CN103889551B - Adsorption heat pump water vapor adsorption material, its manufacture method and use the adsorption heat pump of this water vapor adsorption material - Google Patents
Adsorption heat pump water vapor adsorption material, its manufacture method and use the adsorption heat pump of this water vapor adsorption material Download PDFInfo
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Abstract
The present invention provides the adsorption heat pump water vapor adsorption material that the resistances to water such as a kind of adsorption-desorption excellent performance and resistance to water logging are also excellent.Described water vapor adsorption materials'use at least contains silicon atom, aluminum atom and phosphorus atoms in framing structure and skeletal density is 12.0T/Above, 16.0T/Following zeolite, and containing relative to the periodic table of elements the 11st race's metal that the weight of zeolite is 0.1～15 weight %.If making zeolite support 11 race's metals, then promote that the bronsted acid sites of the hydrolysis of zeolite is replaced by 11 race's metal ions, owing to the bronsted acid sites in zeolite reduces, so the resistances to water such as the resistance to water logging of zeolite improve.
Description
Technical field
The present invention relates to adsorption heat pump water vapor adsorption material, its manufacture method containing zeolite and use this steam
The adsorption heat pump of adsorbing material.
Background technology
In adsorption heat pump, dehumidification air conditioner device, in order to make to have adsorbed the regneration of adsorbent material of adsorbate, such as water, logical
Crossing heating adsorbing material makes adsorbate desorbing regenerate, and the adsorbing material of regeneration is cooled to the temperature for adsorbing adsorbate,
It is re-used for the absorption of adsorbate.It addition, utilize the used heat of higher temperature (more than 120 DEG C), warm as this adsorbing material
The absorption heat pump of regeneration thermal source is the most practical.But, owing to typically being sent out by cogeneration plant, fuel cell, automobile
The relatively low temperature that heat is less than 100 DEG C that cooling water, the solar heat etc. of motivation obtains, so cannot be as the most practical
The driving heat source of absorption heat pump changed is used, it is desirable to having of the low-temperature waste heat of less than 100 DEG C, especially 60 DEG C～80 DEG C
Effect utilizes.
Even if it addition, the operation principle of adsorption heat pump is identical, but according to available heat source temperature difference to adsorption material
The characterization of adsorption that material requires also differs widely.Such as, the gas engine cogeneration of heat and power that uses as the thermal source of high temperature side, solid
The temperature of waste heat of high molecular fuel battery is 60 DEG C～80 DEG C, and the temperature of the cooling water of automobile engine is 85 DEG C～90 DEG C.
Further, the heat source temperature of cold side is also different because of the setting place of device.Such as, in the case of automobile, it is to be obtained by radiator
The temperature arrived, mansion, house etc. are then the temperature of water-cooling tower, river water etc..It is to say, the operating temperature range of adsorption heat pump
It is: when being arranged on mansion etc., low temperature side is 25 DEG C～35 DEG C, and high temperature side is 60 DEG C～80 DEG C；When being arranged on automobile etc., low temperature side
Being 30 DEG C～40 DEG C, high temperature side is 85 DEG C～about 90 DEG C.So, in order to effectively utilize used heat, it is desirable to though low temperature side thermal source
The little device also being able to drive with the temperature difference of high temperature side thermal source.
In order to even if the surrounding of adsorbing material is the high temperature of comparison, device also is able to fully work, and needs in low phase pair
Adsorbate is adsorbed under vapour pressure, and in order to make adsorbing material used for a small amount of and miniaturization of the apparatus, the suction of adsorbing material
Attached desorption quantity have to be many.Further, in order to utilize the thermal source of low temperature, desorbing in the desorbing of adsorbate (regeneration of adsorbing material)
Temperature have to be low.
That is, the adsorbing material used in adsorption heat pump or dehumidification air conditioner device is required as follows:
(1) at low relative vapor pressure absorption adsorbate (the most adsorbable),
(2) adsorption-desorption amount is many,
(3) in high relative vapor pressure desorbing adsorbate (at low temperatures can desorbing).
In the past, as the adsorbing material of adsorption heat pump, use silica gel and the zeolite of low silica-alumina ratio the most always.But,
In the past for adsorbing material adsorption-desorption when utilizing the thermal source of lower temperature as the driving source of adsorption heat pump of adsorption heat pump
Ability is insufficient.Such as, as the typical example of zeolite of adsorption heat pump, it is considered to during the water vapor adsorption isotherms of zeolite 13X,
Drastically adsorbing at relative vapour pressure less than 0.05, at the relative vapor intermediate pressure section higher than 0.05, the water vapor adsorption amount of zeolite is not
Change.During regenerative adsorption material, reduce the relative humidity of ambient gas and make the moisture desorbing temporarily adsorbed remove, in order to make
The hydrolysis being adsorbed in zeolite 13X is inhaled, and needs to reduce relative vapour pressure, the most in general needs 150 DEG C～the thermal source of 200 DEG C.
It addition, as heat pump adsorbing material, have studied Jie synthesized with the micellar structure of surfactant as template
Porous molecular sieve (FSM-10 etc.) (patent documentation 1), is commonly referred to as AlPO it addition, be investigated when desiccant4Porous calcium phosphate
Aluminum system molecular sieve (patent documentation 2).Wherein, mesopore molecular sieve (FSM-10) adsorbs in the scope of relative vapour pressure 0.20 and 0.35
Amount difference is big, for 0.25g/g, is the promising raw material (chart 4 of patent documentation 1: Figure 14；FSM-10).But, relatively low
The scope adsorbance of relative vapour pressure is little, the least in the scope adsorbance difference of adsorbance change relative vapour pressure greatly, heat of adsorption
Pump performance is insufficient.It addition, structural breakdown when being also pointed out Reusability, as the problem of the function reduction of adsorbing material,
Durability becomes problem.
It addition, in patent documentation 3, it is proposed that " the adsorption heat pump zeolite adsorption material being made up of following adsorbing material,
Described adsorbing material, in 25 DEG C of water vapor adsorption isotherms measured, has at relative vapour pressure more than 0.05, less than 0.30
In the range of relative vapour pressure when changing 0.15 the adsorbance of water be changed to the relative vapor intermediate pressure section of more than 0.18g/g ", its
In, describe preferred aluminate or phosphate.Thus, compared with existing silica gel, zeolite, adsorb in the range of identical relative vapour pressure
Amount change is bigger, so using the adsorbing material of almost identical weight can produce bigger effect on moisture extraction.Additionally, make use of
The scope of relatively low relative vapour pressure shows adsorption heat pump or the dehumidification air conditioner dress of the adsorbing material of big adsorption-desorption amount change
Putting, the difference of the water adsorption amount because being caused by the adsorption-desorption of adsorbing material is big, can carry out adsorbing material more at low temperatures
Raw (desorbing), it is possible to drive adsorption heat pump or dehumidification air conditioner device with utilizing the heat source high-efficiency rate of low temperature than ever.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 9-178292 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-197439 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-114067 publication
Summary of the invention
But, it is known that the zeolite proposed in patent documentation 3 resistance to water (resistance to water logging) when water logging is low.
In adsorption heat pump or dehumidification air conditioner device in the case of actually used zeolite adsorption material, stop adsorption heat pump or
During dehumidification air conditioner device, producing dew inside device, the dew of generation is attached to the zeolite of adsorbing material.Further, deposit
The problem causing the absorbability decline of zeolite decomposition, steam at the water droplet because of this attachment.The particularly environment temperature of zeolite
In the case of degree height, the hydrolysis that there is zeolite is more easy to carry out, the problem that the water vapor adsorption ability of zeolite is remarkably decreased.
Consider from such situation, the adsorbing material used in adsorption heat pump or dehumidification air conditioner device required as follows:
(1) at low relative vapor pressure absorption adsorbate (the most adsorbable),
(2) adsorption-desorption amount is many,
(3) in high relative vapor pressure desorbing adsorbate (at low temperatures can desorbing), and,
(4) resistance to water (resistance to water logging) is excellent, there is not the problem causing absorbability to decline because of hydrolysis,
But in the zeolite of patent documentation 3, it is impossible to meet the requirement characteristic of the resistances to water such as resistance to water logging.
The present invention completes in view of this problem, and problem is to provide excellent as the adsorption-desorption performance of adsorbing material
Different, and the adsorption heat pump water vapor adsorption material that the resistance to water such as resistance to water logging is also excellent.
The present inventor etc. conduct in-depth research, found that contain in framing structure in the past to solve above-mentioned problem
The aluminate or phosphate system zeolite having aluminum atom and phosphorus atoms is known as preferred adsorbing material in adsorption heat pump purposes,
And by making such zeolite contain the periodic table of elements the 11st race's metal with the form supported etc., it is possible to it is being maintained as adsorption material
The resistances to water such as resistance to water logging is greatly improved in the case of the performance of material.
That is, the present inventor etc. have studied the water logging test of zeolite, found that the bronsted acid sites in zeolite promotees
Enter the hydrolysis of zeolite.Thus, it is found that by making zeolite support the periodic table of elements the 11st race's metal, the Blang in result zeolite
Si Taide acid site is replaced by 11 race's metal ions, and the bronsted acid sites in zeolite reduces, thus the resistance to water logging of zeolite
Property etc. resistance to water improve.
The present invention completes based on such opinion, is below purport.
[1] a kind of adsorption heat pump water vapor adsorption material, it is characterised in that it is the use of in framing structure at least
It is 12.0T/ containing silicon atom, aluminum atom and phosphorus atoms and skeletal densityAbove, 16.0T/Following
The water vapor adsorption material of zeolite, and containing relative to the periodic table of elements the 11st race that the weight of zeolite is 0.1～15 weight %
Metal.
[2] a kind of adsorption heat pump water vapor adsorption material, it is characterised in that it is the use of in framing structure at least
The water vapor adsorption material of the zeolite containing silicon atom, aluminum atom and phosphorus atoms, under the conditions of being 0.3 by relative humidity (P/Ps)
The suction that water vapor adsorption amount after following water logging test is obtained relative to the ratio of the water vapor adsorption amount before following water logging test
Attached sustainment rate is more than 70%.
(water logging test)
Make 0.5g sample be dispersed in 5g water, the slurry obtained is joined the stainless steel high-pressure equipped with fluororesin inner core
In still.After it is stood 24 hours at 100 DEG C, by filtering, sample is reclaimed, be dried 12 hours at 100 DEG C.
[3] according to the adsorption heat pump water vapor adsorption material described in [2], it is characterised in that containing relative to above-mentioned boiling
The weight of stone is the periodic table of elements the 11st race's metal of 0.1～15 weight %.
[4] according to the adsorption heat pump water vapor adsorption material according to any one of [1]～[3], it is characterised in that above-mentioned
It is zeolite structured for CHA that the IZA of zeolite specifies.
[5] according to the adsorption heat pump water vapor adsorption material described in [1], [3] or [4], it is characterised in that above-mentioned element
Periodic chart the 11st race's metal is copper.
[6] according to the adsorption heat pump water vapor adsorption material according to any one of [1] or [3]～[5], its feature exists
In, it is 0.1～10 weight % relative to the content of the above-mentioned periodic table of elements the 11st race's metal of the weight of above-mentioned zeolite.
[7] according to the adsorption heat pump water vapor adsorption material according to any one of [1]～[6], it is characterised in that in phase
The adsorbance of water when relative vapour pressure changes 0.15 in the scope that vapour pressure is more than 0.05, less than 0.30 is changed to 0.15g-
H2More than O/g.
[8] according to the adsorption heat pump manufacture method of water vapor adsorption material according to any one of [1]～[7], it is special
Levy and be, framing structure at least contains silicon atom, aluminum atom and phosphorus atoms and skeletal density is 12.0T/With
Upper, 16.0T/The periodic table of elements the 11st race's metal is supported on following zeolite.
[9] according to the adsorption heat pump manufacture method of water vapor adsorption material according to any one of [1]～[7], it is special
Levy and be, by containing silicon atom raw material, aluminum atomic raw material, phosphorus atoms raw material, the periodic table of elements the 11st race's raw metal and polyamines
Aqueous gel carry out Hydrothermal Synthesis.
[10] a kind of adsorption heat pump, it is characterised in that use the adsorption heat pump water according to any one of [1]～[7] to steam
Aspiration enclosure material forms.
According to the present invention, it is provided that adsorption-desorption excellent performance and resistance to water loggings such as steam adsorption-desorption durability repeatedly
Property etc. the adsorption heat pump water vapor adsorption material of the resistance to water also problem that absorption property excellent, that do not caused by dew declines
Material and durability when using this adsorption heat pump water vapor adsorption material, life-time service, adsorption heat pump of excellent in reliability.
Accompanying drawing explanation
Fig. 1 be represent embodiment 1～3 and comparative example 1 zeolite water logging test before and after water vapor adsorption isotherms survey
Determine the figure of result.
Fig. 2 is the structure of the adsorption heat pump of the application examples of adsorption heat pump adsorbing material being denoted as the present invention relates to
Become the flow chart of example.
Detailed description of the invention
Hereinafter, the present invention is described in detail, but the explanation of constitutive requirements set forth below is the embodiment party of the present invention
One example (typical example) of formula, the present invention is not by these content special provisions.
[adsorption heat pump water vapor adsorption material]
The adsorption heat pump water vapor adsorption material of the present invention is characterised by, it is the use of and at least contains in framing structure
Having silicon atom, aluminum atom and phosphorus atoms and skeletal density is 12.0T/Above, 16.0T/Following boiling
The water vapor adsorption material of stone, and containing relative to the periodic table of elements the 11st race gold that the weight of zeolite is 0.1～15 weight %
Belong to (following, sometimes referred to simply as " 11 race's metal ").
＜ zeolite ＞
The zeolite used in the present invention at least contains silicon atom, aluminum atom and phosphorus atoms in framing structure.
In framing structure, preferably contain aluminum atom, phosphorus atoms and the silicon in the zeolite of silicon atom, aluminum atom and phosphorus atoms
The existence ratio of atom is to meet following formula (I), (II) and the scope of (III).
0.05≤x≤0.11…(I)
(in (I) formula, x represents rubbing of the silicon atom of the total of the silicon atom relative to framing structure, aluminum atom and phosphorus atoms
That ratio)
0.3≤y≤0.6…(II)
(in (II) formula, y represents the aluminum atom of the total of the silicon atom relative to framing structure, aluminum atom and phosphorus atoms
Mol ratio)
0.3≤z≤0.6…(III)
(in (III) formula, z represents the phosphorus atoms of the total of the silicon atom relative to framing structure, aluminum atom and phosphorus atoms
Mol ratio)
The zeolite that more preferably the existence ratio of silicon is represented by following formula (IV), more preferably by following formula V table
The zeolite shown, particularly preferably for the zeolite represented by following formula (VI).
0.06≤x≤0.105…(IV)
0.07≤x≤0.10…(V)
0.075≤x≤0.095…(VI)
(in (IV)～(VI) formula, x is as defined above)
By x, y, z the most within the above range, it is possible to obtain desired characterization of adsorption, it additionally is able to form zeolite,
Durability also becomes abundant.
Additionally, in the present invention it is possible to the framing structure at zeolite is contained within beyond silicon atom, aluminum atom, phosphorus atoms
Other element.As other element, can enumerate lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, ferrum, cobalt, nickel, palladium, copper, zinc, gallium, germanium, arsenic,
Stannum, calcium, boron etc..These other elements can contain only a kind in the framing structure of zeolite, it is also possible to containing two or more.
Should illustrate, the zeolite that the present invention relates to when its framing structure is contained within 11 race's metal, 11 in framing structure
Race's amount of metal is also included within 11 race's amounts of metal contained by adsorption heat pump water vapor adsorption material of the present invention.
That is, 11 race's metals contained by water vapor adsorption material of the present invention can be contained in the framing structure of zeolite,
Can also be present in outside framing structure, it is also possible to be both.But, in the present invention, it is preferred to 11 race's metal major parts are not
It is present in the framing structure of zeolite, and is present in outside framing structure, i.e. deposited in the framing structure of zeolite by supporting
?.
Should illustrate, above-mentioned atomic ratio can be determined by elementary analysis.In the present invention, elementary analysis is to make sample
Heating for dissolving carries out icp analysis in aqueous hydrochloric acid solution.
It addition, skeletal density (Framework density) is the parameter of reflection crystal structure, the zeolite used in the present invention
Skeletal density is that IZA (International Zeolite Association) is at ATLAS OF ZEOLITE FRAMEWORK
The numerical value represented in TYPES Fifth Revised Edition2001, for 12.0T/Above, 16.0T/Hereinafter, the higher limit of skeletal density is preferably 15.0T/Lower limit is preferably 13.0T/
If skeletal density less than above-mentioned scope, then has structure to become unstable trend, on the other hand, if it exceeds above-mentioned scope,
Then there is the trend that adsorbance diminishes.
It addition, as the structure of the zeolite used in the present invention, be not particularly limited, if the structure specified with IZA
Code represents, then can enumerate AEI, AEL, AET, AFI, AFN, AFR, AFS, AFT, AFX, ATO, ATS, CHA, ERI, LEV, SOD,
VFI etc..Wherein, from the point of view of characterization of adsorption, durability, it is preferably provided with the structure of AEI, AEL, AFI, CHA, LEV, SOD,
Particularly from the point of view of durability and characterization of adsorption, preferably CHA type.
＜ 11 race metal ＞
The 11 race's metals contained in the adsorption heat pump water vapor adsorption material of the present invention are for the Blang removing in zeolite
Si Taide acid site, it is preferable to enumerate copper, silver, gold, particularly preferably copper.As 11 race's raw metals, it is not particularly limited,
Generally use the inorganic acid salts such as the sulfate of 11 race's metals, nitrate, phosphate, chloride, bromide, acetate, oxalates,
The acylates such as citrate, the organo-metallic compound such as pentacarbonyl, ferrocene etc..Wherein, from the deliquescent sight water
Point considers, preferably inorganic acid salt, acylate, such as nitrate, sulfate, acetate, hydrochlorate etc..Can according to circumstances make
With oxide or the oxide of micronized of colloidal.
In the water vapor adsorption material of the present invention, 11 race's metals can contain only a kind, it is also possible in any combination and ratio
Rate contains two or more.
In order to have sufficient water vapor adsorption amount, steam adsorption-desorption durability repeatedly and water logging test durability,
The content of 11 race's metals in the water vapor adsorption material of the present invention is 0.1～15 weight % relative to zeolite, preferably 0.1～
10 weight %, more preferably 0.2～5 weight %, especially preferably 0.3～3 weight %.
If 11 race's tenors in water vapor adsorption material are less than above-mentioned lower limit, then cannot fully obtain by containing 11
The improvement effect of the resistance to water that race's metal brings, if it exceeds the above-mentioned upper limit, then has the trend that absorption property is impaired.
Should illustrate, the reduction of the 11 big multipair bronsted acid sites of race's metal that the framing structure of zeolite is contained within does not has
There is contribution, therefore, in 11 race's metals in the water vapor adsorption material of the present invention more than 5 weight %, more than preferably 10 weight %,
More than more preferably 50 weight %, more than further preferred 70 weight %, particularly preferred its total amount, preferably with the shape supported by zeolite
State is present in outside the framing structure of zeolite.
It addition, the adsorption heat pump water vapor adsorption material of the present invention is characterised by, employ in framing structure extremely
Contain silicon atom, aluminum atom and the zeolite of phosphorus atoms less, relative humidity (P/Ps) after being the following water logging test under the conditions of 0.3
Water vapor adsorption amount test relative to following water logging before the Adsorption Dimension holdup obtained of the ratio of water vapor adsorption amount be 70%
Above.
(water logging test)
Make 0.5g sample be dispersed in 5g water, the slurry obtained is joined the stainless steel high-pressure equipped with fluororesin inner core
In still.After it is stood 24 hours at 100 DEG C, by filtering, sample is reclaimed, be dried 12 hours at 100 DEG C.
As the adsorbing material of the performance meeting such Adsorption Dimension holdup, the most as described above employ at skeleton
Structure at least contains silicon atom, aluminum atom and phosphorus atoms and skeletal density is 12.0T/Above, 16.0T/Following zeolite, and containing relative to the periodic table of elements the 11st that the weight of this zeolite is 0.1～15 weight %
The water vapor adsorption material of race's metal.
[the adsorption heat pump manufacture method of water vapor adsorption material]
As the adsorption heat pump method of water vapor adsorption material of the manufacture present invention, it is not particularly limited, such as, can lift
Go out following method:
(A) after synthetic zeolite, the method supporting 11 race's metals of ormal weight through metal supporting procedures.That is, manufacture at bone
Shelf structure at least contains silicon atom, aluminum atom and phosphorus atoms and skeletal density is 12.0T/Above, 16.0T/Following zeolite so that it is support the side of 11 race's metals relative to the amount that the weight of zeolite is 0.1～10 weight %
Method (hereinafter referred to as " manufacture method (A) ")；Or,
(B), during Hydrothermal Synthesis zeolite, use containing silicon atom raw material, aluminum atomic raw material, phosphorus atoms raw material, 11 race's metal raw
The method that the aqueous gel of material and polyamines carries out Hydrothermal Synthesis.That is, by former containing silicon atom raw material, aluminum atomic raw material, phosphorus atoms
The aqueous gel of material, 11 race's raw metals and polyamines carries out Hydrothermal Synthesis, and obtaining skeletal density is 12.0T/Above,
16.0T/Below and supported the method for zeolite of 11 race's metals relative to the amount that zeolite is 0.1～15 weight %
(hereinafter referred to as " manufacture method (B) ").
{ manufacture method (A) }
First, the method for the adsorption heat pump water vapor adsorption material utilizing manufacture method (A) to manufacture the present invention is carried out
Explanation.
The manufacture ＞ of ＜ zeolite
The method manufacturing the zeolite supporting 11 race's metals is not particularly limited, such as can be based on Japanese Patent Publication 4-
No. 37007 publications, Japanese Patent Publication 5-21844 publication, Japanese Patent Publication 5-51533 publication, U.S. Patent No. 4440871
Method described in number publication etc., profit is manufactured by the following method.
Carry out Hydrothermal Synthesis after i.e., generally aluminum atomic raw material, silicon atom raw material, phosphorus atoms raw material and template being mixed, remove
Template is gone to obtain zeolite.
＜ aluminum atomic raw material ＞
The aluminum atomic raw material of the zeolite in the present invention is not particularly limited, generally can enumerate pseudobochmite, aluminum isopropylate., three
The aluminium-alcohol salts such as aluminum ethylate., aluminium hydroxide, alumina sol, sodium aluminate etc..These can be used alone a kind, it is also possible to mixes 2 kinds
Used above.From the point of view of the angle and reactivity height of processing ease, preferably pseudobochmite is as aluminum atomic raw material.
＜ silicon atom raw material ＞
The silicon atom raw material of the zeolite in the present invention is not particularly limited, generally can enumerate pyrolysis (fumed) silicon dioxide,
Silicon dioxide gel, silica sol, waterglass, silester, methyl silicate etc..These can be used alone a kind, it is possible to
To mix two or more use.From the point of view of high-purity and reactive height, preferably pyrolytic silicon dioxide is former as silicon atom
Material.
＜ phosphorus atoms raw material ＞
The phosphorus atoms raw material of the zeolite in the present invention is usually phosphoric acid, it is possible to use aluminum phosphate.Phosphorus atoms raw material is permissible
It is used alone a kind, it is also possible to mix two or more and use.
＜ template ＞
As template, it is possible to use the various templates used in known method, especially as template, preferably from as follows
The compound often organizing each selection more than a kind at least 2 groups in 3 groups uses, and particularly preferably combination is from (1) group and (2) group
1 kind used above.
(1) containing nitrogen as heteroatomic ester ring type heterocyclic compound
(2) alkylamine
(3) tetra-alkyl ammonium hydroxide
(1) containing nitrogen-atoms as heteroatomic ester ring type heterocyclic compound
It is usually 5～7 rings as the heterocycle of heteroatomic ester ring type heterocyclic compound containing nitrogen-atoms, preferably 6 yuan
Ring.Heteroatomic number contained by heterocycle is usually less than 3, preferably less than 2.Hetero atom beyond nitrogen-atoms is any
, preferably in addition to nitrogen-atoms, possibly together with oxygen atom.Heteroatomic position is not particularly limited, preferably hetero atom the most not phase
Adjacent.
It addition, be usually less than 250, preferably containing nitrogen-atoms as the molecular weight of heteroatomic ester ring type heterocyclic compound
It is less than 200, more preferably less than 150, it addition, usually more than 30, preferably more than 40, more preferably more than 50.
As such containing nitrogen-atoms as heteroatomic ester ring type heterocyclic compound, morpholine, N-methyl can be enumerated
Quinoline, piperidines, piperazine, N, N '-dimethyl piperazine, 1,4-diazabicylo (2,2,2) octane, N-methyl piperidine, 3-methyl piperidine,
Quinuclidine, pyrrolidine, N-Methyl pyrrolidone, hexamethylene imine etc..These can be used alone a kind, it is also possible to mixes 2 kinds
Used above.Wherein, preferably morpholine, hexamethylene imine, piperidines, particularly preferred morpholine.
(2) alkylamine
The alkyl of alkylamine is typically chain-like alkyl, and the number of the alkyl contained by 1 molecular alkyl amine is not particularly limited, excellent
Select 3.
It addition, the alkyl of alkylamine can partly have the substituent groups such as hydroxyl.
The carbon number of the alkyl of alkylamine preferably less than 4, the carbon number of the whole alkyl in more preferably 1 molecule total
It is calculated as 5～10.
It addition, the molecular weight of alkylamine is usually less than 250, preferably less than 200, more preferably less than 150.
As such alkylamine, di-n-propylamine, Tri-n-Propylamine, Tris(isopropylamine)., triethylamine, triethanolamine, N can be enumerated,
N-diethyl ethylene diamine, N, N-dimethylethanolamine, N methyldiethanol amine, N-methylethanolamine, di-n-butylamine, neopentyl amine,
Two n-amylamines, 2-aminopropane., tert-butylamine, ethylenediamine, diisopropylethylamine, N-methyl n-butylamine etc..These can be used alone 1
Kind, it is also possible to mix two or more and use.Wherein, preferably di-n-propylamine, Tri-n-Propylamine, Tris(isopropylamine)., triethylamine, di-n-butylamine,
2-aminopropane., tert-butylamine, ethylenediamine, diisopropylethylamine, N-methyl n-butylamine, particularly preferred triethylamine.
(3) tetra-alkyl ammonium hydroxide
As tetra-alkyl ammonium hydroxide, preferably 4 alkyl are the tetra-alkyl ammonium hydroxide of the alkyl of carbon number less than 4.
Tetra-alkyl ammonium hydroxide can be used alone a kind, it is also possible to mixes two or more and uses.
Combining compound of more than two kinds when using as template, a combination thereof is arbitrary, wherein, preferably and with morpholine and
Triethylamine.
The blending ratio that these templates are respectively organized needs to select according to condition.During 2 kinds of templates of mixing, generally, the 2 of mixing
The mol ratio planting template is 1:20～20:1, preferably 1:10～10:1, more preferably 1:5～5:1.During 3 kinds of templates of mixing, logical
The mol ratio of normal 3rd kind of template contains nitrogen-atoms as miscellaneous former relative to using 2 kinds of templates of above-mentioned mixed in molar ratio, preferably (1)
The ester ring type heterocyclic compound of son adds up to 1:20～20:1 with (2) alkylamine, preferably 1:10～10:1, and more preferably 1:
5～5:1.
Template is not necessarily required to use, if but use template as described above, then there is the Si that can control in zeolite and contain
The advantage of amount.Its detailed reason is not yet clear and definite, but is presumed as follows.
Such as, when synthesizing SAPO (silicoaluminophosphate) of CHA type structure, (1) contains nitrogen-atoms as heteroatomic alicyclic ring
Formula heterocyclic compound, such as morpholine can synthesize the SAPO that Si content is many relatively easily.But, if Si to be synthesized is poor
SAPO, then fine and close composition, amorphous component are many, crystallization difficulty.On the other hand, (2) alkylamine, such as triethylamine as it appears from the above,
Although with the SAPO of limited condition synthesis CHA structure, but the SAPO of various structure can be typically easy to be mixed with.But, anti-mistake
From the point of view of, easily becoming is not fine and close composition, amorphous component but the SAPO of crystal structure.That is, these templates have for importing
The feature of CHA structure, the feature etc. of promotion SAPO crystallization.Think by combining these features, it is possible to play synergy, aobvious
The effect that cannot realize when being now used alone.
＜ utilizes the synthesis ＞ of the zeolite that Hydrothermal Synthesis carries out
Aqueous gel is prepared in the mixing of above-mentioned silicon atom raw material, aluminum atomic raw material, phosphorus atoms raw material, template and water.This
Time order by merging do not limit, according to use condition suitably select, first in water mixing phosphorus atoms raw material
With aluminum atomic raw material, then mixing silicon atom raw material and template wherein.
For the composition of aqueous gel, represent silicon atom raw material, aluminum atomic raw material and phosphorus with the mol ratio of oxide
During atomic raw material, SiO2/Al2O3Value be typically larger than 0, preferably more than 0.02, it addition, usually less than 0.5, preferably 0.4
Hereinafter, more preferably less than 0.3.It addition, P2O5/Al2O3Ratio be usually more than 0.6, preferably more than 0.7, more preferably
More than 0.8, usually less than 1.3, preferably less than 1.2, more preferably less than 1.1.
The composition of the zeolite obtained by Hydrothermal Synthesis is relevant to the composition of aqueous gel, in order to obtain desired group
The zeolite become, can suitably set the composition of aqueous gel.
The usage amount of the total of template with template relative to Al2O3Molar ratio computing, usually more than 0.2, preferably 0.5
Above, more preferably more than 1, usually less than 4, preferably less than 3, more preferably less than 2.5.
The order that the template often organizing each selection more than a kind from the group of above-mentioned more than 2 carries out mixing is limited the most especially
Fixed, can mix with other material after preparation template, it is also possible to each template is mixed with other material respectively.
It addition, the ratio of water is relative to Al2O3Be usually more than 3 with molar ratio computing, preferably more than 5, more preferably 10 with
On, usually less than 200, preferably less than 150, more preferably less than 120.
It addition, the pH of aqueous gel is usually more than 5, preferably more than 6, more preferably more than 6.5, usually 10 with
Under, preferably less than 9, more preferably less than 8.5.
Should illustrate, in aqueous gel, composition other than the above can be made as requested to coexist.As such one-tenth
Point, alkali metal, the hydroxide of alkaline-earth metal or salt can be enumerated, the hydrophilic organic solvent such as alcohol.For the ratio coexisted, alkali gold
In the case of genus, the hydroxide of alkaline-earth metal or salt, relative to Al2O3It is usually less than 0.2 with molar ratio computing, preferably 0.1
Hereinafter, in the case of the hydrophilic organic solvent such as alcohol, be usually less than 0.5 relative to water with molar ratio computing, preferably 0.3 with
Under.
The aqueous gel obtained is put into pressure vessel, at autogenous pressures, or adds at the gas not hindering crystallization
Pressure, keeps set point of temperature with stirring or static condition, thus carries out Hydrothermal Synthesis.The reaction temperature of Hydrothermal Synthesis is usually
More than 100 DEG C, preferably more than 120 DEG C, more preferably more than 150 DEG C, usually less than 300 DEG C, preferably less than 250 DEG C,
More preferably less than 220 DEG C.In this temperature range, during being warming up to as the maximum temperature reached of maximum temperature,
Preferably keep more than 1 hour in 80 DEG C～120 DEG C of temperature ranges, particularly preferably keep more than 2 hours.If this heating-up time is little
In 1 hour, then the durability of the zeolite zeolite containing template obtained calcining obtained became insufficient.On the other hand,
The upper limit of above-mentioned heating-up time is not particularly limited, if but long, not preferred, generally from the point of view of production efficiency
It is less than 50 hours, preferably less than 24 hours.
Temperature-rising method between said temperature region is not particularly limited, such as can use increase monotonously method,
Method that the method for step variation, vibration etc. change up and down and combine the various modes such as mode that these methods carry out heating up.
Under normal circumstances, consider from the easiness controlled, be preferably used and will heat up speed and be maintained at below certain value Andthe Monotonic Temperature Rising Sa
Mode.
It addition, in the present invention, it is preferred to keep the stipulated time near above-mentioned maximum temperature reached, here, up to reach
Referring to temperature～the maximum temperature reached of lower than this temperature 5 DEG C near temperature, the time near maximum temperature reached that is maintained at is subject to
The synthesis easiness impact of desired material, usually more than 0.5 hour, preferably more than 3 hours, more preferably 5 hours
Above, usually less than 30 days, preferably less than 10 days, more preferably less than 4 days.
Reach the cool-down method after maximum temperature reached to be not particularly limited, it is possible to use the method for step variation,
The method that vibration etc. below maximum temperature reached change up and down and combine these methods and carry out the various modes such as the mode lowered the temperature.Logical
In the case of Chang, from the viewpoint of the easiness controlled, the durability of zeolite obtained, drop after preferably keeping maximum temperature reached
Temperature is to 100 DEG C～the temperature of room temperature.
The recovery ＞ of ＜ zeolite
After above-mentioned Hydrothermal Synthesis, from product, separate and recover zeolite.The method separating zeolite from product does not has spy
Do not limit.Generally, first pass through filtration or decant etc. separate solid constituent, after the solid constituent washing that will separate, in room temperature～
The temperature of 150 DEG C is dried and obtains the zeolite containing template as product.
Then, removing template from the zeolite containing template, its method is known method, is not particularly limited.
Generally can utilize under the atmosphere of air or the noble gas containing aerobic or noble gas, 300 DEG C～the temperature of 1000 DEG C
Degree is calcined, or utilize the extractants such as ethanol water, ether containing HCl carry out the methods such as extraction remove containing mould
Plate.
Here, for calcining heat, preferably 400 DEG C～900 DEG C, more preferably 450 DEG C～850 DEG C, further preferably
Being 500 DEG C～800 DEG C, calcining preferably carries out 1 second～about 24 hours.
But, remove template by above-mentioned calcining etc. optional, can the zeolite containing template be supplied follow-up
The supporting procedures of 11 race's metals.
＜ 11 race metal support ＞
It is not particularly limited as the method supporting 11 race's metals to zeolite, it is possible to use the ion exchange generally used
Method, impregnation support method, precipitation supports method, solid state ion exchange method, CVD, spray drying method etc..It is preferably solid state ion exchange
Method, impregnation support method, spray drying method.
As 11 race's raw metals, be not particularly limited, generally use the sulfate of 11 race's metals, nitrate, phosphate,
The inorganic acid salt such as chloride, bromide, the acylate such as acetate, oxalates, citrate, pentacarbonyl, ferrocene etc. are organic
Metallic compound etc..Wherein, from the viewpoint of the dissolubility water, preferably inorganic acid salt, acylate, such as nitric acid
Salt, sulfate, acetate, hydrochlorate etc..Can according to circumstances use the oxide of colloidal or the oxide of micronized.
As 11 race's raw metals, can be by 11 different to 11 race's metal species or classes of compounds race's raw metals
Two or more is also used.
After making zeolite support 11 race's metals, preferably 400 DEG C～900 DEG C, more preferably 450 DEG C～850 DEG C, the most excellent
It is selected in 500 DEG C～800 DEG C, carries out 1 second～24 hours, preferably carry out 10 seconds～8 hours, more preferably carry out 30 minutes～4 hours
The calcining of left and right.This calcining is optional, but by calcining, it is possible to increase support 11 races of framing structure in zeolite
The dispersibility of metal, to improving, resistance to water is effective.
In order to give sufficient water vapor adsorption amount, steam adsorption-desorption durability repeatedly and water logging test durability,
The loading of 11 race's metals is 0.1～15 weight % as discussed previously with respect to the weight of zeolite, preferably 0.1～10 weight %,
More preferably 0.2～5 weight %, more preferably 0.3～3 weight %.
Even if the 11 race's metals so manufactured support zeolite is directly used as water vapor adsorption material with powder, it is also possible to
The known binding agent mixing such as silicon dioxide, aluminium oxide, clay mineral, carry out pelletize, molding and as water vapor adsorption material
Use.
{ manufacture method (B) }
It follows that the method for the adsorption heat pump water vapor adsorption material utilizing manufacture method (B) to manufacture the present invention is entered
Row explanation.
Manufacture method (B) by by containing silicon atom raw material, aluminum atomic raw material, phosphorus atoms raw material, 11 race's raw metals and
The aqueous gel of polyamines carries out Hydrothermal Synthesis and manufactures the zeolite having supported 11 race's metals.
In manufacture method (B), owing to using the aqueous containing 11 race's raw metals and polyamines to coagulate during Hydrothermal Synthesis zeolite
Glue, so 11 race's metals in aqueous gel and polyamines interact and stabilisation consumingly, and is difficult to and zeolitic frameworks unit
Element reaction, it is possible to obtain mainly being supported with dispersedly in the pore of zeolite the boiling of 11 race's metals outside the framing structure of zeolite
Stone.
Should illustrate, in manufacture method (B), polyamines also serves as template and plays a role.Other system in manufacture method (B)
The condition of making is not particularly limited, it is possible to use the known hydrothermal synthesis method manufacture as illustrating in manufacture method (A).Separately
Outward, other template beyond polyamines can be added in aqueous gel.Carried out Hydrothermal Synthesis by aqueous gel, remove polyamines, its
Its template and obtain zeolite.Hereinafter, an example of manufacture method (B) is illustrated.
＜ raw material ＞
As silicon atom raw material, aluminum atomic raw material, phosphorus atoms raw material, 11 race's raw metals, it is possible to use manufacture method (A)
Explanation in above-mentioned raw materials.
＜ polyamines ＞
As the polyamines used in manufacture method (B), preferably by formula H2N-(CnH2nNH)x-H (in formula, n be 2～6 whole
Number, x is the integer of 1～6) represent by polyamine compounds obtained by more than 2 alkylideneimino chain elongations.
In above-mentioned formula, the integer of n preferably 2～5, the integer of more preferably 2～4, further preferred 2 or 3, particularly preferred 2.
X preferably 2～5, the integer of more preferably 2～4, further preferred 3 or 4, particularly preferred 4.
As such polyamines, wherein, ethylenediamine, diethylenetriamines, trien, tetren price
Cheap, thus preferably, wherein, particularly preferred trien, tetren.These polyamines can be used alone a kind,
Can also be mixed two or more use.
Other template ＞ of ＜
In manufacture method (B), can be as other template now, excellent together with above-mentioned polyamines and use other template
Nitrogen is contained as heteroatomic ester ring type heterocyclic compound, (2) alkylamine in (1) that choosing is enumerated from the explanation of manufacture method (A)
(3) compound often organizing each selection more than a kind in the group of more than 2 in tetra-alkyl ammonium hydroxide these 3 groups uses, and they can
With template as above in the explanation by identical condition use manufacture method (A).
11 race's metals that ＜ utilizes Hydrothermal Synthesis to carry out support the synthesis ＞ of zeolite
By above-mentioned silicon atom raw material, aluminum atomic raw material, phosphorus atoms raw material, 11 race's raw metals and polyamines, as desired
Other template used mixes with water prepares aqueous gel.Order by merging now does not limit, and fits according to the condition used
When selecting, such as, in water, first mix phosphorus atoms raw material and aluminum atomic raw material, more wherein mixing silicon atom raw material,
11 race's raw metals, polyamines and other template.
For the composition of aqueous gel, if representing that silicon atom raw material, aluminum atomic raw material, phosphorus are former with the mol ratio of oxide
Sub-raw material and 11 race's metal (M) raw materials, then SiO2/Al2O3Value be typically larger than 0, be less than 0.5, preferably less than 0.4, more excellent
Elect less than 0.3 as.It addition, P2O5/Al2O3Value be usually more than 0.6, preferably more than 0.7, more preferably more than 0.8, logical
It is often less than 1.3, preferably less than 1.2, more preferably less than 1.1.MaOb/Al2O3(wherein, a and b represents that M's with O is former respectively
Son than) value be usually more than 0.01, preferably more than 0.03, more preferably more than 0.05.
The composition of the zeolite utilizing Hydrothermal Synthesis and obtain is relevant to the composition of aqueous gel, therefore, in order to obtain being wished
The zeolite of the composition hoped, the most suitably sets the composition of aqueous gel.
The amount of the polyamines in aqueous gel is in the case of using in the case of other template and not using other template, excellent
Elect following usage amount as.
＜ uses situation ＞ of other template
In the case of using other template, the total amount of polyamines and other template with the total of polyamines and other template relative to
Al2O3Molar ratio computing, usually more than 0.2, preferably more than 0.5, more preferably more than 1, usually less than 4, preferably 3
Hereinafter, more preferably less than 2.5.
Additionally, it is preferred that polyamines with polyamines relative to MaObMolar ratio computing, generally with more than 0.1, preferably with more than 0.5, more
Preferably with more than 0.8, generally with less than 10, preferably with less than 5, more preferably use with the amount of less than 4.
＜ does not use situation ＞ of other template
In the case of not using other template, for reason similar to the above, preferably polyamines amount with polyamines relative to
Al2O3Molar ratio computing, usually more than 0.2, be preferably more than 0.5, more preferably more than 1, usually less than 4, be preferably 3
Below, more preferably less than 2.5；With polyamines relative to MaObMolar ratio computing, generally with more than 1, preferably with more than 5, more preferably
With more than 10, generally with less than 50, preferably with less than 30, more preferably use with the amount of less than 20.
Should illustrate, other template needs suitably to select according to condition, such as, when using morpholine and triethylamine, and morpholine/tri-
The mol ratio of ethamine is 0.05～20, preferably 0.1～10, more preferably 0.2～9.By every group from the group of above-mentioned more than 2
The order that each template selecting more than a kind carries out mixing is not particularly limited, and can mix with other material after preparation template,
Each template can also be mixed with other material respectively.
It addition, the ratio of water is relative to Al2O3, it is usually more than 3 with molar ratio computing, preferably more than 5, more preferably 10
Above, usually less than 200, preferably less than 150, more preferably less than 120.
It addition, the pH of aqueous gel is usually more than 5, preferably more than 6, more preferably more than 6.5, usually 11 with
Under, preferably less than 10, more preferably less than 9.
Should illustrate, in aqueous gel, composition other than the above can be made as requested to coexist.As such one-tenth
Point, alkali metal, the hydroxide of alkaline-earth metal or salt can be enumerated, the hydrophilic organic solvent such as ethanol.For the ratio coexisted, alkali
In the case of metal, the hydroxide of alkaline-earth metal or salt, relative to Al2O3, it is usually less than 0.2 with molar ratio computing, is preferably
Less than 0.1, in the case of the hydrophilic organic solvent such as ethanol, relative to water, it is usually less than 0.5 with molar ratio computing, is preferably
Less than 0.3.
The aqueous gel obtained is joined pressure vessel, at autogenous pressures, or does not hinders the gas of crystallization
Add pressure, keep set point of temperature with stirring or static condition, thus carry out Hydrothermal Synthesis.The reaction temperature of Hydrothermal Synthesis is usually
More than 100 DEG C, preferably more than 120 DEG C, more preferably more than 150 DEG C, usually less than 300 DEG C, preferably less than 250 DEG C,
More preferably less than 220 DEG C.Response time is usually more than 2 hours, preferably more than 3 hours, more preferably more than 5 hours,
Usually less than 30 days, preferably less than 10 days, more preferably less than 4 days.Reaction temperature can be fixed in the reaction, it is also possible to
Periodically change.
The recovery ＞ of ＜ zeolite
After above-mentioned Hydrothermal Synthesis, from product, separate and recover zeolite.The method separating zeolite from product does not has spy
Do not limit.Generally, first pass through filtration or decant etc. separate solid constituent, after the solid constituent washing that will separate, in room temperature～
The temperature of 150 DEG C is dried and obtains the zeolite containing template as product.
Then, removing template from the zeolite containing template, its method is known method, is not particularly limited.
Generally can utilize under the atmosphere of air or the noble gas containing aerobic or noble gas, 300 DEG C～the temperature of 1000 DEG C
Degree is calcined, or utilize the extractants such as ethanol water, ether containing HCl carry out the methods such as extraction remove containing mould
Plate.
Here, for calcining heat, preferably 400 DEG C～900 DEG C, more preferably 450 DEG C～850 DEG C, further preferably
It it is 500 DEG C～800 DEG C.Calcination time is 1 second～24 hours, preferably 10 seconds～8 hours, more preferably 30 minutes～4 hours.
The 11 race's metals so manufactured support zeolite directly can be used as water vapor adsorption material with powder, it is also possible to
The known binding agent mixing such as silicon dioxide, aluminium oxide, clay mineral, carry out pelletize, molding and as water vapor adsorption material
Use.
For the zeolite so obtained, durable in order to give sufficient water vapor adsorption amount, steam adsorption-desorption repeatedly
Property and water logging test durability, the content of 11 race's metals is 0.1～15 weight % as discussed previously with respect to weight zeolite, preferably
It is 0.1～10 weight %, more preferably 0.2～5 weight %, more preferably 0.3～3 weight %.
[containing or be supported with the characteristic of zeolite of 11 race's metals]
＜ adsorbance change ＞
The present invention uses containing or be supported with the zeolite of 11 race's metals relative vapour pressure be more than 0.05,0.30 with
Under scope in relative vapour pressure when changing 0.15, the adsorbance change of water is preferably 0.15g-H2More than O/g, more preferably
0.16g-H2More than O/g, more preferably 0.18g-H2More than O/g, this is as adsorption heat pump water vapor adsorption material
Purposes is preferred.
＜ steam adsorption-desorption performance ＞ repeatedly
The present invention uses containing or be supported with the zeolite of 11 race's metals and can have following performance: steam at following water
In the test of gas adsorption-desorption repeatedly, Adsorption Dimension holdup is more than 80%.
(test of steam adsorption-desorption repeatedly)
Sample is held in the Dewar vessel maintaining 90 DEG C, respectively the saturated steam atmosphere of 5 DEG C and 90 DEG C
Saturated steam atmosphere exposes 90 seconds, repeats this operation.Now, it is adsorbed in examination when being exposed to the saturated steam atmosphere of 90 DEG C
The water of sample moves to be maintained in the tank of 5 DEG C the saturated steam atmosphere next part desorbing of 5 DEG C.From the m time absorption
To n-th desorbing, by the total amount (Qn of the water of the tank moving to 5 DEG C；M (g)) and the dry weight (W (g)) of sample, ask as follows
Go out average adsorption amount (Cn each time；m(g/g)).
[Cn；M]=[Qn；M]/(n-m+1)/W
Adsorption Dimension holdup refers to obtain 1001 times～2000 times of the steam thus tried to achieve adsorption-desorption repeatedly test
The value that average adsorption amount obtains with the ratio of the average adsorption amount of 1 time～1000 times.The Adsorption Dimension holdup height table of average adsorption amount
Even if showing the adsorption-desorption that water is repeated, zeolite does not deteriorates.
The Adsorption Dimension holdup of the zeolite containing or being supported with 11 race's metals preferably used in the present invention is more than 80%, excellent
Elect more than 90% as, more preferably more than 95%.The upper limit of Adsorption Dimension holdup is the situation not causing zeolite to deteriorate, for
100%.
＜ resistance to water ＞
The present invention uses containing or be supported with the zeolite of 11 race's metals and can have following performance: following 100
DEG C, Adsorption Dimension holdup is more than 70% in the water logging of 24 hours test.
(water logging test)
Make 0.5g sample be dispersed in 5g water, the slurry obtained is joined the stainless steel high-pressure equipped with fluororesin inner core
In still.After it is stood 24 hours at 100 DEG C, by filtering, sample is reclaimed, be dried 12 hours at 100 DEG C.
It is the water after the water logging test under the conditions of 0.3 that the Adsorption Dimension holdup of water logging test refers to obtain relative humidity (P/Ps)
Vapor sorption amount and water logging test before the ratio of water vapor adsorption amount and the value that obtains.The resistance to water logging height of zeolite represents 100
After DEG C carrying out water logging in 24 hours test, the water vapor adsorption ability of zeolite does not deteriorates.
Adsorption Dimension holdup after the water logging test of the zeolite containing or being supported with 11 race's metals used in the present invention is preferred
It is more than 80%, more preferably more than 90%, more preferably more than 95%.
[adsorption heat pump]
In the present invention use containing or be supported with the zeolite of 11 race's metals as it has been described above, be have high Adsorption Dimension holdup and
There is the zeolite of the resistances to water such as high resistance to water logging, according to use such containing or be supported with the present invention of zeolite of 11 race's metals
Water vapor adsorption material, it is possible to realize the adsorption heat pump that is driven with the thermal source of the lower temperature of less than 100 DEG C.
To use the present invention water vapor adsorption material the present invention adsorption heat pump be constructed without limit especially, such as
Can enumerate and possess the adsorption heat pump such as lower component:
Adsorber, repeats release heat of adsorption limit, limit and adsorbate (steam) is adsorbed in the operation of above-mentioned adsorbing material
With the warm outside utilization from the desorption operations of above-mentioned desorbed of adsorbed materials adsorbate,
Vaporizer, the evaporation by adsorbate obtained cold and hot is discharged into outside, simultaneously by the adsorbate that produces
Vapor recovery to above-mentioned adsorber, and
Condenser, cold and hot the making outside utilization is condensed, simultaneously by cold by the steam of the adsorbate of desorbing in above-mentioned adsorber
Solidifying adsorbate supplies above-mentioned vaporizer.
Preferably the adsorption heat pump of the present invention is for the method carrying out operating with following condition, and described condition is: work as steam
Adsorption temp (Ta) when being 25～45 DEG C, desorption temperature (Td) and the cold and hot generation temperature (Tcool) of steam meet following formula
(i) and (ii).
Ta+28℃≤Td≤100℃…(i)
Ta-25 DEG C of ＜ Tcool ＜ 25 DEG C ... (ii)
It follows that the adsorption heat pump of the present invention is illustrated based on Fig. 2.Fig. 2 is the suction being denoted as the present invention relates to
The flow chart of one example of the composition of the adsorption heat pump of the application examples of attached heat pump adsorbing material.
The adsorption heat pump of the present invention is the adsorption heat pump using above-mentioned adsorbing material, briefly as in figure 2 it is shown, be to be filled with suction
Enclosure material, possess: adsorber (1) and (2), repeat release heat of adsorption limit, limit and adsorbate is adsorbed in the behaviour of adsorbing material
Warm outside work and utilization is from the operation of desorbed of adsorbed materials adsorbate, simultaneously by by the adsorption operations generation of adsorbate
Heat transfer is to thermal medium；Vaporizer (4), the evaporation by adsorbate obtained cold and hot is discharged into outside, will produce simultaneously
The vapor recovery of adsorbate to adsorber (1) and (2)；With condenser (5), utilize outside cold and hot make adsorber (1) and (2)
The steam condensation of the adsorbate of middle desorbing, simultaneously by adsorbate supply vaporizer (4) of condensation and by by the condensation of adsorbate
And the warm obtained is discharged into outside.
It is filled with the adsorber (1) of adsorbing material and each entrance side of (2) and each outlet side respectively by adsorbate pipe arrangement
(30) it is connected with each other, adsorbate pipe arrangement (30) is provided with control valve (31)～(34).Should illustrate, in adsorbate pipe arrangement (30)
In, adsorbate is presented in the mixture of steam or liquid and steam.
Adsorber (1) in side connects thermal medium pipe arrangement (11), and the adsorber (2) at opposite side connects thermal medium
Pipe arrangement (21).Thermal medium pipe arrangement (11) is provided with switching valve (115) and (116), thermal medium pipe arrangement (21) is provided with switching
Valve (215) and (216).Further, thermal medium pipe arrangement (11) and (21) are each for becoming in heating adsorber (1) and (2)
The thermal medium of heating source of adsorbing material flow through, or flow through for becoming the thermal medium of the cooling source for cooling down adsorbing material
Mode constitute.As thermal medium, as long as the adsorbing material can being effectively heated or cooled in adsorber (1) and (2) just may be used
To use various media.
Adsorber (1) when desorption operations with by switching valve (115) and (116) opening and closing from entrance (113) importing example
Such as warm water, and the mode being discharged to export (114) is constituted.It addition, when adsorption operations, with by switching valve (115) and (116)
Opening and closing import from entrance (111) and such as cool down water, and the mode being discharged to export (112) is constituted.On the other hand, adsorber
(2) when desorption operations, import such as warm water with the opening and closing by switching valve (215) and (216) from entrance (213), and discharge
Mode to outlet (214) is constituted.It addition, when adsorption operations, with the opening and closing by switching valve (215) and (216) from entrance
(211) importing such as cools down water, and the mode being discharged to export (212) is constituted.
Should illustrate, although not shown, but in thermal medium pipe arrangement (11) and (21), in order to supply warm water, connect and have generation
The thermal source of warm water, the pump of circulation warm water, it addition, in order to supply cooling water, connect and have and can carry out the room of heat exchange with ambient atmos
Outer machine.As thermal source, it is possible to use the cogeneration plant such as gas engine, gas turbine, fuel cell etc..
Adsorbate pipe arrangement (30) at adsorber (1) and the entrance side of (2) connects vaporizer (4), at adsorber (1) and
(2) the adsorbate pipe arrangement (30) of outlet side connects condenser (5).That is, above-mentioned adsorber (1) and (2) are arranged in steaming side by side
Send out between device (4) and condenser (5), and be provided with for making by condenser (5) cold between condenser (5) and vaporizer (4)
The backflow pipe arrangement (3) of solidifying adsorbate Returning evaporimeter (4).Should illustrate, symbol (41) represents to be become from vaporizer (4) output
The cold water pipe arrangement of cold air, symbol (42) represents the cold water pipe arrangement of the outlet becoming cold water, at cold water pipe arrangement (41) and cold water pipe arrangement
(42) it is configured between carry out indoor set (300) and the pump of circulating water of heat exchange with the interior space (conditioned space)
(301).It addition, symbol (51) represents the entrance pipe arrangement of the cooling water inputted to condenser (5), symbol (52) represents cooling water
Outlet pipe arrangement.
Embodiment
Hereinafter, enumerate embodiment and comparative example further describes the present invention, but as long as less than the purport of the present invention,
The most not by any restriction of following example.
Should illustrate, in below example and comparative example, the test of steam adsorption-desorption repeatedly, water logging test and water
The isothermal mensuration of vapor sorption is carried out by the following method.
＜ steam adsorption-desorption repeatedly test ＞
Sample is held in the Dewar vessel maintaining 90 DEG C, respectively the saturated steam atmosphere of 5 DEG C and 90 DEG C
Saturated steam atmosphere exposes 90 seconds, repeats this operation.Now, it is exposed to during the saturated steam atmosphere of 90 DEG C be adsorbed in examination
The water of sample moves to be maintained in the tank of 5 DEG C the saturated steam atmosphere next part desorbing of 5 DEG C.From the m time absorption
To n-th desorbing, by the total amount (Qn of the water of the tank moving to 5 DEG C；M (g)) and the dry weight (W (g)) of sample, ask as follows
Go out average adsorption amount (Cn each time；m(g/g)).
[Cn；M]=[Qn；M]/(n-m+1)/W
By so obtain steam adsorption-desorption repeatedly test 1001 times～2000 times average adsorption amount with 1 time～
The average adsorption amount of 1000 times be used for Adsorption Dimension holdup.
＜ water logging test ＞
Make 0.5g sample be dispersed in 5g water, the slurry obtained is joined the stainless steel high-pressure equipped with fluororesin inner core
In still.After it is stood 24 hours at 100 DEG C, by filtering, sample is reclaimed, be dried 12 hours at 100 DEG C.
It is before the water vapor adsorption amount after the water logging test under the conditions of 0.3 is tested relative to water logging by relative humidity (P/Ps)
The ratio (percentage rate) of water vapor adsorption amount as Adsorption Dimension holdup.
＜ water vapor adsorption isotherms ＞
By sample after 120 DEG C of vacuum exhausts 5 hours, utilize water vapor adsorption amount determining device (BELSORP18:BEL
Japan Co., Ltd.), the water vapor adsorption isotherms at measuring 25 DEG C by following condition.
Air temperature chamber temperature: 50 DEG C
Adsorption temp: 25 DEG C
Initial stage imports pressure: 3.0torr
Importing pressure set-point number: 0
Saturated vapour pressure: 23.755torr
Equilibration time: 500 seconds
[embodiment 1]
Utilize the method synthesizing silicoaluminophosphamolecular zeolite disclosed in the embodiment 2 of Japanese Unexamined Patent Publication 2003-183020 publication.
The XRD of the zeolite obtained by mensuration, result is CHA structure (skeletal density=14.6T/).It addition, utilize ICP to divide
Analysis has carried out the composition analysis of zeolite, and result is relative to respectively the becoming of total of silicon atom, aluminum atom and the phosphorus atoms of framing structure
Point composition (mol ratio) be silicon atom be 0.092, aluminum atom is 0.50, and phosphorus atoms is 0.40.
It follows that by this zeolite 2kg, 78g copper acetate (II) monohydrate (Kishida Chemical company system) and
3000g pure water stirs and makes water slurry.This water slurry disc rotary type spray dryer of 1200 φ is dried.Dried strip
Part is inlet temperature 200 DEG C, outlet temperature 120 DEG C.The rotating speed of disk is 18000rpm.Slurry is supplied with the speed of 1.5kg/ hour
Material, reclaimed 577g with 1 hour and is dried powder body.Time needed for being dried is less than 10 seconds.By this dry powder body under air circulates
Calcine 2 hours at 800 DEG C, obtain sample 1.
By icp analysis, obtaining the Cu loading relative to zeolite of sample 1, result is 1.5 weight %.
Water vapor adsorption isotherms measurement result before and after the water logging of sample 1 being tested is shown in Fig. 1.It addition, by steam
Adsorption Dimension holdup after adsorption-desorption test and after water logging test is shown in table 1 repeatedly.
[embodiment 2]
Synthetic zeolite similarly to Example 1.
It follows that by copper acetate (II) monohydrate of zeolite 2kg, 117g (Kishida Chemical company system) and
3000g pure water stirs and makes water slurry.Similarly to Example 1 this water slurry is spray-dried, calcining, obtains sample
2。
By icp analysis, obtaining the Cu loading relative to zeolite of sample 2, result is 1.0 weight %.
Water vapor adsorption isotherms measurement result before and after the water logging of sample 2 being tested is shown in Fig. 1.It addition, by steam
Adsorption Dimension holdup after adsorption-desorption test and after water logging test is shown in table 1 repeatedly.
[embodiment 3]
The phosphoric acid 8.1g of 85 weight % and pseudobochmite it is slowly added to (containing the water of 25 weight %, Condea in water 10g
Company's system) 5.4g, stirs 1 hour.Add pyrolytic silicon dioxide (AEROSIL200, NIPPON AEROSIL company system) 0.6g
With water 10g, stir 1 hour.Then, it is slowly added to morpholine 3.4g, triethylamine 4.0g, stirs 1 hour.As A liquid.
With A liquid differently by Cu (CH3COO)2·H2O (Kishida Chemical company system) 1.0g is dissolved in water 13.4g
After, add tetren (Kishida Chemical company system) 1.0g and mix, preparing B liquid.
B liquid is slowly added in A liquid.It is stirred for 1 hour, obtains the aqueous gel with consisting of.
＜ aqueous gel composition (mol ratio) ＞
SiO2: 0.25
Al2O3: 1
P2O5: 0.875
CuO:0.125
Tetren: 0.125
Morpholine: 1
Triethylamine: 1
Water: 50
The aqueous gel so obtained is joined in the stainless steel autoclave of the 100ml equipped with fluororesin inner core, limit
React 36 hours at 190 DEG C with 15rpm stirring limit.Cool down after Hydrothermal Synthesis, remove supernatant by decant, reclaim precipitation
Thing.Leach after cleaning precipitate 3 times with water, be dried at 100 DEG C.Then 550 DEG C, calcine under air draught, removing has
After machine thing, then by 800 DEG C, the steam of 10 volume % 5 hours under the air atmosphere of space velocity SV=3000/ hour,
Carry out hydrothermal treatment consists, obtain sample 3.
Measuring the XRD of the zeolite so obtained, result is CHA structure (skeletal density=14.6T/).Utilize
EDX analyzes and obtains the Cu loading relative to zeolite, and result is 6.2 weight %.It addition, utilize EDX to carry out the group composition of zeolite
Analysis, result is relative to the composition (mol ratio) of each composition of the total of the silicon atom of framing structure, aluminum atom and phosphorus atoms
Be silicon atom be 0.10, aluminum atom is 0.49, and phosphorus atoms is 0.41.
Water vapor adsorption isotherms measurement result before and after the water logging long duration test of sample 3 is shown in Fig. 1.It addition, by water
Adsorption Dimension holdup after the test of steam adsorption-desorption repeatedly and after water logging test is shown in table 1.
[comparative example 1]
The method disclosed in the embodiment 2 of Japanese Unexamined Patent Publication 2003-183020 publication is utilized to synthesize similarly to Example 1
Silicoaluminophosphate zeolite, obtains sample 4.
Water vapor adsorption isotherms measurement result before and after the water logging long duration test of sample 4 is shown in Fig. 1.It addition, by water
Adsorption Dimension holdup after the test of steam adsorption-desorption repeatedly and after water logging test is shown in table 1.
[table 1]
From result above, according to the adsorption heat pump of present invention water vapor adsorption material, it is possible to realize with 100 DEG C with
Under the adsorption heat pump that is driven of the thermal source of lower temperature, it addition, the resistance to water logging of this adsorbing material is the best.
Use specific mode that the present invention has been described in detail, but those skilled in the art understand without departing from this
Various deformation can be carried out in the case of bright intention and scope.
Should illustrate, the application is based on Japanese patent application (Japanese Patent Application 2011-filed in 26 days October in 2011
235052), and by entire contents it is incorporated herein.
Claims (11)
1. an adsorption heat pump water vapor adsorption material, it is characterised in that it is by by former containing silicon atom raw material, aluminum atom
The aqueous gel of material, phosphorus atoms raw material, copper raw material and polyamines carries out Hydrothermal Synthesis and makes, and it is the use of in framing structure
At least contain silicon atom, aluminum atom and phosphorus atoms and skeletal density isAbove,
The water vapor adsorption material of following zeolite, and containing relative to the copper that the weight of zeolite is 0.1～15 weight %, this polyamines is
The polyamine compounds represented by following formula,
Formula H2N-(CnH2nNH)x-H
In formula, n is the integer of 2～6, and x is the integer of 1～6.
Adsorption heat pump water vapor adsorption material the most according to claim 1, it is characterised in that the IZA rule of described zeolite
Fixed is zeolite structured for CHA.
Adsorption heat pump water vapor adsorption material the most according to claim 1 and 2, it is characterised in that relative to described boiling
The content of the described copper of the weight of stone is 0.1～10 weight %.
Adsorption heat pump water vapor adsorption material the most according to claim 1 and 2, it is characterised in that at relative vapour pressure
When being that relative vapour pressure changes 0.15 in the scope of more than 0.05, less than 0.30, the adsorbance of water is changed to 0.15g-H2O/g with
On.
Adsorption heat pump water vapor adsorption material the most according to claim 3, it is characterised in that be at relative vapour pressure
When in the scope of more than 0.05, less than 0.30, relative vapour pressure changes 0.15, the adsorbance of water is changed to 0.15g-H2O/g with
On.
6. the manufacture method of water vapor adsorption material of the adsorption heat pump according to any one of claims 1 to 3, its feature exists
In, the aqueous gel containing silicon atom raw material, aluminum atomic raw material, phosphorus atoms raw material, copper raw material and polyamines carry out Hydrothermal Synthesis.
7. an adsorption heat pump, it is characterised in that be the adsorption heat pump using water vapor adsorption material, this water vapor adsorption
Materials'use zeolite, this zeolite at least contains silicon atom, aluminum atom and phosphorus atoms in framing structure and skeletal density isAbove,Hereinafter, described water vapor adsorption material has 11 race's metals, and these are 11 years old
The pore of the zeolite that race's metal is supported outside described framing structure.
Adsorption heat pump the most according to claim 7, it is characterised in that the zeolite structured of IZA regulation of described zeolite is
CHA。
9. according to the adsorption heat pump described in claim 7 or 8, it is characterised in that relative vapour pressure be more than 0.05,0.30 with
Under scope in relative vapour pressure when changing 0.15, the adsorbance of water is changed to 0.15g-H2More than O/g.
10. according to the adsorption heat pump described in claim 7 or 8, it is characterised in that containing relative to the weight of described zeolite being
The copper of 0.1～1.5 weight %.
11. adsorption heat pumps according to claim 9, it is characterised in that containing relative to the weight of described zeolite be 0.1～
The copper of 1.5 weight %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-235052 | 2011-10-26 | ||
| JP2011235052 | 2011-10-26 | ||
| PCT/JP2012/075333 WO2013061728A1 (en) | 2011-10-26 | 2012-10-01 | Steam-adsorbing material for adsorption heat pump, method for manufacturing same, and adsorption heat pump using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103889551A CN103889551A (en) | 2014-06-25 |
| CN103889551B true CN103889551B (en) | 2016-11-30 |
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ID=
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| JP2003114067A (en) * | 2001-10-05 | 2003-04-18 | Mitsubishi Chemicals Corp | Adsorption heat pump |
| CN1495398A (en) * | 2002-08-15 | 2004-05-12 | 三菱化学株式会社 | Adsorbent, heat storage system containing the same, iron-aluminium phosphate and its producing method |
| CN1809508A (en) * | 2003-06-20 | 2006-07-26 | 三菱化学株式会社 | Zeolite, method for production thereof, adsorbent comprising said zeolite, heat utilization system, adsorption heat pump, heating and cooling storage system and humidity controlling air-conditioning a |
| CN1880882A (en) * | 2001-02-21 | 2006-12-20 | 三菱化学株式会社 | Adsorption heat pump and use of adsorbent as adsorbent for adsoprtion heat pump |
| CN101124161A (en) * | 2004-11-12 | 2008-02-13 | 苏德-化学股份公司 | Method for the synthesis of zeolite beta with diethylentriamine |
| WO2010084930A1 (en) * | 2009-01-22 | 2010-07-29 | 三菱化学株式会社 | Catalyst for removing nitrogen oxides and method for producing same |
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