CN102491362A - Method for preparing cation exchange content W type zeolite molecular sieve - Google Patents
Method for preparing cation exchange content W type zeolite molecular sieve Download PDFInfo
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- CN102491362A CN102491362A CN2011103837103A CN201110383710A CN102491362A CN 102491362 A CN102491362 A CN 102491362A CN 2011103837103 A CN2011103837103 A CN 2011103837103A CN 201110383710 A CN201110383710 A CN 201110383710A CN 102491362 A CN102491362 A CN 102491362A
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- molecular sieve
- type zeolite
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Abstract
The invention provides a method for preparing a cation exchange content W type zeolite molecular sieve, comprising main steps of: A) contacting the W type zeolite molecular sieve containing initial cations in Ci form with a water-soluble ammonium compound containing ammonium ions, wherein (NH4)2O/A12O3 is not less than 0.8 in the obtained W type zeolite molecular sieve containing ammonium ions; B) contacting the W type zeolite molecular sieve containing ammonium ions obtained in A with a solution containing final cation Cf, replacing the ammonium ions with at least one kind of cations, and removing volatile ammonia from a reaction zone, wherein CfO/Al2O3 is not less than 0.7 and (NH4)2/Al2O3 is not more than 0.1 in the prepared product; and C) washing the product obtained in B with a solution containing Cf, drying and finally obtaining the cation exchange content W type zeolite molecular sieve.
Description
Technical field
The present invention relates to a kind of polynary cationic exchange and produce the method for high-cation exchange capacity W type molecular sieve; More particularly; Relate to through W type molecular sieve is at first formed the w-type zeolite molecular sieve that contains ammonium form with ammonium ion exchange; To contain the w-type zeolite molecular sieve and the target cationic source of ammonium form then, under the condition of evicting ammonia from the zone of action from, contact, produce the method for high-cation exchange capacity W type molecular sieve.
Background technology
W-type zeolite molecular sieve SiO
2/ Al
2O
3Ratio be 3.2-4.8, its positively charged ion is generally potassium ion, structural formula is generally 1.02K
2O:Al
2O
3: 3.65SiO
2: 5.1H
2O.The w-type zeolite molecular sieve belongs to phillipsite family, has a series of tetra-atomic rings, the long band of the bending that its limit forms, and the main channel is an octatomic ring, free aperture is 4.8A to the maximum.As stated, the positively charged ion of w-type zeolite is generally potassium ion, has useful function although contain the potassium w-type zeolite in many-sides such as industry and environmental protection fields, preferably they is carried out IX, with its absorption property of further enhancing.Conventional exchange step can be used for preparing many single cationic exchange zeolites economically; Yet; The conventional in all cases potassium w-type zeolite that contains exchanges a large amount of excess metal positively charged ion of needs; With the moderate of carrying out initial cationic or highly exchange, these salt itself are expensive, and it is much more expensive than the zeolite of the conventional sorbent material grade of production that this just causes producing these special ion exchange form.For the cost that reduces final form zeolite and prevent that these ions are discharged in the environment; Must carry out very big effort; From residual exchange solution and washings, reclaim excessive interested ion; Because high-cation exchange capacity W type molecular sieve has very big actual utility value as the high-efficiency adsorbent in environmental protection field, so this problem is the obvious interested problem in environmental protection field.
Usually, contain initial cationic C
iThe w-type zeolite molecular sieve of form is difficult to and final positively charged ion C
fPrimary ions exchanging form through routine makes and contains C
fThe w-type zeolite molecular sieve of form.
Summary of the invention
The object of the present invention is to provide a kind of polynary cationic exchange to produce the method for high-cation exchange capacity W type molecular sieve, to overcome the defective that exists in the known technology.
Be the realization above-mentioned purpose, the method for preparing cation exchange capacity w-type zeolite molecular sieve provided by the invention, key step is:
A) will contain initial cationic C
iThe w-type zeolite molecular sieve of form contacts with the water-soluble ammonium compound that contains ammonium ion, (NH in the w-type zeolite molecular sieve that contains ammonium ion that obtains
4)
2O/Al
2O
3>=0.8;
B) the w-type zeolite molecular sieve that contains ammonium ion that steps A is obtained with contain final positively charged ion C
fSolution contact, with at least a said positively charged ion substituted ammonium ion, and remove volatile ammonia, C in the product that makes from reaction zone
fO/Al
2O
3>=0.7, (NH
4)
2O/Al
2O
3≤0.1;
C) product that step B is obtained is with containing C
fSolution washing, drying finally obtains cation exchange capacity w-type zeolite molecular sieve.
The method for preparing cation exchange capacity w-type zeolite molecular sieve provided by the invention can also be reacted with solid-state heating with final positively charged ion after preparing the w-type zeolite molecular sieve that contains ammonium ion, makes volatile ammonia from system evaporation or distillation.
The w-type zeolite molecular sieve drying that contains ammonium ion that specifically steps A is obtained with contain final positively charged ion C
fPowder mixing post-heating, make volatile ammonia evaporation, C in the product that makes
fO/Al
2O
3>=0.7, (NH
4)
2O/Al
2O
3≤0.1, then with containing C
fSolution washing, drying finally obtains cation exchange capacity w-type zeolite molecular sieve.
Described preparation method, wherein, initial cationic C
iWith final positively charged ion C
fSelectivity coefficient Sf
i f≤0.5.
Described preparation method, wherein, the temperature of reaction of steps A is 0-50 ℃, reaction soln pH is less than 7.
Described preparation method, wherein, the pH value of solution of step B >=7 (preferred pH is greater than 10), temperature is 0-100 ℃.
Described preparation method wherein, washes with purge gas between the reaction period of step B.
Described preparation method, wherein, the water-soluble ammonium compound in the steps A comprises: ammonium sulfate, ammonium chloride, an ammonium nitrate, ammonium acetate or mixture.
Described preparation method, wherein, the final positively charged ion of step B is calcium, sodium ion, mg ion or lithium ion (preferably by calcium ion, recommending calcium ion source to be preferably calcium hydroxide).
The method for preparing high-cation exchange capacity W type molecular sieve provided by the invention need not used a large amount of excessive cationic expensive salt, need not use expensive and the strong positively charged ion recovery scheme of motility simultaneously.
Embodiment
The present invention is a kind of method of utilizing the preparation of polynary cationic exchange to have high-cation exchange capacity W type molecular sieve; At first with the ammonium ion exchange in w-type zeolite molecular sieve and the ammonium thing; Replace the positively charged ion in the w-type zeolite molecular sieve with ammonium ion thus; The w-type zeolite that to cross with ammonium ion exchange then with contain final cationic solution and contact; The pH that keeps solution simultaneously is 9-12, and final acquisition contains final cationic w-type zeolite molecular sieve with high-cation exchange capacity, and wherein the target positively charged ion accounts for more than 70% of w-type zeolite positively charged ion total amount.
Technical scheme of the present invention is specific as follows:
1) will contain initial cationic C
iThe w-type zeolite molecular sieve of form contacts with the water-soluble ammonium compound that contains ammonium ion.Contain initial cationic C
iThe w-type zeolite molecular sieve of form and contain reaction between the water-soluble ammonium compound of ammonium ion and be preferably under about 0-50 ℃ and carry out.This reaction is preferably in less than carrying out under 7 the pH.Water-soluble ammonium compound comprises: the mixture of ammonium sulfate, ammonium chloride, an ammonium nitrate, ammonium acetate or these ammonium compounds.Ammonium concentration is 0.5mol/L-2.5mol/L, and the reaction times is controlled at 2-4h, makes final (NH
4)
2O/Al
2O
3>=0.8; Generally speaking, C
iBe potassium ion.Reaction realizes solid-liquid separation through the centrifugal mode with mixed solution after finishing, and the solid that separation is obtained repeats above-mentioned experiment 3 times, promptly carries out ammonium ion exchange 3 times.Again solid is washed 3 times with the water-soluble ammonium compound that contains ammonium ion at last, centrifugal back decanted solution, the solid sample that obtains is the w-type zeolite molecular sieve that contains ammonium ion.
2) the w-type zeolite molecular sieve that contains ammonium ion that step 1 is obtained with contain final positively charged ion C
fSolution contact, with at least a final positively charged ion substituted ammonium ion, and remove reaction product ammonia from reaction zone.C wherein
iAnd C
fSelectivity coefficient Sf
i f≤0.5, final positively charged ion C
fConcentration is 0.5mol/L-2.5mol/L; PH value of solution>=7 more preferably are higher than 10 times at pH and carry out.In 0-100 ℃ of water-bearing media, react, reaction times 10-24h makes final C
fO/Al
2O
3>=0.7, (NH
4)
2O/Al
2O
3≤0.1; This reaction during reaction with the purge gas flushing, is guaranteed to remove volatile reaction product ammonia from reaction zone.Generally speaking, the positively charged ion of substituted ammonium ion is calcium, sodium ion, mg ion or lithium ion.Aspect more preferably, ammonium ion replaces with calcium ion.Aspect more preferably, calcium ion source is preferably calcium hydroxide.
By substituted w-type zeolite molecular sieve of ammonium ion and final positively charged ion C
fReaction also can carry out with solid-state, for example carry out with dryness basically.Aspect this, this reaction is preferably under about 100-400 ℃ to be carried out.Wherein at least a reaction product (as by the substituted w-type zeolite molecular sieve of ammonium ion) is a gaseous state or volatile, from system evaporation or distillation.
3) the W type molecular sieve that step 2 is obtained is with containing C
fConcentration is the solution washing of 0.02mol/L, and drying finally obtains high-cation exchange capacity w-type zeolite molecular sieve.
The present invention's preparation has high-cation exchange capacity W type molecular sieve, has overcome the problem of present implementation method.Compare with other method of producing high-cation exchange capacity W type molecular sieve, present method need not used a large amount of excessive expensive exchange cation salt, need not use expensive positively charged ion recovery scheme simultaneously.Ion exchange method of the present invention is carried out under the condition of removing a kind of reaction product from reaction zone.IX can be carried out in liquid phase, and wherein a kind of reaction product is a gaseous state or volatile, can blow out reaction zone; Perhaps IX can be solid state reaction, wherein also is that at least a reaction product is a gaseous state or volatile, from system evaporation or distillation.
Embodiment 1
1) 30g is contained the w-type zeolite molecular sieve k of potassium ion
2W and 2L concentration are the ammoniumsulphate soln reaction of 2mol/L.PH value of solution is 6.5, is reflected under the room temperature (25 ℃) to carry out, and the reaction times is 2h, realizes solid-liquid separation through the centrifugal mode then.The solid that separation is obtained repeats above-mentioned experiment 3 times, promptly carries out ammonium ion exchange 3 times.Use 2L concentration to be the ammoniumsulphate soln of 0.01mol/L washing 3 times solid at last, 1. centrifugal back decanted solution obtains sample, and 1. sample is carried out proximate analysis.
2) sample that 10g step 1 is obtained 1. (the w-type zeolite molecular sieve that contains ammonium ion) is the Ca (OH) of 2mol/L with 1L concentration
2Solution reaction is blown into nitrogen to prevent CO in solution in the reaction process
2Get in the solution and Ca (OH)
2React, and remove reaction product ammonia from reaction zone.60 ℃ of temperature of reaction, reaction times 18h, and pH of mixed remains at 9-12 in the 18h of reaction.After reaction is accomplished, with acid pH of mixed is transferred to about 7.0, then that mixed solution is centrifugal, decanted solution obtains solid sample again.
3) solid sample that step 2 is obtained uses the Ca (OH) of 1L concentration as 0.02mol/L
2Solution washing, centrifugal, it is dry again to obtain solid behind the decanted solution, finally obtains the w-type zeolite molecular sieve 2., and 2. sample is carried out proximate analysis.
4) the 2. also residual lower ammonium ion of w-type zeolite molecular sieve that obtains of step 3 adopts 500ml to contain 2mol/L CaCl
2/ NaCl (CaCl
2Be 1.5mol/L, NaCl is 0.5mol/L) 2. react with the w-type zeolite molecular sieve, 60 ℃ of temperature of reaction, reaction times 24h, and pH of mixed remains at 9-12 in the 24h of reaction.After reaction is accomplished, with acid pH of mixed is transferred to about 7.0, then that mixed solution is centrifugal, decanted solution obtains solid sample again.
(5) solid sample that step (4) is obtained uses the CaCl of 500ml concentration as 0.02mol/L
2Solution washing 33 times, centrifugal, it is dry again to obtain solid behind the decanted solution, finally obtains the w-type zeolite molecular sieve 3., and 3. sample is carried out proximate analysis.The chemical composition analysis result that 3. 1., 2. W type molecular sieve reach sees table 1.
Table 1:W type molecular sieve chemical composition analysis
Embodiment 2:
1) will contain initial cationic C
iThe w-type zeolite molecular sieve of form contacts with the water-soluble ammonium compound that contains ammonium ion.Contain initial cationic C
iThe w-type zeolite molecular sieve of form and contain reaction between the water-soluble ammonium compound of ammonium ion and be preferably under about 0-50 ℃ and carry out.This reaction is preferably in less than carrying out under 7 the pH.Water-soluble ammonium compound comprises: the mixture of ammonium sulfate, ammonium chloride, an ammonium nitrate, ammonium acetate or these ammonium compounds.Ammonium concentration is 0.005mol/L-0.1mol/L, and the reaction times is controlled at 2-4h, makes final (NH
4)
2O/Al
2O
3>=0.8; Generally speaking, C
iBe potassium ion.
2) by substituted w-type zeolite molecular sieve of ammonium ion and final positively charged ion C
fReaction also can carry out with solid-state, for example carry out with dryness basically.This reaction is preferably under about 100-400 ℃ to be carried out.Wherein at least a reaction product is a gaseous state or volatile, from system evaporation or distillation.
3) the W type molecular sieve that step 2 is obtained is with containing final positively charged ion C
fConcentration is the solution washing of 0.002mol/L, and drying finally obtains high-cation exchange capacity w-type zeolite molecular sieve.
Claims (8)
1. method for preparing cation exchange capacity w-type zeolite molecular sieve, key step is:
A) will contain initial cationic C
iThe w-type zeolite molecular sieve of form contacts with the water-soluble ammonium compound that contains ammonium ion, (NH in the w-type zeolite molecular sieve that contains ammonium ion that obtains
4)
2O/Al
2O
3>=0.8;
B) the w-type zeolite molecular sieve that contains ammonium ion that steps A is obtained with contain final positively charged ion C
fSolution contact, with at least a said positively charged ion substituted ammonium ion, and remove volatile ammonia, C in the product that makes from reaction zone
fO/Al
2O
3>=0.7, (NH
4)
2O/Al
2O
3≤0.1;
C) product that step B is obtained is with containing C
fSolution washing, drying finally obtains cation exchange capacity w-type zeolite molecular sieve.
2. method for preparing cation exchange capacity w-type zeolite molecular sieve, key step is:
A) will contain initial cationic C
iThe w-type zeolite molecular sieve of form contacts with the water-soluble ammonium compound that contains ammonium ion, (NH in the w-type zeolite molecular sieve that contains ammonium ion that obtains
4)
2O/Al
2O
3>=0.8;
B) the w-type zeolite molecular sieve drying that contains ammonium ion that steps A is obtained with contain final positively charged ion C
fPowder mixing post-heating, make volatile ammonia evaporation, C in the product that makes
fO/Al
2O
3>=0.7, (NH
4)
2O/Al
2O
3≤0.1;
C) product that step B is obtained is with containing C
fSolution washing, drying finally obtains cation exchange capacity w-type zeolite molecular sieve.
3. preparation method according to claim 1 and 2, wherein, initial cationic C
iWith final positively charged ion C
fSelectivity coefficient Sf
i f≤0.5.
4. preparation method according to claim 1 and 2, wherein, the temperature of reaction of steps A is 0-50 ℃, reaction soln pH is less than 7.
5. preparation method according to claim 1, wherein, the pH value of solution of step B >=7, temperature is 0-100 ℃.
6. preparation method according to claim 1 wherein, washes with purge gas between the reaction period of step B.
7. preparation method according to claim 1 and 2, wherein, the water-soluble ammonium compound in the steps A comprises: ammonium sulfate, ammonium chloride, an ammonium nitrate, ammonium acetate or mixture.
8. preparation method according to claim 1 and 2, wherein, the final positively charged ion of step B is calcium, sodium ion, mg ion or lithium ion.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196976A (en) * | 1996-12-27 | 1998-10-28 | 美国Boc氧气集团有限公司 | Method of manufacture of molecular sieves |
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2011
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196976A (en) * | 1996-12-27 | 1998-10-28 | 美国Boc氧气集团有限公司 | Method of manufacture of molecular sieves |
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Application publication date: 20120613 |