CN1225335A - Method for synthesizing zeolite molecular sieve using minerals as raw material - Google Patents
Method for synthesizing zeolite molecular sieve using minerals as raw material Download PDFInfo
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- CN1225335A CN1225335A CN 98117045 CN98117045A CN1225335A CN 1225335 A CN1225335 A CN 1225335A CN 98117045 CN98117045 CN 98117045 CN 98117045 A CN98117045 A CN 98117045A CN 1225335 A CN1225335 A CN 1225335A
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Abstract
The present invention relates to the synthesis method of zeolite molecular sieve. It uses minerals as raw material, after mixed with NaOH slution, proceed pre-reaction, then add aluminium liquid, guide agent, etc. after crystallization, type A and type X molecular sieves are produced. The pre-reaction is carried out at 100 deg.C to 240 deg.C for 18-40 hours, and the crystallization is carried out at 90 deg.C to 100 deg.C for 4-6 hours. The advantages include easily available raw materials, low production cost, etc.
Description
The invention belongs to domain of inorganic chemistry, particularly synthesis method of zeolite molecular sieve.
In washing composition, general with " tripoly phosphate sodium STPP " as inorganic assistant agent, it can softening of water, has good dirt-carrying soil removability.But it contains phosphorus, and wash water can cause water pollution, destroys the eubiosis, and zeolite is the desirable surrogate of " tripoly phosphate sodium STPP " by generally acknowledging.
The zeolite production method the most close with the present invention is " research of synthetic X type zeolite from natural mordenite zeolite ", and this method is by the synthetic X type molecular sieve of batch mixing, pre-treatment, crystallization and last handling process.Batch mixing is that natural mordenite zeolite is made raw material, with Na
2CO
3Or/and the NaOH solid mixes.Pre-treatment is that aforesaid batch mixing is carried out roasting under 900 ℃ of conditions.Crystallization is to add NaOH or NaOH-NaCl solution after roasting, and its composition is dropped within the synthetic scope of X type zeolite, aging 48 hours, and crystallization 10 hours under 90 ℃～100 ℃ hydrothermal condition again.Productive rate is 55～60%.This method is owing to be that solid material is baking mixed, reaction needed high temperature, and not only required time is long, and production efficiency is low, also a large amount of consumes energy; Also weathering process need be arranged in the crystallization process, make the crystallization overlong time; The productive rate of this method is also lower.
The objective of the invention is to improve synthesis method of zeolite molecular sieve, make reaction conditions gentle more, reduce energy consumption, reduce preparation time, enhance productivity, and improve the productive rate and the ion-exchange capacity of zeolite.
The present invention utilizes minerals as raw material.Said raw mineral materials mainly refers to the silicate starting materials that natures such as natural zeolite powder, kaolin exist, and its main chemical compositions has SiO
2, Na
2O, K
2O, Al
2O
3, Fe
2O
3Deng, SiO wherein
2Account for 40～90wt% of each composition total amount.Because the present invention makes raw material with the silicate that nature exists, thereby raw material sources are extensive and cheap.
Synthesis method of zeolite molecular sieve with minerals as raw material of the present invention comprises processes such as batch mixing, pre-treatment, crystallization, aftertreatment, compared with the prior art, in the batch mixing is not and solid NaOH or Na
2CO
3Mix, but mix with NaOH solution; Pre-treatment is not to adopt high-temperature roasting, but in NaOH solution, reaction at a lower temperature; Crystallization is to add aluminium liquid and directed agents, without ageing process.Concrete building-up process is that said batch mixing is with raw mineral materials and NaOH solution uniform mixing; Said pre-treatment be with batch mixing under 100 ℃～240 ℃ conditions, reacted 18～40 hours; Said crystallization is with pretreated raw material cooling, adds aluminium liquid, directed agents again, makes its composition drop on the synthetic scope of A type or X type zeolite, and crystallization is 4～6 hours under 90 ℃～100 ℃ temperature.Aftertreatment is that the product behind the crystallization is cooled off, filters, washs, and at room temperature dries at last, makes A type or X type zeolite molecular sieve.
Aforesaid aluminium liquid is by NaOH, NaAlO
2And H
2O is formulated, such as, with 0.4 kilogram of NaOH, 1.0 kilograms of NaAlO
2, add about 5 liters of H
2O can make about 5 liters aluminium liquid.Directed agents is the silico-aluminate solution that contains sodium.Can prepare with following raw material and mol ratio: (17～19) NaOH: Al
2O
3: (17～19) SiO
2: (340～380) H
2O is 25 ℃～45 ℃ following ageings about 12 hours.
Aforesaid adding aluminium liquid, directed agents make its composition drop on the synthetic scope of A type or X type zeolite, and the mol ratio of its composition can roughly descended about column data:
Composition: Na
2O Al
2O
3SiO
2H
2O
A type 2.6 1.0 1.9 85
X type 2.3 1.0 3.0 117
In the process of crystallization, drop on the synthetic scope of A type zeolite for making its composition, except that adding aluminium liquid, directed agents, can add NaOH solution, make alkalescence stronger, also can when batch mixing, just strengthen the concentration of NaOH; The amount of the aluminium liquid that adds comparatively speaking more greatly so that the mol ratio of Si, Al is roughly suitable.And, then should correspondingly reduce NaOH concentration for making X type zeolite molecular sieve, and suitably reduce the consumption of aluminium liquid, make the mol ratio of Si and Al be about 1.5.
Embodiment:
In the following example, the aluminium liquid and the directed agents of use are identical, and its composition is aforesaid configuration proportion.Use different raw mineral materials samples among each embodiment, the composition of each raw mineral materials sample is as follows:
Raw mineral materials composition Na
2O K
2O SiO
2Al
2O
3Fe
2O
3
Sample A (wt%) 1.16 0.95 69.56 12.63 2.54
Sample B (wt%) 0.66 0.99 70.94 23.50 3.24
Sample C (wt%) 0.29 0.72 78.46 5.20 2.51
Integrating paradigm (wt%) 0.25～1.20 0.7～1.0 65～80 5.0～24 2.5～3.5
Embodiment 1 makes the synthetic A type molecular sieve of raw material with mineral samplers A
Batch mixing: 5 gram mineral samplers A+2.3 gram NaOH+20 milliliter H
2O mixes.
Pre-treatment: with batch mixing under 100 ℃ of conditions, pre-reaction 25～30 hours.
Crystallization: cooling adds 1.6 gram NaOH, 53 milliliters of H
2O adds 56.5 ml aluminium liquid and 20 milliliters of directed agents, stirs, and under 97 ℃ of conditions, reacts 4～6 hours.
Aftertreatment: take out, cooling is filtered product, wash, and at room temperature dries.
Product is carried out X-ray powder diffraction, learn to be purer A type molecular sieve.Product and former mineral samplers are carried out the ion-exchange performance test, and the ion-exchange capacity of products obtained therefrom is 266mmolCa
2+/ 100g product, and former mineral samplers does not have ion-exchange capacity.
Embodiment 2 makes the synthetic A type molecular sieve of raw material with mineral samplers B
The synthetic process is with embodiment 1.The dosage and the reaction conditions that add aluminium liquid, directed agents when batch mixing composition proportion, crystallization are as follows:
5 gram mineral samplers B+2.3 gram NaOH+20 milliliter H
2O, under 100 ℃ of conditions, pre-reaction 25～30 hours.
Add 2 gram NaOH, 53.8 milliliters of H
2O adds 51.1 ml aluminium liquid and 20 milliliters of directed agents, under 96 ℃ of conditions, and crystallization 4～6 hours.
Product carries out X-ray powder diffraction, learns to be purer A type molecular sieve.The ion-exchange capacity of product is 262mmol Ca
2+/ 100g product, former mineral samplers does not have ion-exchange capacity.
Embodiment 3 makes the synthetic A type molecular sieve of raw material with mineral samplers C
The synthetic process is with embodiment 1.Proportioning raw materials and reaction conditions are as follows:
5 gram mineral samplers C+20 gram NaOH+50 milliliter H
2O, under 100 ℃ of conditions, pre-reaction 18～24 hours.
Add 500 milliliters of H
2O, 65 ml aluminium liquid and 20 milliliters of directed agents, under 100 ℃ of conditions, crystallization 4～5 hours.
Because added NaOH amount is bigger in batch mixing, no longer adds NaOH in the crystallization process.In entire synthesis process, added H
2The O amount is bigger, makes reaction conditions gentle more.
After testing, learn that product is an A type molecular sieve, ion-exchange capacity is 268mmol Ca
2+/ 100g product, former mineral samplers does not have ion-exchange capacity.
Embodiment 4 makes the synthetic X type molecular sieve of raw material with mineral samplers A
The synthetic process is with embodiment 1.Proportioning raw materials and reaction conditions are as follows:
5 gram mineral samplers A+2.3 gram NaOH+20 milliliter H
2O, under 240 ℃ of conditions, pre-reaction 36～39 hours.
Add 30 milliliters of H
2O, 7.8 ml aluminium liquid and 20 milliliters of directed agents, under 100 ℃ of conditions, crystallization 5～6 hours.Crystallization process does not add NaOH, is for weakening alkalescence, making composition drop on X type zeolite molecular sieve synthetic scope.
X-ray powder diffraction learns that product is purer X type molecular sieve.Ion-exchange capacity is 105mmol Ca
2+/ 100g product.
Embodiment 5 makes the synthetic X type molecular sieve of raw material with mineral samplers B
The synthetic process is with embodiment 1.Proportioning raw materials and reaction conditions are as follows:
5 gram mineral samplers B+2.3 gram NaOH+20 milliliter H
2O, under 240 ℃ of conditions, pre-reaction 39 hours.
Add 33 milliliters of H
2O, 15 ml aluminium liquid and 20 milliliters of directed agents, under 100 ℃ of conditions, crystallization 5～6 hours.This process does not equally add NaOH with embodiment 4.
Product is purer X type zeolite.Ion-exchange capacity is 114mmol Ca
2+/ 100g product.Embodiment 6 makes the synthetic X type molecular sieve synthetic process of raw material with embodiment 1 with mineral samplers C.Proportioning raw materials and reaction conditions are as follows:
5 gram mineral samplers C+2.1 gram NaOH+53 milliliter H
2O, under 100 ℃ of conditions, pre-reaction 24 hours.
Add 15 ml aluminium liquid and 20 milliliters of directed agents, under 100 ℃ of conditions, crystallization 5～6 hours.This process does not equally add NaOH with embodiment 4.Product is purer X type zeolite.Ion-exchange capacity is 117mmol Ca
2+/ 100g product.
Synthesis method of zeolite molecular sieve with minerals as raw material of the present invention is without NaOH or Na
2CO
3Solid and raw mineral materials are baking mixed, only under 100 ℃～240 ℃ conditions, react pre-treatment 18～40 hours, carry out the synthetic finished product of crystallization with directed agents, aluminium liquid again, greatly reduce reaction conditions, make reaction conditions gentle more, thereby also reduced the consumption of the energy.Owing to added directed agents in the crystallization process, do not have digestion time, thereby shortened crystallization time, improved production efficiency, because raw mineral materials derives from nature and extensively exists, reduced the cost of raw material.Use the inventive method synthetic product to have higher ion-exchange capacity, at aspects such as ion-exchange, catalyzer, siccative, air separation many application are arranged all, particularly can replace the auxiliary agent that " tripoly phosphate sodium STPP " makes washing composition, have the advantages that to guarantee washing composition quality and safety economy.
Claims (2)
1. the synthesis method of zeolite molecular sieve with minerals as raw material through processes such as batch mixing, pre-treatment, crystallization, aftertreatments, is characterized in that said batch mixing is with raw mineral materials and NaOH solution uniform mixing; Said pre-treatment be with batch mixing under 100 ℃～240 ℃ conditions, reacted 18～40 hours; Said crystallization is with pretreated raw material cooling, adds aluminium liquid, directed agents again, makes its composition drop on the synthetic scope of A type or X type zeolite, and crystallization is 4～6 hours under 90 ℃～100 ℃ temperature.
2. according to the described synthesis method of zeolite molecular sieve of claim 1, it is characterized in that in the composition of said raw mineral materials SiO with minerals as raw material
2Account for 40～90wt%; Said aluminium liquid is by NaOH, NaAlO
2And H
2O is formulated; Said directed agents is the silico-aluminate solution that contains sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117045A CN1084711C (en) | 1998-11-21 | 1998-11-21 | Method for synthesizing zeolite molecular sieve using minerals as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117045A CN1084711C (en) | 1998-11-21 | 1998-11-21 | Method for synthesizing zeolite molecular sieve using minerals as raw material |
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| Publication Number | Publication Date |
|---|---|
| CN1225335A true CN1225335A (en) | 1999-08-11 |
| CN1084711C CN1084711C (en) | 2002-05-15 |
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ID=5225342
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| CN98117045A Expired - Fee Related CN1084711C (en) | 1998-11-21 | 1998-11-21 | Method for synthesizing zeolite molecular sieve using minerals as raw material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028373A (en) * | 2012-12-03 | 2013-04-10 | 姜英杰 | Preparation method of adsorbent for removing polar organic pollutants |
| CN102107882B (en) * | 2009-12-23 | 2013-05-15 | 深圳市海川实业股份有限公司 | Method for preparing NaY zeolite |
| CN103570032A (en) * | 2012-07-18 | 2014-02-12 | 中国石油大学(北京) | Preparation method for active aluminosilicate |
| CN108033461A (en) * | 2017-12-18 | 2018-05-15 | 深圳海川新材料科技股份有限公司 | A kind of mineral foaming warm-mixing agent and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106921A (en) * | 1986-10-23 | 1988-05-04 | 核工业部北京第五研究所 | Synthesizing of a kind of modified zeolite |
-
1998
- 1998-11-21 CN CN98117045A patent/CN1084711C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107882B (en) * | 2009-12-23 | 2013-05-15 | 深圳市海川实业股份有限公司 | Method for preparing NaY zeolite |
| CN103570032A (en) * | 2012-07-18 | 2014-02-12 | 中国石油大学(北京) | Preparation method for active aluminosilicate |
| CN103028373A (en) * | 2012-12-03 | 2013-04-10 | 姜英杰 | Preparation method of adsorbent for removing polar organic pollutants |
| CN108033461A (en) * | 2017-12-18 | 2018-05-15 | 深圳海川新材料科技股份有限公司 | A kind of mineral foaming warm-mixing agent and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1084711C (en) | 2002-05-15 |
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