds are purchased, cheaply and in addition have such effect easily: handle and be not easy to suffer structure deteriorate easily with its (Me-) aluminosilicophosphate that makes.

Elaborate those amine that are preferably used as organic formwork below.

The cycloaliphatic heterocycle compound that contains heteroatoms nitrogen:

The cycloaliphatic heterocycle compound that contains heteroatoms nitrogen is 5 to 7 membered ring compounds normally, are preferably 6 membered ring compounds.The heteroatomic number that is contained in the heterocycle is at most 3 usually, preferably is at most 2.The heteroatomic kind that can contain is not particularly limited, as long as comprised nitrogen.Yet from easy synthetic viewpoint, preferred heterogeneous ring compound is also to contain a kind of of aerobic except nitrogen.Although heteroatomic position is not particularly limited,, preferably do not contain the heteroatomic heterogeneous ring compound of position located adjacent one another from easy synthetic viewpoint.The molecular weight of heterogeneous ring compound is 250 or lower, and is preferably 200 or lower from easy synthetic viewpoint, more preferably 150 or lower.

The example that contains these cycloaliphatic heterocycle compounds of heteroatoms nitrogen comprises: morpholine, N-methylmorpholine, piperidines, piperazine, N, N '-lupetazin, 1,4-diazabicyclo [2,2,2] octane, N-methyl piperidine, 3-methyl piperidine, rubane (quinuclidine), tetramethyleneimine, N-crassitude and hexamethylene imine.From easy synthetic viewpoint, preferably morpholine, hexamethylene imine and piperidines in the middle of these.Especially be preferably morpholine.

The amine that contains one or more cycloalkyl:

In containing the amine of one or more cycloalkyl, in every amine molecule, the number of cycloalkyl preferably is at most 2, and more preferably 1.The carbon atom number of each cycloalkyl is generally 5-7, is preferably 6.The number of cycloalkyl ring is not particularly limited, but is preferably 1 usually.From easy synthetic viewpoint, preferably contain the amine compound of the cycloalkyl on the nitrogen-atoms that is connected to this compound.The molecular weight of these amine is 250 or lower, and is preferably 200 or lower from easy synthetic viewpoint, more preferably 150 or lower.

The example that contains these amine of one or more cycloalkyl comprises: hexahydroaniline, dicyclohexyl amine, N-methylcyclohexylamine, N, N-dimethylcyclohexylamine and cyclopentamine.Especially be preferably hexahydroaniline.

The amine that contains one or more alkyl:

In containing the amine of one or more alkyl, in every amine molecule, alkyl can exist by arbitrary number.Yet its number is preferably 3.Carbon atom number in each alkyl is preferably 4 or littler, and the total number of carbon atoms of all alkyl is preferably 10 or littler in the per molecule.The molecular weight of these amine is 250 or lower, and is preferably 200 or lower from easy synthetic viewpoint, more preferably 150 or lower.

The example that contains these amine of one or more alkyl comprises: di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, triethylamine, trolamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, N methyldiethanol amine, N-Mono Methyl Ethanol Amine, Di-n-Butyl Amine, neopentyl amine, two n-amylamines, Isopropylamine, TERTIARY BUTYL AMINE, quadrol, diisopropylethylamine and N-methyl n-Butyl Amine 99.From easy synthetic viewpoint, preferred di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, triethylamine, Di-n-Butyl Amine, Isopropylamine, TERTIARY BUTYL AMINE, quadrol, diisopropylethylamine and N-methyl n-Butyl Amine 99.N more preferably, N-diethylethanolamine, N, N-dimethylethanolamine and triethylamine.Most preferably be N, N-diethylethanolamine and triethylamine.

Those preferred compounds, promptly (1) contains the amine that one or more alkyl are contained in the cycloaliphatic heterocycle compound of heteroatoms nitrogen, amine that (2) contain one or more cycloalkyl and (3), can be separately or with its two or more be used in combination.Using under wherein a kind of situation of those amine, contain in (1) in the middle of the cycloaliphatic heterocycle compound of heteroatoms nitrogen, it is morpholine preferably, perhaps contain the amine of one or more cycloalkyl in (2) in the middle of, it is hexahydroaniline preferably.Especially preferred morpholine in the middle of these.

On the other hand, in order to synthesize the material with desirable composition and high purity, preferably combination is used two or more amine.As the preferably combination of organic formwork is so a kind of: it comprises at least two kinds of compounds that are selected from following group, promptly (1) contains the cycloaliphatic heterocycle compound of heteroatoms nitrogen, the amine that (2) contain one or more cycloalkyl, (3) contain the amine of one or more alkyl, belong to this compound of two groups separately so that include two kinds.Adopt such combination to have such advantage: the synthetic easily zeolite that has desirable element ratio or have high degree of crystallinity.Because the easily synthetic zeolite that has desirable element ratio or have high degree of crystallinity, therefore more effective this combination is so a kind of: it comprises that two or more include the compound that (1) contains the cycloaliphatic heterocycle compound of heteroatoms nitrogen.The specific examples of these preferably combination comprises two or more morpholine, triethylamine or N, N-diethylethanolamine, and hexahydroaniline.More preferably such combination: it comprises at least two kinds of these compounds that include morpholine.

When the organic formwork that will be selected from those groups respectively mixes, should select its ratio aptly according to condition.Mol ratio between two kinds of mixed organic formworks can be 1: 20 to 20: 1, and be preferably 1: 10 to 10: 1 from synthesizing the viewpoint of zeolite easily with desirable element ratio or high-crystallinity.The organic formwork that can contain other.Yet in this case, its mol ratio is preferably 20% or lower usually, more preferably 10% or lower.Those organic formworks are cheap and have these advantages: wait and compare their reductions such as processing and corrodibility easily with the organic formwork (for example tetraethylammonium hydroxide) in using so far.

In zeolite preparation method of the present invention, in preparation, be used in combination two or more organic formworks and select the condition of preparation can produce following effect: (i) can improve the degree of crystallinity during the zeolite synthesis; (ii) can suppress the formation of impurity, preparation easily has the zeolite of desired structure thus; (iii) can make and have the zeolite that is not easy the destructive rock steady structure.

In zeolite preparation method of the present invention, the preferred use comprises that two or more are selected from the organic formwork of the combination of compounds of above-mentioned (1)-(3).This method has such advantage: because therefore the synergy of these organic formworks can realize those effects (i)-(iii), this is different from the method that only adopts single organic formwork.

Next will be set forth in according to the hydro-thermal in the zeolite preparation method of the present invention synthetic.It below is explanation to the situation of wherein introducing Me.

At first, mix to include the constitutive material of Me source, aluminium source, source of phosphoric acid, organic formwork and water or be to mix the constitutive material that includes these compositions and silicon source under the situation of aluminosilicophosphate at zeolite, prepare aqueous gel.The order of mixing these constitutive materials without limits and can be according to the condition that adopts is selected aptly.Yet, at first source of phosphoric acid and aluminium source and water randomly are mixed together with the silicon source usually, and Me source and organic formwork are mixed with it.

The composition of aqueous gel influences target product synthetic easiness.When the amount of aluminium source, Me source and source of phosphoric acid is represented with the mol ratio of oxide compound, MeO/A1 then ₂O ₃Value usually greater than 0 and be not more than 1.0, be preferably 0.02 or bigger and be not more than 0.9, more preferably no more than 0.8.P ₂O ₅/ Al ₂O ₃Scale effect target product synthetic easiness, this ratio is generally 0.6 or bigger, is preferably 0.8 or bigger, and more preferably 1 or bigger, and be generally 1.8 or littler, be preferably 1.7 or littler, more preferably 1.6 or littler.

At zeolite is under the situation of aluminosilicophosphate, SiO ₂/ Al ₂O ₃Ratio makes 0.0001≤SiO ₂/ Al ₂O ₃≤ 2.From easy synthetic viewpoint, this ratio preferably makes 0.005≤SiO ₂/ Al ₂O ₃≤ 1.8, more preferably make 0.05≤SiO ₂/ Al ₂O ₃≤ 1.5.

The total amount of organic formwork influences target product synthetic easiness and rentability.Organic formwork and P ₂O ₅Mol ratio (organic formwork/P ₂O ₅) be generally 0.2 or bigger, be preferably 0.5 or bigger, more preferably 1 or bigger, and be generally 4 or littler, be preferably 3 or littler, more preferably 2.5 or littler.In addition, two or more are with the scale effect target product synthetic easiness of mixed organic formwork and should select aptly according to condition.Yet under the situation that adopts for example aforesaid morpholine and triethylamine, morpholine/triethylamine mol ratio can be 0.03-20, is preferably 0.05-10, and more preferably 0.1-9 most preferably is 0.2-4.

Be selected from the organic formwork of at least two groups so that including two kinds all belongs in this compound of two groups in mixing, the template blended is not particularly limited in proper order.Can adopt the preparation organic formwork and then with other materials blended method, perhaps organic formwork is mixed and prepares then the method for these mixture respectively with other materials.

About the ratio of water, its lower limit is with Al ₂O ₃Mol ratio (water/Al ₂O ₃) be expressed as 3 or bigger, and be preferably 5 or bigger, more preferably 10 or bigger from easy synthetic viewpoint.The upper limit of water is with mol ratio (water/Al ₂O ₃) be expressed as 200 or littler, and be preferably 150 or littler, more preferably 120 or littler from easy viewpoint synthetic and high yield.

The pH of aqueous gel is 4-10, and is preferably 5-9 from easy synthetic viewpoint, more preferably 5.5-7.5.Amount by adjusting the organic formwork that will add or by adding acid for example hydrochloric acid or sulfuric acid are regulated its pH.Can make except above-mentioned component those to coexist as in the aqueous gel, with the solvability that improves raw material or expect that it can play for example effect of mineralizer.The example of these components comprises for example alcohol of the oxyhydroxide of basic metal or alkaline-earth metal or salt and hydrophilic organic solvent.The scale effect target product synthetic easiness of these coexistence components.

Under the situation of the oxyhydroxide of basic metal or alkaline-earth metal or salt, its ratio is with Al ₂O ₃Mol ratio (coexistence component/Al ₂O ₃) represent to be generally 0.2 or littler, be preferably 0.1 or littler.For example under the situation of alcohol, the mol ratio of itself and water is generally 0.5 or littler, is preferably 0.3 or littler at hydrophilic organic solvent.

To place pressurized vessel and be accompanied by at the aqueous gel that makes under those conditions and stir or remain under the given temperature, and adopt pressurization automatically or, carry out hydro-thermal thus and synthesize with not suppressing the crystalline gas pressurization with stationary state.

Temperature effect target product synthetic easiness during hydro-thermal is synthetic, this temperature is generally 100 ℃ or higher, is preferably 120 ℃ or higher, more preferably 130 ℃ or higher, and be generally 300 ℃ or lower, be preferably 250 ℃ or lower, more preferably 180 ℃ or lower.

Reaction times influences target product synthetic easiness, and the reaction times is generally 2 hours or longer, is preferably 3 hours or longer, and more preferably 5 hours or longer, and be generally 30 days or shorter, be preferably 10 days or shorter, more preferably 4 days or shorter.Temperature of reaction can be constant or can progressively change temperature of reaction during entire reaction.

After hydro-thermal is synthetic with product separation.Although the method that is used for product separation is not particularly limited, pass through filtration, decantation etc. usually with product separation.Isolating product washes with water and is dry under from room temperature (25 ℃) to 150 ℃ temperature.Thereby the zeolite precursor that contains organic formwork can be separated as product.

Next will set forth the calcination steps in the zeolite preparation method of the present invention.

Calcination steps is such process: under the given condition in airflow of nitrogen dilution etc. or under vacuum, will use aforesaid way hydro-thermal synthetic and isolating zeolite precursor thermal treatment.As a result, made zeolite of the present invention.

In this calcination steps, regulate roasting condition to control removing of nitrogenous organic formwork, to make the carbon that contains specified rate at least thus or to contain the nitrogen of specified rate at least and the zeolite of carbon.Can adopt such method: after by roasting organic formwork being removed fully, with nitrogenous compound such as organic compound, for example organic amine such as methylamine or ethamine are adsorbed onto on the hole wall to make the nitrogen that contains specified rate and the zeolite of carbon thus.In the zeolite of so preparation, nitrogenous organic formwork molecule can keep the structure that has kept them simultaneously.Yet preferably, organic formwork is carried out chemical reaction and reservation, so that have the structure of at least partly removing carbon elimination and hydrogen.

Making nitrogenous compound be retained under the situation in the zeolite, this nitrogenous compound preferably has a kind of of higher nitrogen content than employed organic formwork for carbon.For example, nitrogen content represents preferably to be about 1.0-3.5 with the C/N weight ratio.Can determine that reservation still is not keep organic formwork by analyzing for example CHN ultimate analysis or pyrolysis weight mass spectrum (TG-MASS).

Maturing temperature is generally 200 ℃-800 ℃, and is preferably 250 ℃ or higher, more preferably 280 ℃ or higher, especially is 300 ℃ or higher.On the other hand, maturing temperature is preferably 700 ℃ or lower, more preferably 500 ℃ or lower.When zeolite was the Me-aluminosilicophosphate, maturing temperature especially was preferably 450 ℃ or lower.When zeolite was the Me-aluminate or phosphate, maturing temperature especially was preferably 440 ℃ or lower.From preferred temperature range, select the effect that maturing temperature has easy adjusting carbon and nitrogen content.About roasting time, the hold-time under maximum temperature can be 1 minute-15 hours, and is preferably 2 minutes-10 hours, more preferably 5 minutes-8 hours.Pressure during the roasting can be decompression or elevated pressure.Yet under atmospheric pressure or at normal atmosphere carry out roasting on every side usually.

Roasting can or contain in the rare gas element of aerobic at oxygen-free gas usually to be carried out.At zeolite is under the situation of Me-aluminate or phosphate, preferably carries out roasting in containing the rare gas element of aerobic.In oxygen-containing gas, the lower limit of oxygen concn can be 0.1 volume %, and is preferably 0.5 volume % or higher, 1 volume % or higher more preferably, even 2 volume % or higher more preferably.On the other hand, the upper limit of concentration of the oxygen that contains can be 20 volume %, and is preferably 15 volume % or lower, more preferably 10 volume % or lower.Oxygen concn in adopting oxygen-containing gas and adjustments of gas so that its when being in this scope, this has produced and has been suppressed at during the roasting by the effect of organic formwork heating, helps to control roasting thus.

Can also adopt zeolite precursor in for example roasting in the nitrogen of inert gas flow, and the method for roasting in oxygen-containing gas stream then, unexpected heating produced to avoid being accompanied by the oxygenolysis of organic formwork.In this case, be in the rare gas element during the roasting that part is removed organic formwork, thereby can be suppressed at the heating in the subordinate phase roasting of carrying out in the oxygen-containing gas.Therefore, as above-mentioned situation, the control during the roasting is easy.Except oxygen, the gas that can be used for calcination atmosphere is for example nitrogen, argon gas and helium of rare gas element.In some cases, water vapour or the oxynitride amount mixing of 10 volume % at the most.

Obtain in the roasting condition of zeolite of the present invention being identified for, preferably precheck the hydrolysis susceptibility of zeolite precursor and carry out roasting under low relatively temperature, this temperature approaches the temperature that this precursor begins hydrolysis.Therefore from the improved viewpoint of weather resistance, preferably adopt the low relatively temperature in this temperature range and in the presence of gas, carry out roasting with low relatively oxygen level.

The method example that is used for preparing the zeolite with performance of the present invention comprises: according to kind and ratio, its framework density etc. of required Me-aluminate or phosphate and Me-aluminosilicophosphate component, select from above-mentioned condition.Especially, when adopting preferred construction directing agent and selection condition so that include maturing temperature 300-450 ℃, roasting time 2-8 hour and inert gas atmosphere or when containing the inert gas atmosphere of aerobic with the ratio in the preferable range that illustrates above will obtain target product.

At zeolite is under the situation of Me-aluminate or phosphate, and the example of preferred roasting condition is included in the reaction conditions of roasting under the inert gas atmosphere that contains 3-7 volume % oxygen and 300-440 ℃ and 4-8 hour.At zeolite is under the situation of Me-aluminosilicophosphate, and the example of preferred roasting condition is included in the reaction conditions of roasting in the rare gas element and 300-450 ℃ and 4-8 hour.

In addition, containing under the situation of Me as the essentially consist element, when under the inert gas atmosphere that contains aerobic with the ratio in the preferable range that illustrates above, carrying out roasting, under the low relatively temperature in the maturing temperature scope that ought illustrate in the above especially, for example under 300-400 ℃, when under the inert gas atmosphere that contains aerobic with the ratio in the preferable range that illustrates above, carrying out roasting, will obtain target product.

Can make roasting gas by calciner or can not need to make gas by carrying out roasting.Under the situation that gas is passed through, with respect to will be by the air speed of the zeolite precursor of roasting (GHSV: gas hourly space velocity) preferably be in the given scope.Its air speed (GHSV) is preferably 10hr ^-1-10,000hr ^-1, 20hr more preferably ^-1-3,000hr ^-1GHSV is too low, and it is slow to cause removing organic formwork, and too high GHSV is undesirable economically, because the necessary gas flow speed of roasting is too high.As calciner, can adopt any required heating unit, for example retort furnace, tube furnace or kiln.Can fixed bed or fluid bed mode carry out roasting.Incidentally, the GHSV here is expressed as time per unit " (gas volume that passes through)/(volume of zeolite precursor) ".

By aforesaid method, made zeolite of the present invention, it contains carbon or the carbon of specified rate and the zeolite of nitrogen of specified rate.

(application of zeolite of the present invention)

The catalyzer, segregation material, optical material that zeolite of the present invention can be widely used as sorbent material, acid-reaction, oxidizing reaction etc. for example quantum dot and quantum wire, as the fine semiconductor grain of magneticsubstance, perhaps be used for the material of main part of fluorescent substance, dyestuff etc.Especially, because the crystalline structure of this zeolite in being not easy to be reused destroys and absorption property is seldom degenerated, so this zeolite is suitable for as sorbent material.

(as sorbent material)

Because zeolite of the present invention has good weather resistance, for example be not easy to structure deteriorate, so this zeolite is advantageously used for reusable sorbent material.

Especially preferably this zeolite is used as the sorbent material that heat utilization system is used.For example, it is suitable for use as the sorbent material that following heat utilization system is used, and this heat utilization system utilization is by the latent heat of the heat of adsorption that is adsorbed onto adsorbable material on the sorbent material to be produced and/or the adsorbate evaporation that produces when adsorbate evaporates.The term here " heat utilization system " is meant: the heat energy that reclaims with the heat of adsorption form is used as thermal source that heats another kind of material and/or the system that is used as the thermal source of the another kind of material of cooling with the heat energy (low-temperature receiver) that the vaporization heat form reclaims.Its example comprises cold/heat storage system, adsorption heat pump and is used for moisture control, promptly is used to dehumidify/air handling unit of humidification.

Zeolite of the present invention itself has adsorptive power.Yet, in order to be used for heat utilization system, zeolite preferably has following absorption property: it has produced the adsorption isothermal line with relative vapor pressure district under 25 ℃, when changing 0.15 in the scope of relative vapor pressure at 0.01-0.5, the respective change of the adsorptive capacity of then adsorbable material (for example water) is 0.1g/g or bigger in this zone.That is, can be not less than desorption under 0.01 the relative vapor pressure and can be suitable not being higher than the hydrophilic relatively zeolite that adsorbs under 0.5 the relative vapor pressure.Some heat utilization systems can adopt temperature height to 150 ℃ or above thermal source, and enough low relative humidity be can be used for desorption.Yet under the situation of absorption,, therefore be difficult to the necessary relative humidity of absorption is increased to more than 0.5 because humidity is subjected to the envrionment conditions influence of (comprising envrionment temperature).

Relative vapor pressure (φ 1a) by the desorption side and the relative vapor pressure (φ 2a) of absorption side are identified for the operation vapor pressure scope of heat utilization system.Adopt following equation 5 and 6, can calculate φ 1a and φ 2a.The scope of φ 1a to φ 2a is the manipulable relative vapor pressure scope of system wherein.

The relative vapor pressure of desorption side (φ 1a)=[equilibrium vapour pressure power (Tlow1)]/[equilibrium vapour pressure power (Thigh)] ... 5

Relative vapor pressure (φ 2a)=[equilibrium vapour pressure power (Tcool)]/[equilibrium vapour pressure power (Tlow2)] of absorption side ... 6

Equilibrium vapour pressure power (Tlow1), equilibrium vapour pressure power (Thigh), equilibrium vapour pressure power (Tcool) and balance vapor pressure (Tlow2) are meant the equilibrium vapour pressure power under the temperature of Tlow1, Thigh, Tcoo1 and Tlow2 respectively.

In these equations, Thigh (high temperature heat source temperature) be with adsorbate from sorbent material desorption and with adsorbent reactivation the temperature of the thermal medium that is used to heat; Tlow1 (low-temperature heat source temperature) is the temperature of adsorbable material in the condenser; Tlow2 (low-temperature heat source temperature) makes the regenerated sorbent material be used for the temperature of refrigerative thermal medium in adsorbing; Tcool (cold regeneration temperature) is the temperature of adsorbable material in the vaporizer, i.e. the temperature of the low-temperature receiver of Chan Shenging.Incidentally, can adopt the equilibrium vapour pressure force curve of adsorbable material to determine each equilibrium vapour pressure power from these temperature.

In the adsorption process in above-mentioned heat utilization system, low-temperature heat source temperature Tlow2 is low more, and it is high more then to adsorb essential relative humidity, and available relative humidity scope is wide more.Yet, in fact be difficult to remove fully the heat of adsorption that is produced by being adsorbed onto adsorbable material on the sorbent material.In addition, absorption is subjected to comprising the Effect of Environmental of envrionment temperature.Therefore, be difficult to usually low-temperature heat source temperature Tlow2 is adjusted to 20 ℃ or lower.Promptly, at adsorbable material is under the situation of water, when for example obtaining 10 ℃ cold regeneration temperature Tcool when adopting 20 ℃ low-temperature heat source temperature Tlow2, then the operation in the relative water vapour pressure scope of the operation that is higher than 0.52 relative humidity is not suitable for heat utilization system.

On the other hand, in the desorption process in above-mentioned heat utilization system, high temperature heat source temperature T high is high more, and then the essential relative humidity of desorption is low more, and available relative humidity scope is wide more.Incidentally, it is 100 ℃ or higher that some systems can obtain temperature T high, is 120 ℃ or higher in some cases, perhaps approaches the high temperature heat source of 200 ℃ temperature.In this case, even make low-temperature heat source temperature Tlow1 increase to for example 50 ℃ owing to removing the trouble pine for, Effect of Environmental etc., but when high temperature heat source temperature T high was 200 ℃, relative humidity was about 0.01.

Therefore, preferably zeolite of the present invention is used as the sorbent material in the heat utilization system of the present invention, zeolite of the present invention has the absorption property of adsorptive capacity variation in the relative humidity scope of 0.01-0.5.

The adsorptive capacity of adsorbable material variation 0.1g/g or bigger performance are meant when relative vapor pressure changes 0.15: along with the relatively little variation in this relative vapor pressure scope of relative vapor pressure, the adsorptive capacity of adsorbable material (for example water) changes suddenly.The variation of adsorptive capacity is meant that having obtained big adsorptive capacity in narrow relatively relative vapor pressure scope changes.Therefore, can reduce the quantity that obtains the necessary adsorbable material of identical adsorptive capacity under the same conditions, even and the temperature contrast between the thermal source of refrigerative thermal source and heating little in, also can operate heat utilization system.

When the sorbent material, the form that it can moulded products is used at zeolite of the present invention.Under the situation of molded zeolite, should notice that the absorption property that prevents zeolite of the present invention as much as possible reduces.Can be by for example tackiness agent (as the known tackiness agent that is used for sorbent material), adsorbent etc. except zeolite of the present invention mix the mixture that makes and form moulded product by components that zeolite of the present invention and other are optional.The example of tackiness agent comprises inorganic adhesive for example aluminum oxide, silicon-dioxide and clay.By stirring granulation, spraying granulation etc. or passing through isotactic pressing (CIP) with the mixture granulation, to obtain moulded product.Can as required moulded product be pulverized.

The ratio of zeolite of the present invention in sorbent material can be 60wt% or higher, is preferably 70wt% or higher, and can be 100% under the situation of zeolite of the present invention as unique composition material of sorbent material.

(being applied to cold/heat storage system)

Next set forth the embodiment that the sorbent material will include zeolite of the present invention or to contain zeolite of the present invention is used for cold/heat storage system.

Fig. 1 be explanation of the present invention cold/sketch of an embodiment of heat storage system.Of the present invention cold/heat storage system 11 comprises the cold/thermmal storage device of adsorptive type, it comprises recirculated water feeder 12, absorption/desorption apparatus 13 and evaporator/condenser 14 as major parts.Absorption/desorption apparatus 13 contains sorbent material, and be with adsorbable material (for example water) from evaporator/condenser 14 be fed to wherein and with adsorbable material from wherein being fed to the device of evaporator/condenser 14.Evaporator/condenser 14 is to comprise following both device: be used for the adsorbate evaporation and it is fed to the vaporizer of absorption/desorption apparatus 13; With the condenser that is used to cool off from the adsorbable material of absorption/desorption apparatus 13 feeds.Recirculated water feeder 12 is the devices that high-temperature water A or water at low temperature B are fed to absorption/desorption apparatus 13.

This cold/heat storage system 11 is the systems with following structure: be used for used heat (recirculated water of recirculated water feeder 12) is fed to sorbent material (in absorption/desorption apparatus 13 the insides) so that the structure of adsorbate (for example water) desorption from the sorbent material (structure a); With will give the structure (structure b-1) that is required with the device of heating mode operation with heat (heat of adsorption) feed that adsorbable material is adsorbed onto on the sorbent material to be produced by passing through of providing of evaporator/condenser 14, and/or the latent heat feed of the adsorbate evaporation that will adsorbate will be adsorbed onto on the sorbent material to be produced by passing through of providing of evaporator/condenser 14 is to the structure (b-2) of the heat-eliminating medium of the refrigerator that cycles through cooling usefulness.

In the cold/thermmal storage device of the adsorptive type of the effect that utilizes sorbent material, the ability of the adsorbable material of adsorbents adsorb/desorption is as operation source.Although water, ethanol, acetone etc. can be used as the adsorbable material in the cold/thermmal storage device of adsorptive type, from the viewpoint of the quantity of safety, cost and vaporization heat, water most preferably in the middle of these.This adsorbable material is adsorbed on the sorbent material as steam.

As mentioned above, sorbent material of being made up of zeolite of the present invention or the sorbent material that contains this zeolite have mechanical property (comprising good structural strength) and the absorption property during reusing.The sorbent material that this sorbent material therefore can/heat storage system cold by being advantageously used for be used.Especially, especially preferably have so that in narrow relatively relative vapor pressure scope, obtained the sorbent material that big adsorptive capacity changes such absorption property, obtain the necessary sorbent quantity of identical adsorptive capacity under the same conditions because it has reduced effectively.In addition, it has such advantage: even the temperature contrast between the thermal source of refrigerative thermal source and heating hour also can be operated cold/thermmal storage device.

(being applied to adsorption heat pump)

Next set forth the embodiment that the sorbent material that will comprise or contain zeolite of the present invention is used for adsorption heat pump.

Fig. 2 is the sketch of an embodiment of explanation adsorption heat pump of the present invention.Adsorption heat pump of the present invention 21 main by adsorbable material, be used to adsorb/sorbent material of the adsorbable material of desorption, be filled with sorbent material and formed from the vaporizer 24 that wherein will transfer to the absorption/desorption apparatus 22 and 23 of thermal medium, by its cold type that will obtain with by the condenser 25 that its heat that will obtain by means of the condensation of adsorbable material is discharged into the outside by means of the evaporation of adsorbate by the heat that absorption/desorption produced of adsorbable material.High-temperature water or water at low temperature are fed to absorption/desorption apparatus 22 and 23 from recirculated water feeder 26 and 27.Valve 28-31 be configured in absorption/desorption apparatus 22 and 23 and vaporizer 24 and condenser 25 separately between.

Adsorption heat pump is for example according to following principle work.(1) under the situation that valve 29 and 30 is opened, water at low temperature is fed to absorption/desorption apparatus 22 from recirculated water feeder 26, and high-temperature water is fed to absorption/desorption apparatus 23 from recirculated water feeder 27, (i) is in absorption/desorption apparatus 22 then, the adsorbable material (for example water) of adsorbents adsorb feed from vaporizer 24, and because the heat of adsorption that is produced by absorption has obtained warm water, (ii) in absorption/desorption apparatus 23, adsorbate desorption and because the vaporization heat that produces by desorption has obtained cold water from the sorbent material.On the other hand, (2) under the situation that valve 28 and 31 is opened, high-temperature water is fed to absorption/desorption apparatus 22 from recirculated water feeder 26, and water at low temperature is fed to absorption/desorption apparatus 23 from recirculated water feeder 27, (i) is in absorption/desorption apparatus 22 then, adsorbate desorption and because the vaporization heat that produces by desorption has obtained cold water from the sorbent material, (ii) in absorption/desorption apparatus 23, the adsorbable material (for example water) of adsorbents adsorb feed from vaporizer 24, and because the heat of adsorption that is produced by absorption has obtained warm water.

Adsorption heat pump 21 is can operate the heat utilization system that obtains cold water to repeat those two kinds by operating these valves usually.This structure of adsorption heat pump and the other details of principle of work are for example providing among the JP-A-2002-372332.

Adsorption heat pump of the present invention is that the sorbent material that will include the sorbent material of zeolite of the present invention or contain this zeolite is used for adsorption heat pump wherein.As mentioned above, this sorbent material has mechanical property (comprising good structural strength) and the absorption property during reusing.Therefore this sorbent material can be advantageously used for the sorbent material that adsorption heat pump is used.Especially, especially preferably have so that in narrow relatively relative vapor pressure scope, obtained the sorbent material that big adsorptive capacity changes such absorption property, obtain the necessary sorbent quantity of identical adsorptive capacity under the same conditions because it has reduced effectively.In addition, it has such advantage: even the temperature contrast between the thermal source of refrigerative thermal source and heating hour also can be operated adsorption heat pump.

The air handling unit of usefulness (be used to dehumidify)

Next set forth the sorbent material to comprise or to contain zeolite of the present invention be used to the to dehumidify embodiment of air handling unit of usefulness.

Fig. 3 is the sketch of an embodiment of the explanation air handling unit that is used to dehumidify of the present invention.The air handling unit that is used to dehumidify 61 of the present invention be include can be to the sorbent material of adsorbable material (for example water) absorption/desorption, contain the absorption/desorption apparatus 61 of sorbent material and be used for device the device 63 of adsorbent reactivation.The air handling unit 61 of this dehumidifying usefulness can randomly be equipped with and make humidity with the air passageways (not shown) that the air 62 that is conditioned (be also referred to as with by the air of moisture control) passes through, and perhaps is used to force to discharge by the device (not shown) of the air of moisture control.

Absorption/desorption apparatus 61 can make sorbent material and the shape that will fully be contacted by the air 62 of moisture control as long as it has without limits.The example of this shape comprises the rotor shapes with honeycomb structure.

Be used for the device 63 of adsorbent reactivation as follows.(i) under the situation of dehumidifying, this device 63 can be the heat supply device that can about 80 ℃ heat that adsorbent reactivation is required be fed to absorption/desorption apparatus 61.(ii) producing in device by means of for example electrically heated under the situation of heat, this device 63 can be to include thermal source for example well heater or heater coil and be used for the abundant device that heat is sent to the blower of absorption/desorption apparatus 61.(iii) obtain under the situation of thermal source in the outside from device, this device 63 can be the device that is used for from thermal source feed high-temperature gas, for example pipeline.As in the adsorption heat pump, outer thermal source in this case without limits, and its example comprises gas engine and internal combustion turbine and fuel cell.In addition, (iv) under the situation of humidification, the passage that this device 63 can be the damp atmosphere that is used for again humidification by wherein.

Set forth a example of moisture control method below with reference to Fig. 4 by means of the air handling unit of dehumidifying usefulness.Yet, and should not be considered as the moisture control method and be limited to following example.

Fig. 4 is the sketch of explanation as an example of the moisture eliminator air regulator of the air handling unit of dehumidifying usefulness.This moisture eliminator air regulator 70 comprises original air passage 71, regeneration air passage 72, contain the sorbent material that adheres on it moisture eliminator rotor 73, two temperature-sensitive interchangers 74 and 75, be used for providing the heat supply device 76 of heat and humidifier 77 as main parts from thermal source.Temperature rises original air with 73 dehumidifying of moisture eliminator rotor and owing to be adsorbed onto the heat of the water on the moisture eliminator.After this in the first temperature-sensitive interchanger 74 by original air being cooled off with the regeneration air heat exchange, use humidifier 77 humidifications subsequently, and be fed to then by the space 78 of artificial atmosphere.On the other hand, regeneration air from space outerpace introduce, the first temperature-sensitive interchanger 74 by temperature rises with the original air heat exchange, and then with 76 heating of heat supply device.Make this regeneration air of being in the relative humidity state with reduction by moisture eliminator rotor 73, so that water desorption on the dryer rotor 73, with its regeneration.Corresponding to the regenerative heat after the regeneration of sensible heat by in the second temperature-sensitive interchanger 75 with do not have heated regeneration air heat exchange to reclaim.After this, regeneration air is discharged to outside 79.

The sorbent material that comprises the sorbent material of zeolite of the present invention or contain this zeolite can be advantageously used for the sorbent material of the air handling unit of this dehumidifying usefulness, because as mentioned above, this sorbent material has mechanical property (comprising good intensity) and the absorption property during reusing.

In addition, can also be according to above-mentioned principle for example by means of sending into the such method of spatial and carry out humidification by making water desorption from the sorbent material be used for the regenerated air.

(using and absorption property)

The heat utilization system that zeolite of the present invention is used as sorbent material is the system that the heat energy that heat of adsorption reclaims is used as the thermal source of another material of heating and/or is used as the thermal source of another material of cooling with the heat energy (low-temperature receiver) that the vaporization heat form reclaims.As mentioned above, its example comprises cold/heat storage system, adsorption heat pump and is used to dehumidify and the air handling unit of humidification.

In this heat utilization system, adsorbable material (for example water) is adsorbed on the sorbent material as steam.This sorbent material has preferably experienced a kind of material that the big adsorptive capacity of adsorbable material changes in narrow relative vapor pressure scope.Depend on the application of sorbent material, this absorption property changes slightly.

At first be set forth in sorbent material of the present invention is used for preferred absorption property under the situation of adsorption heat pump.

With the sorbent material that is used to adsorption heat pump is so a kind of with wishing: the zeolite of the present invention that wherein is contained in this sorbent material has produced the adsorption isothermal line with relative vapor pressure district under 25 ℃, when changing 0.15 in the scope of relative vapor pressure at 0.05-0.30, then the respective change of the adsorptive capacity of adsorbable material is 0.1g/g or bigger in this zone.In this zeolite, change to be preferably 0.12g/g or bigger as the adsorptive capacity of the water of adsorbable material, 0.15g/g or bigger more preferably, even 0.18g/g or bigger more preferably.

Below with respect to wherein adopt by the gas engine cogeneration or by the fuel cell of solid polymer type or motor car engine produce have 100 ℃ or following cryogenic relatively used heat and the situation of operating adsorption heat pump to be interpreted as what these absorption property are preferred reasons.In the following explanation, make water adopt operation vapor pressure scope under as the situation of adsorbable material.

Operate under the situation of adsorption heat pump adopting by the gas engine cogeneration or by have 100 ℃ or following cryogenic relatively used heat that the fuel cell of solid polymer type or motor car engine produce, when high temperature heat source temperature and low-temperature heat source temperature for example are respectively 80 ℃ and 30 ℃, then operate vapor pressure scope (φ 1a-φ 2a) and be 0.09-0.29.Equally, when high temperature heat source temperature and low-temperature heat source temperature are respectively 60 ℃ and 30 ℃, then operate relative water vapour pressure scope (φ 1a-φ 2a) and be 0.21-0.29.In addition, be used to operate based on the used heat that provides among the JP-A-2000-140625 for being obtained from motor car engine adsorption heat pump situation statement and the calculating made shows: when high temperature heat source temperature and low-temperature heat source temperature are about 90 ℃ and 30 ℃ respectively, then operate relative water vapour pressure scope (φ 1a-φ 2a) and be 0.06-0.29.

Be understood that in the middle of these adopting used heat to operate under the situation of adsorption heat pump, operate relative water vapour pressure scope (φ 1a-φ 2a) and be preferably 0.05-0.30, more preferably 0.06-0.29.Therefore, by reducing under the situation that relative water vapour pressure makes adsorbent reactivation by means of heating, preferred adopt to have make and be not less than 0.05, preferably be not less than the sorbent material of finishing the such absorption property of desorption under 0.06 the relative water vapour pressure.On the other hand, from the viewpoint of adsorptive capacity, preferred adopt to have make and be not higher than 0.30, preferably be not higher than the sorbent material that 0.29 relative water vapour pressure obtains the such absorption property of enough adsorptive capacitys down.

Generally speaking, preferably in adopted operational humidity scope, show the material that big adsorptive capacity changes, usually, preferably at 0.05-0.30, be preferably and show the material that such as mentioned above big adsorptive capacity changes in the relative water vapour pressure scope of 0.06-0.29.

Sorbent material with above-mentioned absorption property can be selected in the sorbent material that comprises or contain zeolite of the present invention.Yet, preferred select to contain the aluminate or phosphate of at least a Me element that especially is selected from Fe, Ni, Co, Mg and Zn or contain at least a aluminosilicophosphate that especially is selected from the Me element of Fe, Ni, Co, Mg and Zn.Especially preferred in the middle of these is that wherein Me is a kind of of Fe.About skeleton construction, it preferably is selected from the structure of AEI, CHA and LEV.At zeolite of the present invention is under the situation of aluminate or phosphate, hope be that the ratio of the Me metal that is contained is 0.01-0.15, is preferably 0.02-0.1 according to the mol ratio ((Me)/(Me+Al+P)) of Me with all elements of forming skeleton construction except oxygen.At zeolite of the present invention is under the situation of aluminosilicophosphate, what wish is according to " Me+Si " and the mol ratio ((Me+Si)/(Me+Si+Al+P)) of forming all elements of skeleton construction except oxygen, the ratio of the Me metal that is contained is 0.01-0.15, is preferably 0.02-0.1.

Next be set forth in sorbent material of the present invention is used for preferred absorption property under the situation of cold/heat storage system.

The sorbent material that is applied to cold/heat storage system is so a kind of with wishing: the zeolite of the present invention that is contained in this sorbent material has produced adsorption isothermal line under 55 ℃, wherein the adsorptive capacity of adsorbate is 0.15g/g or littler under 0.02 relative vapor pressure, and the adsorptive capacity of adsorbate is 0.10g/g or bigger under 0.1 relative vapor pressure, and has relative vapor pressure district, when changing 0.05 in the scope of relative vapor pressure at 0.02-0.1, then the respective change of the adsorptive capacity of adsorbable material is 0.05g/g or bigger in this zone.What more wish is, this zeolite has produced adsorption isothermal line under 55 ℃, wherein the adsorptive capacity of adsorbate is 0.12g/g or littler under 0.02 relative vapor pressure, and the adsorptive capacity of adsorbate is 0.13g/g or bigger under 0.1 relative vapor pressure, and has relative vapor pressure district, in this zone when changing 0.05 in the scope of relative vapor pressure at 0.02-0.1, then the respective change of the adsorptive capacity of adsorbable material is 0.05g/g or bigger, is in particular 0.08g/g or bigger.What especially wish is so a kind of: wherein the adsorptive capacity of adsorbate is 0.04g/g or littler under 0.02 relative vapor pressure, and the adsorptive capacity of adsorbate is 0.15g/g or bigger under 0.1 relative vapor pressure, and this adsorption isothermal line has relative vapor pressure district, when changing 0.05 in the scope of relative vapor pressure at 0.02-0.1, then the respective change of the adsorptive capacity of adsorbable material is 0.10g/g or bigger in this zone.

Being interpreted as what these absorption property with respect to situation on the motor car engine that cold/heat storage system is placed in below is preferred reasons.

In the cold/heat storage system that will be positioned on the motor car engine, with about 90 ℃ hot water of waste heating will adsorb/desorption apparatus is heated to about 90 ℃, and makes the sorbent material in the absorption/desorption apparatus of heating discharge adsorbate.Cycle through the vaporization heat cooling of heat-eliminating medium by producing of water cooler, thus condenser is cooled to about 10 ℃ by this desorption.In this operation, the relative vapor pressure between those devices is about 0.02.Therefore, preferably under 0.02 relative vapor pressure the adsorptive capacity of adsorbate little.Become the low temperature that is not higher than 90 ℃ (for example about 60-85 ℃) or the temperature of condenser becomes under the situation of the temperature that is higher than 10 ℃ (for example about 15-30 ℃) in the temperature of absorption/desorption apparatus, the relative vapor pressure between these is higher than 0.02.Thereby must be issued to enough desorptions at this relative vapor pressure that is higher than 0.02 in this case.Therefore, preferably the adsorptive capacity of adsorbate should be littler under 0.02 relative vapor pressure condition.

Have such situation in Motor vehicles etc.: the temperature of absorption/desorption apparatus is owing to becoming about 45-60 ℃ with scatterer refrigerative cold water, and the temperature of vaporizer owing to heat exchanger becomes about 10 ℃.In this case, absorption/desorption apparatus is about 0.10 with relative vapor pressure between the vaporizer, and therefore, sorbent material preferably has a kind of of the big adsorptive capacity of adsorbate under 0.10 relative vapor pressure.That is, preferably adopt the sorbent material that in this operational humidity scope, shows big adsorptive capacity variation.

Sorbent material with above-mentioned absorption property can be selected in the sorbent material that comprises or contain zeolite of the present invention.Yet, be to select (a) (Me-) aluminate or phosphate with wishing, promptly wherein Me is the iron aluminium phosphate of Fe or (b) (Me-) aluminosilicophosphate, promptly wherein Me is the iron aluminosilicophosphate of Fe.About skeleton construction, it is preferably the CHA structure.Under the situation of above (a), hope be that the ratio of the Me metal that is contained is 0.03-0.25, is preferably 0.04-0.20 according to the mol ratio ((Me)/(Me+Al+P)) of Me with all elements of forming skeleton construction except oxygen.Under the situation of above (b), hope be that the ratio of the Me metal that is contained is 0.03-0.25, is preferably 0.04-0.20 according to " Me+Si " mol ratio ((Me+Si)/(Me+Si+Al+P)) with all elements of forming skeleton construction except oxygen.

More than adopt adsorption heat pump and cold/heat storage system to set forth relation between heat utilization system and the absorption property as the example of system.When selecting to have the zeolite of above-mentioned preferred absorption property and sorbent material that employing comprises this zeolite, then not only obtained sorbent material weather resistance owing to the performance of zeolite of the present invention, and with adopt before the situation of employed sorbent material compare, adsorption process and desorption process respectively lower relative vapor pressure with under higher relative vapor pressure, carry out.Therefore, the only slight variation of relative humidity makes the adsorptive capacity of this adsorbable material change.Thus, sorbent material of the present invention can be advantageously used in to have produced a large amount of used heat with being positioned in and had and use air regulator and caused mileage number further to reduce the adsorption heat pump on the Motor vehicles of such problem and be used for cold/heat storage system.

As mentioned above, especially when zeolite of the present invention was used as the sorbent material of the absorption/desorption that repeats adsorbable material with the sorbent material that comprises this zeolite, it has such preferred properties: during reusing, their adsorptive power was seldom degenerated.Therefore, this zeolite or sorbent material have useful like this effect: as at the heat utilization system that utilizes by the heat of adsorption that is adsorbed onto adsorbable material on the sorbent material to be produced and/or the vaporization heat that evaporation produced by adsorbate, like that, it is adsorbed onto on the sorbent material and this material desorption from the sorbent material is repeated to have withstood use under hundreds of thousands of time or the more this stringent condition at adsorbable material in the air handling unit of for example cold/heat storage system, adsorption heat pump or dehumidifying usefulness.

Embodiment

Set forth the present invention in more detail with reference to embodiment and comparative example below.In any case the present invention should not be considered to be subjected to the restriction of following examples.

The zeolite of following examples 1-1 to 1-3 and embodiment 2-1 to 2-3 all is by the such zeolite of the skeleton construction that zeolite had when kept roasting when carbon content is lower than 0.3wt% by roasting before.

In embodiment and comparative example, service check carries out under the following conditions.

(the X-ray powder diffraction is measured the condition of (XRD))

X-ray source: Cu-K _αLine (λ=1.54

)

Set output: 40kV, 30mA

The optical condition of measuring:

Divergent slit: 1 °

Scatter slit: 1 °

Accept slit: 0.2mm

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

Useful range: 2 θ=4-50 °

Sample: the sample that uses about 100mg to pulverize with agate mortar by means of manpower.Employing has identical shaped sample clamp and sample is clogged wherein with constant quantity almost.

(CN analysis)

Analyze with PERKIN ELMER 2400 serial II CHNS/O analyzers.

(ultimate analysis)

With roasting 6 hours in the airflow of sample under 550 ℃, be dissolved in the hydrochloric acid, and carry out compositional analysis by the ICP method then.

(weight loss measurement)

Under the condition of the sample size of 10 ℃/minute heating rate and about 10mg, make sample in 10mL/ minute airflow, carry out thermogravimetric analysis.Determine weight loss (g1) and weight loss (g2) in the mode above by the weight under 200 ℃, 350 ℃ and 700 ℃.

(absorption property (25 ℃))

Water vapor adsorption amount under measuring 25 ℃ with water vapor adsorption measuring apparatus (Belsorb 18, by Bel Japan Inc. make).

The temperature of Tempeerature-constant air chamber: 50 ℃

Adsorption temp: 25 ℃

The initial pressure of introducing: 3.0 holders

Introduce the number of pressure set-point: 0

Saturated vapour pressure: 23.755 holders

Starting time: 500 seconds

Sample: before measuring, under 120 ℃, carry out 5 hours vacuum-treat.

(absorption property (55 ℃))

Water vapor adsorption amount under measuring 55 ℃ with water vapor adsorption measuring apparatus (Belsorb 18, by Bel Japan Inc. make).

The temperature of Tempeerature-constant air chamber: 60 ℃

Adsorption temp: 55 ℃

The initial pressure of introducing: 3.0 holders

Introduce the number of pressure set-point: 0

Saturated vapour pressure: 118.11 holders

Starting time: 500 seconds

Sample: before measuring, under 120 ℃, carry out 5 hours vacuum-treat.

(the effectively measurement of water adsorption amount)

Adopt thermogravimeter (TGA-50, make by Shimadzu Corp), will about 10mg have allowed in vacuum drier to keep 1 day sample under the steam-laden atmosphere of room temperature (25 ℃) in being heated to 250 ℃ from room temperature (25 ℃) in the dry air stream at 10mL/ minute under 10 ℃/minute the heating rate.To get in the ratio (wt%) of the weight that is heated to during 100 ℃ the sample that under steam-laden atmosphere, is adsorbed by the quantity of the water of desorption and at room temperature (25 ℃) from room temperature (25 ℃) and make effective water adsorption amount.

(durability test 1)

Will about 0.5g sample place internal diameter to be about 20mm (internal diameter of opening is about 15mm) and highly be about the Glass Containers of 40mm.This container is put into baking oven, and this baking oven can be to temperature program(me) control and has been placed under the environment that remains in 25 ℃ and 60% relative humidity.In baking oven, repeat the temperature cycle formed by following steps for 100 times: remain on 40 ℃ following 20 minutes, under 2 ℃/minute speed, be heated to 100 ℃ subsequently, remain on 100 ℃ following 20 minutes, and under 2 ℃/minute speed, be cooled to 40 ℃ subsequently.

(durability test 2)

Sample is placed the vacuum vessel that remains under 90 ℃, and repeats the operation below 500 times, wherein sample is exposed to following 90 seconds of vacuum and 90 ℃ of steam-laden atmosphere each once.

(durability test 3: hydrothermal test)

The pure water of 0.2g amount is placed the bottom of the stainless steel autoclave (the about 100mL of capacity (internal diameter 42mm)) of using Teflon (trade mark) lining.The sample of 0.2g amount placed by Teflon (trade mark) make and have on the sample disc (external diameter 40mm) that length is about the support of 20mm, contact with liquid water at duration of test to prevent sample.This sample disc is placed autoclave, then it is closed.This autoclave was kept 24 hours in the freeze-day with constant temperature baking oven that remains under 100 ℃,, and allow cool to room temperature (25 ℃) subsequently with its taking-up.

(embodiment 1-1)

Carry out the synthetic and roasting of hydro-thermal in the following manner, to make nitrogenous zeolite.

At first the phosphoric acid with 11.53g 85% joins in the 28.05g water.To wherein adding 5.44g pseudobochmite (contain 25% water, produce) gradually by Condea.The mixture of gained is stirred.This mixture is called liquid A.Except that liquid A,, 5.56g ferrous sulfate heptahydrate, 4.35g morpholine, 5.06g triethylamine and 29g water prepares a kind of liquid by being mixed.This liquid joined in the liquid A gradually and the mixture of gained was stirred 3 hours, to obtain having the gel initial reactant material of following composition.

0.4FeSO ₄: 0.8Al ₂O ₃: P ₂O ₅: 1.0 morpholines: 1.0 triethylamines: 70H ₂O

The initial reactant material that obtains is introduced 200-cc to be equipped with in the stainless steel autoclave of Teflon (trade mark) inner cylinder.This parent material was reacted 1 day down at 180 ℃ with static state.After reaction, supernatant liquor is removed to reclaim throw out with the reaction mixture cooling and by decantation.This throw out water is cleaned 3 times, filtered and recycled, dry to obtain zeolite precursor down at 120 ℃ then.

(XRD) differentiates this zeolite precursor by x-ray powder diffraction.Found that this precursor has pure CHA structure.

Make a part (13mg) exsiccant zeolite precursor carry out thermogravimetric analysis.In thermogravimetric analysis, use thermogravimeter (TGA-50, make by Shimadzu Corp.) under 10 ℃/minute this precursor is heated to 700 ℃ from room temperature (25 ℃), the air that made the helium dilution simultaneously under 30mL/ minute is by (oxygen concn, 7 volume %).It the results are shown among Fig. 5.

From the zeolite precursor that obtains, take out the part of 3g subsequently, and the vertical silica tube that places roasting to use.Mixed gas (oxygen concn at the nitrogen of the air that includes 175mL/ minute and 325mL/ minute, 7 volume %) when passing through, down this precursor is heated to 350 ℃ and just in time remain on 350 ℃ (this temperature is in the thermogravimetric analysis by as shown in Figure 5 and near the temperature definite decomposition temperature) then at 0.35 ℃/minute, carried out 6 hours to make roasting thus.Thereby the roasting product that obtains is nitrogenous zeolite.Differentiate this roasting product by XRD.The diffractogram that obtains is shown among Fig. 6.Find that this roasting product has pure CHA structure (FD, 14.5T/nm ³).

The CN analysis of this roasting product demonstrates carbon content and nitrogen content is respectively 2.3wt% and 1.1wt%, and the C/N weight ratio is 2.12.The result of ultimate analysis is to find that the ratio (mol ratio) of component Al, P and Fe and these summations is as follows respectively: Al, 37.8mol%; P, 50mol%; Fe, 12.2mol%.Water vapor adsorption amount (25 ℃) is 27wt%.The result that the absorption property of roasting product (55 ℃) detects is to have obtained being shown in the adsorption isothermal line among Fig. 7.Adopting the equation 3 definite hole utilization coefficients that above provide is 0.9.This roasting product after durability test 1 25 ℃ with 0.5 relative vapor pressure P/Ps under the water vapor adsorption amount measured be 27wt%, and do not observe decline.

Fig. 8 represents the XRD figure of roasting product after durability test 1.Confirm the CHA structure and do not observed the remarkable reduction of degree of crystallinity.In XRD analysis, before repeating and adopt much at one example weight afterwards.Before durability test 1 and detect the particle of roasting product afterwards.The result does not observe breakage of particles.Fig. 9 represents the XRD figure of roasting product after durability test 2, and has confirmed the CHA structure.Roasting product after durability test 2 25 ℃ with 0.5 relative vapor pressure under the water vapor adsorption amount measured be 27wt%.Further measure the weight loss (g1) and the weight loss (g2) of roasting product.

These the results are shown in the table 1.

(embodiment 1-2)

With with embodiment 1-1 in identical mode obtain roasting product as nitrogenous zeolite, except the oxygen concn in maturing temperature and the gas that passes through being changed over 340 ℃ and 5 volume % respectively.

The nitrogen content of the roasting product that obtains is that 1.7wt%, carbon content are 3.1wt%, and the C/N weight ratio is 1.83.From with embodiment 1-1 find that roasting product has pure CHA structure (FD, 14.5T/nm in the XRD figure that obtains of identical mode ³).

Its water vapor adsorption amount (25 ℃) is 27wt%.The hole utilization coefficient that adopts equation 3 to determine is 0.9.Carry out durability test 1, reduction and degree of crystallinity that the result does not observe adsorptive capacity remain unchanged.Further measure the weight loss (g1) and the weight loss (g2) of roasting product.It the results are shown in the table 1.

(embodiment 1-3)

With with embodiment 1-1 in identical mode obtain roasting product as nitrogenous zeolite, except the oxygen concn in maturing temperature and the gas that passes through being changed over 400 ℃ and 0.2 volume % respectively.

The nitrogen content of the roasting product that obtains is that 1.7wt%, carbon content are 5.0wt%, and the C/N weight ratio is 2.86.From with embodiment 1 find that roasting product has pure CHA structure (FD, 14.5T/nm in the XRD figure that obtains of identical mode ³).Its water vapor adsorption amount (25 ℃) is 23wt%.The hole utilization coefficient that adopts equation 3 to determine is 0.77.Carry out durability test 1, reduction and degree of crystallinity that the result does not observe adsorptive capacity remain unchanged.Further measure the weight loss (g1) and the weight loss (g2) of roasting product.It the results are shown in the table 1.

(comparative example 1-1)

With with embodiment 1-1 in identical mode to obtain be the roasting product of iron aluminium phosphate, except maturing temperature is changed over 550 ℃.

The nitrogen content of the roasting product that obtains and carbon content are lower than limit of detection (0.3wt%).From with embodiment 1-1 find that roasting product has pure CHA structure (FD, 14.5T/nm in the XRD figure that obtains of identical mode ³).Its water vapor adsorption amount (25 ℃) is 30wt%.The hole utilization coefficient that adopts equation 3 to determine is 1.Carry out durability test 1, the adsorptive capacity after result's test significantly is reduced to 15wt%.Figure 10 and Figure 11 are illustrated in before the durability test 1 and XRD figure afterwards; Observe in test period degree of crystallinity and reduce.Further measure the weight loss (g1) and the weight loss (g2) of roasting product.It the results are shown in the table 1.

(comparative example 1-2)

The phosphoric acid of 11.5g 85% is joined in the 26g water.(contain 25% water to wherein adding the 5.44g pseudobochmite gradually; Produce by Condea).The mixture of gained was stirred 2 hours.To wherein adding by 8.3g ferrous sulfate heptahydrate is dissolved in the liquid for preparing in the 26g water.To add wherein gradually by making the 2.18g morpholine mix the liquid for preparing in addition with the 7.43g hexahydroaniline.Mixture with gained stirred 2 hours in addition.Thereby obtain having the gel initial reactant material of following composition.

0.6FeSO ₄: 0.8Al ₂O ₃: P ₂O ₅: 0.5 morpholine: 1.5 hexahydroaniline: 60H ₂O

The initial reactant material that obtains is introduced 0.2-L to be equipped with in the stainless steel autoclave of Teflon (trade mark) inner cylinder.This parent material was reacted 12 hours down at 200 ℃ with static state.After reaction, supernatant liquor is removed to reclaim throw out with the reaction mixture cooling and by decantation.This throw out water is cleaned 3 times, filtered and recycled, dry down at 120 ℃ then.With with comparative example 1-1 in identical mode with the solid roasting that obtains, to obtain roasting product as iron aluminium phosphate.

The nitrogen content of the roasting product that obtains and carbon content are lower than limit of detection (0.3wt%).The result of ultimate analysis is to find that the ratio (mol ratio) of component Al, P and Fe and these summations is as follows respectively: Al, 36.9mol%; P, 50mol%; Fe, 13.1mol%.

Find that from XRD figure roasting product has pure CHA structure (FD, 14.5T/nm ³).Its water vapor adsorption amount (25 ℃) is 30wt%.The hole utilization coefficient that adopts equation 3 to determine is 1.Carry out durability test 1, the adsorptive capacity after result's test significantly is reduced to 10wt%.Figure 12 and Figure 13 are illustrated in before the durability test and XRD figure afterwards; Observe in test period degree of crystallinity and reduce.Detect the particle stood durability test, found that powdering fully.Further measure the weight loss (g1) and the weight loss (g2) of roasting product.It the results are shown in the table 1.

(comparative example 1-3)

With with comparative example 1-1 in identical mode carry out that hydro-thermal is synthetic, drying and roasting.The resulting solid of 1g is clogged in the Pyrex that internal diameter is 6mm (trade mark) pipe, and in 500mL/ hour helium flow, handled 2 hours under 300 ℃.Allow this solid cool to room temperature (25 ℃) in helium flow.After this, with 500mL/ hour the 10 volume % ammonia (NH that contain ₃) helium replace the gas passed through, and under room temperature (25 ℃) with it to solids treatment 2 hours.Subsequently, the gas that replaces being passed through with helium is to purge under room temperature (25 ℃).

Resulting solid CN analyzes and demonstrates nitrogen content is 11.5wt%.Carbon content is lower than limit of detection (0.3wt%).Carry out under 80 ℃ at this solid after 3 hours the vacuum, its 25 ℃ with 0.5 relative vapor pressure under the water vapor adsorption amount be 30wt%.The hole utilization coefficient that adopts equation 3 to determine is 1.Figure 14 uses NH ₃The solid XRD figure of handling, and express this solid and have CHA structure (FD, 14.5).Figure 15 is NH ₃-handle, stood the solid XRD figure of durability test 1; It is unbodied that it confirms that this solid has become.Obviously find out from these results: the pore texture of zeolite almost completely destroys, and the water vapor adsorption amount of zeolite significantly reduces.Further measure the weight loss (g1) and the weight loss (g2) of roasting product.It the results are shown in the table 1.

(comparative example 1-4)

With with embodiment 1-1 in identical mode obtain solid, except replacing roasting gas with nitrogen and maturing temperature being changed over 325 ℃.

The CN analytical table reveals nitrogen content and carbon content is respectively 2.7wt% and 10.0wt%, and this shows that this solid is in outside the scope of the present invention.This solid water vapor adsorption amount (25 ℃) is 7.1wt%.The hole utilization coefficient that adopts equation 3 to determine is 0.24.Be apparent that this solid adsorptive capacity is poorer than the water vapor adsorption amount (27wt%) of the zeolite that is in the embodiment 1-1 in the scope of the invention.Further measure the weight loss (g1) and the weight loss (g2) of roasting product.It the results are shown in the table 1.

(comparative example 1-5)

According to United States Patent (USP) 4,554,143 embodiment 11 synthesizes the iron aluminium phosphate that nitrogen content is lower than scope lower limit given to this invention.

The phosphoric acid of 11.6g 85% is joined in the 32g water.To wherein adding the 16.4g aluminum isopropylate gradually.The mixture of gained was stirred 3 hours.To wherein adding 5.6g ferrous sulfate heptahydrate.The liquid that the aqueous solution of tetraethyl ammonium hydroxide (TEAOH) that in addition will be by making 42.1g 35wt% prepares joins wherein.Mixture with gained stirred 3 hours in addition.Thereby obtain to have the gel initial reactant material of following composition.

0.4FeSO ₄∶0.8Al ₂O ₃∶P ₂O ₅∶2.0TEAOH∶68H ₂O

The initial reactant material that obtains is introduced 0.2-L to be equipped with in the stainless steel autoclave of Teflon (trade mark) inner cylinder.This parent material was reacted 42 hours down at 200 ℃ with static state.After reaction, reclaim throw out with the reaction mixture cooling and with separating centrifuge.This throw out water is cleaned, filtered and recycled, and dry down at 120 ℃.Find that from XRD figure institute's exsiccant solid has the CHA structure.The result of ultimate analysis is to find that the ratio (mol ratio) of component Al, P and Fe and these summations is as follows respectively: Al, 44.7mol%; P, 50mol%; Fe, 4.3mol%.

From the zeolite that contains template that obtains, take out a part, and with embodiment 1-1 in identical mode roasting, except maturing temperature being changed over 450 ℃, replace the gas that passed through, and roasting time was changed over outside 2 hours with nitrogen.

XRD analysis demonstrates this solid that obtains by roasting and has CHA structure (FD, 14.5T/nm ³).Nitrogen content by the zeolite that roasting obtained is lower than limit of detection (0.3wt%), and its carbon content is about 1.0wt%, and this shows that this solid is in outside the scope of the present invention.The solid of gained 25 ℃ with 0.5 relative vapor pressure under the water vapor adsorption amount be 20wt%.

Make the solid of gained carry out durability test 2.After the test this solid 25 ℃ with 0.5 relative vapor pressure under the water vapor adsorption amount measured be reduced to 10wt%, this be before the test the absorption value 50%.Further measure the weight loss (g1) and the weight loss (g2) of roasting product.It the results are shown in the table 1.

(embodiment 2-1)

Prepare carbonaceous aluminosilicophosphate in the following manner.

At first the phosphoric acid with 87.1g 85% joins in the 180g water.To wherein adding 57.2g pseudobochmite (contain 25% water, produce) gradually by Condea.The mixture of gained was stirred 3 hours.This mixture is called liquid A.Except that liquid A,, 5.04g pyrogenic silica (Aerosil 200), 36.6g morpholine and 240g water prepares a kind of liquid by being mixed.This liquid is joined in the liquid A gradually.In addition, the 47.0g triethylamine joined wherein and the mixture of gained was stirred 3 hours, to obtain having the gel initial reactant material of following composition.

0.2SiO ₂: Al ₂O ₃: 0.9P ₂O ₅: 1 morpholine: 1.1 triethylamines: 60H ₂O

The initial reactant material that obtains is introduced 1-L to be equipped with in the stainless steel autoclave of Teflon (trade mark) inner cylinder.Being accompanied by to stir under 100rpm makes this parent material react 60 hours down at 190 ℃.After reaction, supernatant liquor is removed to reclaim throw out with the reaction mixture cooling and by decantation.This throw out water is cleaned 3 times, filtered and recycled, dry down at 120 ℃ then.Exsiccant solid (aluminosilicophosphate precursor) is carried out ultimate analysis.Found that the ratio of aluminium, phosphorus and silicon and these summations (mol ratio) is as follows respectively: silicon, 7.9%; Aluminium, 48.7%; Phosphorus, 43.3%.

Be about 6 at GHSV subsequently, 000hr ^-1Airflow under about 1 ℃/minute, the solid (aluminosilicophosphate precursor) that obtains is heated to 350 ℃ from room temperature (25 ℃), and roasting 6 hours in airflow under 350 ℃ is to obtain roasting product.

The XRD analysis of this roasting product has produced XRD figure shown in Figure 16, and it shows CHA structure (FD, 14.5T/nm ³).Adopting the equation 4 definite hole utilization coefficients 2 that above provide is 0.89.The result that the absorption property of this roasting product (25 ℃) is measured is to have obtained being shown in the adsorption isothermal line among Figure 17.CN analysis by this roasting product has confirmed that it contains the carbon of 3.5wt% and the nitrogen of 1.0wt%.Effective water adsorption amount of finding this roasting product is 20.4wt%.

After durability test 3, the XRD analysis of this roasting product has produced XRD figure shown in Figure 180, and it shows the CHA structure.The effective water adsorption amount of this roasting product after durability test 3 is 18.4wt%.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.In addition, make this roasting product carry out durability test 2, the result has confirmed enough weather resistance.

The multiple number is increased in several thousand times the durability test 2 even circulate therein, and this roasting product also shows enough weather resistance.

This roasting product has weather resistance in repeating the inferior absorption/desorption of hundreds of thousands of when being used to adsorption heat pump or humidity control system.

(embodiment 2-2)

Prepare carbonaceous iron aluminosilicophosphate in the following manner.

At first the phosphoric acid with 11.5g 85% joins in the 28.05g water.To wherein adding 6.26g pseudobochmite (contain 25% water, produce) gradually by Condea.The mixture of gained was stirred 3 hours.In this mixture, add a kind of by 2.78g ferrous sulfate heptahydrate being dissolved in the 29g water and 1.2g pyrogenic silica (Aerosil 200) being added the liquid that wherein prepares.In addition, will add wherein gradually, and in addition the mixture of gained be stirred 3 hours by making the 4.35g morpholine mix the liquid for preparing with the 5.64g triethylamine.Thereby obtain having the gel initial reactant material of following composition.

0.2FeSO ₄: 0.4SiO ₂: 0.92Al ₂O ₃: P ₂O ₅: 1.0 morpholines: 1.0 triethylamines: 60H ₂O

The initial reactant material that obtains is introduced 0.2-L to be equipped with in the stainless steel autoclave of Teflon (trade mark) inner cylinder.This parent material was reacted 1 day down at 180 ℃ with static state.After reaction, supernatant liquor is removed to reclaim throw out with the reaction mixture cooling and by decantation.This throw out water is cleaned 3 times, filtered and recycled, dry down at 120 ℃ then.Make exsiccant solid (iron aluminosilicophosphate precursor) carry out ultimate analysis.Found that the ratio of aluminium, phosphorus, iron and silicon and these summations (mol ratio) is as follows respectively: Al, 43.9mol%; P, 40.3mol%; Fe, 6.1mol%; Si, 9.7mol%.

A solid part (12.7mg) that is dried is carried out thermogravimetric analysis.In thermogravimetric analysis, use thermogravimeter (TGA-50, make by Shimadzu Corp.), under 10 ℃/minute, solid is heated to 700 ℃ from room temperature (25 ℃), the air (oxygen concn, 7 volume %) of helium dilution was passed through under 30mL/ minute.It the results are shown among Figure 19.

Subsequently, be that the air of 7% nitrogen dilution is about 6 at GHSV, 000hr at oxygen concn ^-1When passing through down, under about 0.5 ℃/minute, the solid (iron aluminosilicophosphate precursor) that obtains is heated to 420 ℃ from room temperature (25 ℃), and under 420 ℃ (this temperature be by as be shown near the decomposition temperature that the thermogravimetric analysis among Figure 19 determines temperature) roasting 6 hours, to obtain roasting product.

The XRD analysis of this roasting product has produced XRD figure shown in Figure 20, and it shows CHA structure (FD, 14.5T/nm ³).Adopting the equation 3 definite hole utilization coefficients 1 that above provide is 0.77, and the hole utilization coefficients 2 that adopt equation 4 to determine are 0.91.The result that the absorption property of this roasting product (55 ℃) is measured is to have obtained being shown in the adsorption isothermal line among Figure 21.CN analysis by this roasting product confirms that it contains the carbon of 3.2wt% and the nitrogen of 1.1wt%.Effective water adsorption amount of finding this roasting product is 16.7wt%.After durability test 3, the XRD analysis of this roasting product has produced the XRD figure that is shown among Figure 22, and it shows the CHA structure.The effective water adsorption amount of this roasting product after durability test 3 is 15.5wt%.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.

(embodiment 2-3)

With with embodiment 2-2 in identical mode carry out roasting, except replacing roasting gas with nitrogen and maturing temperature being changed over 450 ℃.Thereby obtain carbonaceous iron aluminosilicophosphate.

The XRD analysis of this roasting product has produced XRD figure shown in Figure 23, and it shows CHA structure (FD, 14.5T/nm ³).The hole utilization coefficient 2 that adopts equation 4 to determine is 0.85.CN analysis by this roasting product confirms that it contains the carbon of 5.0wt%.Yet its nitrogen content is lower than limit of detection (0.3wt%).Effective water adsorption amount of finding this roasting product is 15.7wt%.After durability test 3, the XRD analysis of this roasting product has produced the XRD figure that is shown among Figure 24, and it shows the CHA structure.The effective water adsorption amount of this roasting product after durability test 3 is 15.7wt%.After durability test 2, the XRD analysis of this roasting product has produced the XRD figure that is shown among Figure 25, and it shows the CHA structure.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.

(comparative example 2-1)

With with embodiment 2-1 in identical mode will with embodiment 2-1 in identical mode synthetic and dry solid roasting in airflow that obtains by hydro-thermal, except maturing temperature is changed over 550 ℃.Thereby obtain carbon-free aluminosilicophosphate.

The XRD analysis of this roasting product has produced the XRD figure that is shown among Figure 26, and it shows CHA structure (FD, 14.5T/nm ³).Adopt equation 3 and the 4 hole utilization coefficients of determining 1 and 2 to be respectively 1.The CN analysis of this roasting product demonstrates its carbon content and nitrogen content all is lower than limit of detection (0.3wt%).Effective water adsorption amount of finding this roasting product is 22.8wt%.After durability test 3, the XRD analysis of this roasting product has produced XRD figure shown in Figure 27, and it shows amorphous state.Think destroyed and its loading capacity significantly reduction of the pore texture of this roasting product from these results.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.

(comparative example 2-2)

With with embodiment 2-2 in identical mode will with embodiment 2-2 in identical mode by hydro-thermal the synthetic and dry solid that obtains at airflow (oxygen concn, the 7 volume % of nitrogen dilution; GHSV, about 6,000hr ^-1) middle roasting, except maturing temperature is changed over 550 ℃.Thereby obtain carbon-free iron aluminosilicophosphate.

The XRD analysis of this roasting product has produced the XRD figure that is shown among Figure 28, and it shows CHA structure (FD, 14.5T/nm ³).Adopt equation 3 and the 4 hole utilization coefficients of determining 1 and 2 to be respectively 1.The CN analysis of this roasting product demonstrates its carbon content and nitrogen content all is lower than limit of detection (0.3wt%).Effective water adsorption amount of finding this roasting product is 18.3wt%.After durability test 3, the XRD analysis of this roasting product has produced the XRD figure that is shown among Figure 29, and it shows amorphous state.After durability test 3, effective water adsorption amount of this roasting product is 6.8wt%.After durability test 2, the XRD analysis of this roasting product has produced the XRD figure that is shown among Figure 30, and it shows amorphous state.Think destroyed and its loading capacity significantly reduction of the pore texture of this roasting product from these results.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.

(comparative example 2-3)

With with embodiment 2-2 in identical mode will with embodiment 2-2 in identical mode by hydro-thermal the synthetic and dry solid roasting that obtains, except in nitrogen gas stream, carrying out the roasting under 325 ℃ the temperature.Thereby obtain containing iron aluminosilicophosphate above the carbon of the amount of defined range limit among the present invention.

The result of the XRD analysis of this roasting product is to confirm that this product has CHA structure (FD, 14.5T/nm ³).The hole utilization coefficient that adopts equation 4 to determine is 0.57.CN analysis by this roasting product confirms that it contains the carbon of 8.9wt% and the nitrogen of 1.9wt%.Effective water adsorption amount of finding this roasting product is 10.5wt%.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.Find out obviously that from those results the existence that surpasses the carbon of the quantity of defined range limit among the present invention has caused little adsorptive capacity.

(comparative example 2-4)

According to United States Patent (USP) 6,395,674 embodiment 5 is with the precursor roasting of SAPO-34, to obtain SAPO-34.

That is, phosphoric acid and the 9.2g pseudobochmite (containing 25% water) with 15.4g 85% joins in the 18g water gradually.The mixture of gained is stirred.In addition the adding of 10g water wherein and with this mixture was stirred 1 hour.This mixture is called liquid A.Except that liquid A,, 4.1g pyrogenic silica (Aerosil 200), 11.6g morpholine and 15g water prepares a kind of liquid by being mixed.This liquid is joined in the liquid A gradually.To wherein adding 24g water in addition.The mixture of gained was stirred 3 hours.The mixture that obtains is introduced 200-mL to be equipped with in the stainless steel autoclave of Teflon inner cylinder.Mixture was reacted 24 hours down at 200 ℃.After reaction, remove supernatant liquor to reclaim throw out with the reaction mixture cooling and by decantation.The throw out water that obtains is cleaned 3 times, filtered and recycled, and following dry 12 hours at 120 ℃ then.Confirm that by x-ray powder diffraction the solid that obtains has pure CHA structure (FD, 14.5T/nm ³).With United States Patent (USP) 6,395, the mode described in 674 the embodiment 5 is with the roasting 1 hour in helium flow under 450 ℃ of this solid.Thereby obtain the SAPO-34 that carbon content is 8.5wt%.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.

(comparative example 2-5)

With with comparative example 2-4 in identical mode obtain being described in United States Patent (USP) 6,395, the SAPO-34 among 674 the embodiment 5 is except changing over the maturing temperature in helium flow 625 ℃.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.

(comparative example 2-6)

According to the R.T.Yang etc. of citation hereinbefore, Langmuir, 2003,19, the statement among the 2193-2200 comes synthesizing silicoaluminophosphamolecular.

That is, the phosphoric acid with 5g 85% joins in the 52g water.Be accompanied by stirring to wherein adding the 8.9g aluminum isopropylate gradually.This mixture was stirred 3 hours.To wherein adding 4.55g silica gel (LUDOX-As; 40wt%SiO ₂).In addition, be accompanied by stirring to wherein dripping the 25.6g Isopropylamine, to obtain having the starting mixt of following composition.

Al ₂O ₃: P ₂O ₅: 0.7SiO ₂: 10 Isopropylamines: 50H ₂O

The starting mixt introducing capacity that obtains thus is 150mL and is equipped with in the stainless steel autoclave of Teflon inner cylinder.This mixture was reacted 120 hours down at 160 ℃.The reaction after with the reaction mixture cool to room temperature.Isolate throw out and after filtration and water cleaning, reclaim product by decantation.

The product that obtains is carried out the X-ray powder diffraction.The result has confirmed pure GIS structure (FD, 15.3T/nm ³).It the results are shown among Figure 31.

The product that roasting obtains under the condition in the document shown in the table 2, and carry out thermogravimetric analysis then.That is, adopt pyrolysis analysis device (TGA-50 is made by Shimadzu Corp.), the resulting product of about 10mg is being heated to 325 ℃ under 5 ℃/minute in helium flow (30cc/ minute), handled 1 hour down at 325 ℃, then cool to room temperature.After this, replace helium flow with airflow (30cc/ minute), and under 10 ℃/minute, roasting product is heated to 700 ℃, to carry out its thermogravimetric analysis.What obtain the results are shown in the table 2.

(comparative example 2-7)

According to the condition shown in the document table 2, with comparative example 2-6 in identical mode in helium flow, carry out roasting, except the heating rate in the helium flow is changed over 40 ℃/minute.Make the roasting product that obtains in airflow, carry out thermogravimetric analysis.It the results are shown in the table 2.

(comparative example 2-8)

At first phosphoric acid and the 9.52g pseudobochmite with 16.1g 85% (contains 25% water; Produce by Condea) join gradually in the 30g water.The mixture of gained is stirred.This mixture is known as liquid B.Except that liquid B,, 2.52g pyrogenic silica (Aerosil 200), 6.1g morpholine, 7.1g triethylamine and 40g water prepares a kind of liquid by being mixed.This liquid joined in the liquid B gradually and the mixture of gained was stirred 3 hours, to obtain having the initial reactant material of following composition.

0.6SiO ₂: Al ₂O ₃: 1P ₂O ₅: 1 morpholine: 1 triethylamine: 60H ₂O

The initial reactant material that obtains is introduced 200-cc to be equipped with in the stainless steel autoclave of Teflon (trade mark) inner cylinder.Be accompanied by rotation this parent material was reacted 24 hours down at 190 ℃, under 200 ℃ elevated temperature, reacted 24 hours then.After reaction, reaction mixture is cooled off, and remove supernatant liquor to reclaim throw out by decantation.This throw out water is cleaned 3 times, filtered and recycled, and dry down at 120 ℃ then.The solid (aluminosilicophosphate precursor) that is dried is carried out ultimate analysis.Found that the ratio of aluminium, phosphorus and silicon and these summations (mol ratio) is as follows respectively: silicon, 11.6%; Aluminium, 49.0%; Phosphorus, 39.4%.

Subsequently, with embodiment 2-1 in identical mode with solid (aluminosilicophosphate precursor) roasting that obtains, except nitrogen is changed over 450 ℃ as roasting gas with maturing temperature.

XRD analysis by this roasting product confirms that this product has CHA structure (FD, 14.5T/nm ³).The hole utilization coefficient 1 that adopts equation 3 to determine is 0.83, and the hole utilization coefficient 2 that adopts equation 4 to determine is 0.77.CN analysis by this roasting product confirms that it contains the carbon of 7.5wt% and the nitrogen of 0.6wt%.Effective water adsorption amount of finding this roasting product is 14.0wt%.XRD analysis by this roasting product that carries out after durability test 3 confirms that this product has the CHA structure.The effective water adsorption amount of this roasting product after durability test 3 is 12.0wt%.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.

(comparative example 2-9)

According to United States Patent (USP) 4,440,871 synthetic aluminosilicophosphates with AFI structure.

That is, the phosphoric acid with 7.69g 85wt% mixes with 33.29g water.To wherein adding the 4.58g pseudobochmite.These components are mixed together up to mixture become evenly, and continuously stirring 3 hours.Adding the HCl of 1.08g 37wt% in this mixture, then is 2.16g pyrogenic silica (Aerosil200).These components are mixed together up to mixture become even.At last, add the aqueous solution of the tetraethyl ammonium hydroxide (TEAOH) of 18.6g 35wt%, and the mixture stirring of gained is become even up to it.The part of this reaction mixture is placed the stainless steel autoclave of using the Teflon lining.Close autoclave and mixture is descended heating 168 hours at 150 ℃ in baking oven.Clean and filter and reclaim the solid reaction product by decantation, water, and water cleans then.The solid that obtains is at room temperature dry in air.Confirm that by XRD analysis this solid has almost pure AFI structure (FD, 17.3T/nm ³).The nitrogen content of the roasting product that obtains is 1.0wt%, and carbon content is 7.2wt%, and the C/N weight ratio is 7.20.Further measure the weight loss (g1) and the weight loss (g2) of this roasting product.It the results are shown in the table 2.

Incidentally, ferruginous aluminate or phosphate that obtains in embodiment 1-1 to 1-3 and the carbonaceous aluminosilicophosphate that obtains in embodiment 2-1 to 2-3 and carbonaceous iron aluminosilicophosphate are the zeolites that has kept the crystalline structure that has separately before test when carrying out the cycling durable property testing by the following method.

The cycling durable property testing:

Zeolite is placed the vacuum vessel that remains under 90 ℃, and repeats the operation below 500 times, wherein zeolite is exposed to following 90 seconds of vacuum and 90 ℃ of steam-laden atmosphere each once.

After carrying out the cycling durable property testing by the method that illustrates above, 25 ℃ with 0.5 relative vapor pressure under the water vapor adsorption amount measured be at least 80% of the water vapor adsorption amount before the test.

Although at length and with reference to its particular described the present invention, will be apparent that for those skilled in the art, can make various changes and modifications therein, only otherwise depart from its spirit and scope.

The application is based on the Japanese patent application (application number 2003-176319) of Japanese patent application of submitting on January 20th, 2003 (application number 2003-176318) and submission on January 20th, 2003, and its whole contents in this combination as a reference.

Industrial applicibility

Zeolite of the present invention has such excellent results: especially when this zeolite when the adsorbent, It not only has high adsorption capacity, and can not suffer particle to be reduced into powder, also can not suffer Therefore the destruction of crystal structure during reusing can not experience the corresponding reduction of adsorption capacity.

In addition, adopt the heat utilization system of the adsorbent that includes zeolite of the present invention to have such effect: Because include the use of the adsorbent of zeolite of the present invention, this system has good durability.

Claims (24)

1. zeolite, its framework density is 10T/nm ³-16T/nm ³, carbon content is 1wt%-6wt%, and below satisfying (1) or (2):

(1) this zeolite is an aluminate or phosphate, its nitrogen content be 0.5wt%-12wt% and wherein aluminium can the part replace by Me;

(2) this zeolite is an aluminosilicophosphate, and wherein aluminium can part be replaced by Me, and when by roasting when carbon content is lower than 0.3wt%, it has kept the roasting skeleton construction that aluminosilicophosphate had before;

Condition is that the Me in above (1) and (2) is at least a element that is selected from periodictable 2A, 7A, 8,1B and the 2B family element,

Said frame density T/nm ³Be the every nm of expression ³The unit of the T atom number that exists, wherein symbol T represents to constitute the atom of zeolite framework and is not Sauerstoffatom.

2. according to the zeolite of claim 1, it has the skeleton construction that is selected from by code designation AEI, AFR, AFS, AFT, AFX, ATS, CHA, ERI, LEV, LTA and the VFI of IZA definition.

3. according to the zeolite of claim 1 or 2, wherein Me is at least a element that is selected among Fe, Ni, Co, Mg and the Zn.

4. according to each zeolite of claim 1-3, wherein satisfy following formula 1-1 to 1-3 as Me, the Al of the skeleton construction component of aluminate or phosphate and the mol ratio of P:

0≤x≤0.3...1-1, wherein, x represents the mol ratio of Me and Me, Al and P summation;

0.2≤y≤0.6...1-2, wherein, y represents the mol ratio of Al and Me, Al and P summation; With

0.3≤z≤0.6...1-3 wherein, z represents the mol ratio of P and Me, Al and P summation.

5. according to the zeolite of claim 4, wherein the mol ratio of Me satisfies following expression 1-1 ':

0.001≤x≤0.3...1-1 ', wherein, x represents the mol ratio of Me and Me, Al and P summation.

6. according to each zeolite of claim 1-5, wherein the weight ratio of carbon in the aluminate or phosphate and nitrogen is 1.0-4.0.

7. according to each zeolite of claim 1-6, wherein the mol ratio of nitrogen and Me is 0.2-2 in the aluminate or phosphate.

8. according to each zeolite of claim 1-3, be characterised in that it is an aluminosilicophosphate, wherein the mol ratio as Me, Al, P and the Si of the skeleton construction component of this aluminosilicophosphate satisfies following formula 2-1 to 2-4:

0≤x≤0.3...2-1, wherein, x represents the mol ratio of Me and Me, Al, P and Si summation;

0.2≤y≤0.6...2-2, wherein, y represents the mol ratio of Al and Me, Al, P and Si summation;

0.3≤z≤0.6...2-3, wherein, z represents the mol ratio of P and Me, Al, P and Si summation; With

0.001≤w≤0.3...2-4, wherein, w represents the mol ratio of Si and Me, Al, P and Si summation.

9. according to each zeolite of claim 1-8, wherein when zeolite being carried out the cycling durable property testing, kept the crystalline structure that zeolite had before the test in the mode shown in following:

The cycling durable property testing:

Zeolite is placed the vacuum vessel that remains on 90 ℃, and repeats the operation below 500 times, wherein zeolite is exposed to following 90 seconds of vacuum and 90 ℃ of steam-laden atmosphere each once;

The reservation of crystalline structure:

When adopt identical device, identical testing conditions, when identical sample clamp detects zeolite with identical example weight by XRD, then at least 50% of the highest peak value of strength of the highest peak value of strength after the test before for test, condition is that peak strength is meant peak height and is the numerical value that obtains by by summit reading subtracting background reading.

10. according to each zeolite of claim 1-9, wherein when zeolite being carried out the cycling durable property testing in the mode shown in following, then 25 ℃ with 0.5 relative vapor pressure under the water vapor adsorption amount of zeolite after the test of measuring for test before determined its water vapor adsorption amount at least 80%:

The cycling durable property testing:

Zeolite is placed the vacuum vessel that remains under 90 ℃, and repeats the operation below 500 times, wherein zeolite is exposed to following 90 seconds of vacuum and 90 ℃ of steam-laden atmosphere each once.

11. one kind prepares each the method for zeolite of claim 1-10, wherein in the presence of at least a structure direction agent, at least a metallic element compound as zeolite component is carried out hydro-thermal to be synthesized, and is roasting under 20 volume % or the lower atmosphere with the zeolite precursor that obtains at oxygen concn, described structure direction agent is to be selected from the structure direction agent that contains in (1) nitrogenous cycloaliphatic heterocycle compound, (2) in the amine of one or more cycloalkyl and the amine that (3) contain one or more alkyl two or more sets.

12., be roasting under 0.1 volume % or the higher atmosphere at oxygen concn wherein with zeolite precursor according to the method for preparing zeolite of claim 11.

13. according to the method for preparing zeolite of claim 11 or 12, wherein with the roasting temperature of zeolite precursor at 300 ℃-450 ℃.

14. according to each the method for preparing zeolite of claim 11-13, wherein with zeolite precursor roasting 4 hours-8 hours.

15. according to each the method for preparing zeolite of claim 11-14, wherein zeolite precursor is a synthetic zeolite in the presence of the structure direction agent that includes at least a organic compounds containing nitrogen that is selected from following material: morpholine, hexahydroaniline, triethylamine, Isopropylamine, N, N-diisopropylethylamine, N-methyl-n-Butyl Amine 99, isobutylamine, hexamethylene imine, N, N-diethylethanolamine and N, the N-dimethylethanolamine.

16., wherein be at oxygen concn under the atmosphere of 0.1 volume %-20 volume % 300 ℃-440 ℃ roasting temperature 4 hours-8 hours with zeolite precursor according to each the method for preparing zeolite of claim 11-15.

17. a sorbent material, it comprises each zeolite of claim 1-10.

18. sorbent material according to claim 17, its mesolite has produced the adsorption isothermal line with relative vapor pressure district under 25 ℃, when changing 0.15 in the scope of relative vapor pressure at 0.01-0.5, then the respective change of the adsorptive capacity of adsorbable material is 0.1g/g or bigger in this zone.

19. a utilization, is characterised in that this sorbent material is each a sorbent material of claim 17 or 18 by the heat utilization system of the vaporization heat of the heat of adsorption that is adsorbed onto adsorbable material on the sorbent material to be produced and/or adsorbate.

20. cold/heat storage system, this stocking system has: (a) be used for used heat is offered sorbent material so that the structure of adsorbate desorption, (b-1) be used for the heat of adsorption that adsorbable material is adsorbed onto on the sorbent material to be produced is offered the structure of requirement with the device of type of heating operation, and/or the latent heat that (b-2) is used for adsorbate evaporation that adsorbate is adsorbed onto on the sorbent material to be produced offers through the structure of cooling with the heat-eliminating medium of GM Refrigerator Working, wherein, adopted each sorbent material of claim 17 or 18.

21. cold/heat storage system according to claim 20, it is the sorbent material that is used for cold/heat storage system, and the zeolite that wherein is contained in this sorbent material has produced the adsorption isothermal line with relative vapor pressure district under 55 ℃, when changing 0.05 in the scope of relative vapor pressure at 0.02-0.1, then the respective change of the adsorptive capacity of adsorbable material is 0.05g/g or bigger in this zone.

22. cold/heat storage system according to claim 21, wherein in the adsorption isothermal line that under 55 ℃, obtains, the adsorptive capacity of adsorbate is 0.12g/g or littler under 0.02 relative vapor pressure, and the adsorptive capacity of adsorbate is 0.13g/g or bigger under 0.1 relative vapor pressure.

23. an adsorption heat pump, it has adopted each sorbent material of claim 17 and 18.

24. an air handling unit that is used for moisture control, it has adopted the sorbent material of claim 17 or 18.

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