CN103204518A - Method for synthesizing zeolite by circulating fluidized-bed coal ash and bottom ash - Google Patents
Method for synthesizing zeolite by circulating fluidized-bed coal ash and bottom ash Download PDFInfo
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Abstract
The invention discloses a method for synthesizing zeolite by circulating fluidized-bed coal ash and bottom ash. The method comprises the following steps of: carrying out decarburization treatment on the coal ash by a screening machine and mixing the treated coal ash with the bottom ash which is milled by a ball mill; adding alkali liquor in a liquid-solid weight ratio of (5:1) to (9:1); reacting for 1-2 hours under the condition of 50r/min-70r/min by stirring, and the reaction temperature being 95 DEG C to 100 DEG C, and crystallizing by stirring for 4-6 hours at the speed of 20 revolutions/minute to 40 revolutions/minute and the crystallizing reaction being 95 DEG C to 100 DEG C; washing and crystallizing until the pH value is 9-10, dehydrating and filtering, and drying for 3-5 hours under the condition of 85 DEG C to 100 DEG C to a dried zeolite product with the content of 76w%-81w%. According to the method for synthesizing zeolite by circulating fluidized-bed coal ash and bottom ash disclosed by the invention, the synthesis material coal ash is free of any roasting pre-treatment and calcining pre-treatment; the synthesis process is a hydro-thermal synthesis process under normal pressure; and the obtained zeolite has the characteristics of being high in cation exchange capacity, high in specific surface area and the like.
Description
Technical field
The present invention relates to the method for the synthetic zeolite of a kind of circulating fluid bed coal ash, particularly the synthetic A type of a kind of circular fluid bed flyash and bottom ash, X type, P type zeolite and preparation method thereof.
Background technology
Zeolite is the general name of zeolite family mineral, is a kind of moisture basic metal or the manosil AS mineral of alkaline-earth metal.Have natural and branch synthetic, the method for traditional mode of production zeolite is synthetic through complicated technology with pure chemistry raw material or natural mineral, need expend ample resources and the energy.
Flyash is the particulate dispersed resistates behind the coal dust firing, and the flyash of China mainly is used to building materials, building trades such as manufacture of cement, embankment, materials for wall.Existing many reports about the flyash synthesis of molecular sieve.As the CN02138756.7 patent, the method for flyash synthetic zeolite.It provides a kind of method of utilizing the flyash synthetic zeolite, adopt hydrothermal synthesis method, choose NaOH concentration 1.0～2.0mol/L, the aqueous solution and flyash than 1.25～2.5L/S, 90～190 ℃ of synthesis temperatures, synthesis pressure 0～1.0MPa, generated time 22～72h, at first, respectively with the NaOH and the flyash that weigh up, be added to the water to mix to stir and make basic pattern, carry out hydrothermal treatment consists, adopt autoclave that basic pattern is heated then, and continue to stir, make its crystallization, after reaching certain hour, stop heating and synthetic sample is filtered, is drying to obtain the synthetic zeolite product.Directly utilize the flyash synthetic zeolite, flyash is converted into zeolite rate 60%～80%.This patented method prepares needs extra pressure treatment in the zeolite process, and the reaction times is longer.
Prior art is about to using coal-powder boiler flyash more as the report that raw material carries out synthetic zeolite, but less to the research report of circulating fluidized bed (CFBC) flyash synthetic zeolite, especially do not see the report of mixing the bottom ash preparation.Coal-powder boiler flyash, general grinding is sent into the coal-powder boiler internal combustion to particle diameter≤0.08mm with the coal of calorific value greater than 18837KJ, and temperature of combustion reaches 1350 ℃, receive the flue gas behind coal dust firing and catch the thin ash that gets off and be called flyash, its crystallization phases ratio height, poor activity.Need calcination activation processing in advance in the time of coal-powder boiler flyash synthetic zeolite, and the difficult control of the reaction of preparation zeolite.The high-temp combustion environment of coal-powder boiler also produces a large amount of oxynitride simultaneously simultaneously, and a kind of greenhouse gases have a strong impact on environmental protection.In recent years, because the popularization of clean coal technology, circulating fluid bed coal ash has occupied certain proportion in the flyash total amount.So fluid bed powder coal ash processing and utilizing should be subjected to more attention.
Circulating fluid bed coal ash is the flyash that circulating fluidized bed combustion low calorific value coal (mainly being coal gangue) forms.Coal gangue is the solid waste that discharges in coal mining process and the coal washing process, be a kind of lower with a kind of carbon content of coal seam association in the coal-forming process, than the hard grey black look rock of coal, its combustion heat value is about 13395KJ, and the coal-fired calorific value used than coal-powder boiler is low.Coal gangue burns in circulating fluidized bed with particle diameter 3～5mm, temperature range is at 950-1100 ℃ (usually below 1000 ℃) in the burner hearth, because temperature is lower, the crystallization phases that resulting flying dust contains is less, has stronger activity, and its particle diameter is usually about 45 microns, but wherein contain more carbon granule (15-20w%) usually, thereby the performance of the cement that absorbs water, and can have a strong impact on easily, be difficult to be applied to building trade.Because it is calcium, silicone content are higher in the coal gangue, different with the flyash that coal-powder boiler produces again, in the application of the zeolite of preparation, also be subjected to very big obstruction.The circular fluid bed bottom ash is that the gac of coking shape changes into branch, is difficult to especially be used, and still has nothing to do in the prior art in using the circulating fluidized bed bottom ash to prepare the report of zeolite, and only only a few prepares the report of zeolite about circulating fluid bed coal ash.
Shi Zehua etc. utilize the research of fluid bed powder coal ash synthesis of molecular sieve, and " Shanxi coal " the 27th rolled up June 14～16 2007 the 2nd phase.People such as stone pool China has studied and has utilized circular fluid bed flyash in the literary composition, handles without the high-temperature roasting pre-activated, directly feasibility and the advance of synthetic zeolite.The activity of the product that obtains and coal-powder boiler flyash are suitable as the product property that the raw material synthetic zeolite obtains, and need in the reactor of sealing, be prepared, through characterizing test, recording synthetic zeolite conversion degree of crystallinity is the more excellent test example of 55～75%(), degree of crystallinity is relatively poor.
Summary of the invention
The objective of the invention is to overcome and utilize the synthetic zeolite condition of circulating fluid bed coal ash comparatively complicated in the prior art, transformation efficiency is lower, specific surface area is less, ion-exchange performance is relatively poor, can't use the circulating fluidized bed bottom ash to prepare deficiencies such as zeolite, the method for a kind of circular fluid bed flyash and bottom ash synthetic zeolite is provided.
In order to realize the foregoing invention purpose, the invention provides following technical scheme:
The method of a kind of circular fluid bed flyash and bottom ash synthetic zeolite may further comprise the steps:
(1) flyash is taken off charcoal with sieve apparatus and handle the back and mix through the levigate bottom ash of ball mill, the bottom ash add-on accounts for the 20w%～30w% of total amount.
(2) in the mixed powder that obtains to step (1), the weight ratio of pressing flowing fluid ratio pressed powder 5:1～9:1 adds alkali lye, obtains mixed solution.
(3) mixed solution that step (2) is obtained, with 50～70 rev/mins speed stirring reactions 1～2 hour, 95～100 ℃ of temperature.
(4) continue speed with 20～40 rev/mins, stir 4～6 hours crystallization, 95～100 ℃ of temperature.
(5) dewatering and filtering, wash crystallization thing are to pH=9～10, and dewatering and filtering discards washings again, collect crystallization, dry under 85～100 ℃ of conditions and namely get dry zeolite product in 3～5 hours.
Described flyash is circular fluid bed flyash, and bottom ash is the circular fluid bed bottom ash.
Flyash takes off the charcoal processing with sieve apparatus in the step (1), sloughs the charcoal of 60%-80% in the flyash.Take off the charcoal that contains 15w%-20w% in the preceding circular fluid bed flyash of charcoal, have a strong impact on the zeolite quality of preparation.Take off the flyash behind the charcoal, carbon content is about 3w%～10w%, has higher activity, the zeolite of easier preparation high-crystallinity, and the zeolite for preparing simultaneously has better adsorption rate and exchange capacity, and its mechanism is not clear and definite as yet.
Bottom ash particle diameter＜0.046mm behind levigate in the step (1).Bottom ash after levigate easily dissolves, and fully flyash and the bottom ash after the dissolving has the more crystalline degree, and the transformation efficiency that forms zeolite is higher, and absorption property is better.The circular fluid bed bottom ash is that the gac of coking shape changes into branch, by sufficient grinding, mixes with circular fluid bed flyash, reacts more complete, and it is higher to generate the zeolite transformation efficiency.
Step is mixed with dry-mixed machine in (1).Dry-mixed machine powder mix coal ash and bottom ash have been avoided flying dust and bottom ash because make moist caking, and mixed effect is better, and Si, Al element are evenly distributed in follow-up zeolite crystal process of growth, and the purity of the crystal that obtains is higher, is worth bigger.
The described alkali lye of step (2) is the NaOH solution of 2.5～3.2mol/L.OH in the alkali lye
-Ionic concn is less than 2.5mol/L(such as 1.7mol/L) time, the flyash dissolving is not good, and in the follow-up crystallisation process, crystal formation impurity is more, is not easy to control reaction result.OH in the alkali lye
-Concentration greater than 3.2mol/L after (as 4.2mol/L), the crystallization transformation efficiency is no longer increased, even descends, waste raw material, increase cost.
Further, the alkali lye in the step (2) is technical grade NaOH and KOH, the compound alkali lye that mixed preparing forms.The preferred 1:0.4-0.6 mol ratio of pressing is mixed NaOH and KOH, is mixed with OH
-Ionic concn is the compound alkali lye of 2.5～3.2mol/L.The contriver finds unexpectedly that in the process of preparation zeolite the compound alkali lye of potassium sodium more is conducive to nucleation and the further growth of crystal in preparation zeolite process.And the various physicochemical properties of gained zeolite are better.It has been generally acknowledged that NaOH has higher activity than KOH in the technology of tradition fly-ash Preparation zeolite, the crystallization that more is conducive to zeolite transforms, and the contriver finds that under certain proportion, mixing solutions has the effect that more outstanding short flyash is converted into zeolite.Preparation zeolite technical grade NaOH and KOH, cost is lower.Further, more industrial waste alkali lye can be used, namely eliminate the pollution of industrial alkali waste to environment, can be used as renewable resource again.
Further, described step (3) is for opening wide system.Described unlimited system is the synthesis under normal pressure system, need not extra pressure boost.Prepared in reaction zeolite under condition of normal pressure has been eliminated the danger of condition of high voltage, and is simple to operate, reduced the zeolite production cost, is more conducive to the popularization of technology.
Further, described step (4) is for opening wide system.Namely the reaction environment that communicates with atmosphere need not extra pressurization, and reaction conditions is gentleer.
Further, washings in the recycling step (5) is used for step (2) behind the adjusting pH.Reclaim washings, be used, reduced the discharging of waste liquid, improved the availability of alkali lye, can effectively preserve the ecological environment.
Each weight percentages of components of circular fluid bed flyash (percentage that does not specify among the present invention all is weight percentage) content: SiO
240w%～60w%, Al
2O
320w%～40w%, loss on ignition 10%～20w%, SiO
2+ Al
2O
370w%, particle diameter 0.046mm.
According to different manufacturers/batch, select no flyash and bottom ash for use, then, regulate flyash and bottom ash ratio, make SiO
2=40w%～50w%, Al
2O
3=40w%～45w%, SiO
2+ Al
2O
380w%, SiO
2/ Al
2O
3=1～1.3(mass ratio), can prepare A type coal ash zeolite by high conversion;
Regulate flyash and coal bottom ash ratio, make SiO
2=45w%～55w%, Al
2O
3=30w%～45w%, SiO
2+ Al
2O
370w%, SiO
2/ Al
2O
3=1.2～1.5(mass ratio), can prepare X type coal ash zeolite by high conversion;
Regulate flyash and coal bottom ash ratio, make SiO
2=50w%～65w%, Al
2O
3=20w%～30w%, SiO
2+ Al
2O
370w%, SiO
2/ Al
2O
3=1.4～2.0(mass ratio), can prepare P type coal ash zeolite by high conversion.
Zeolite preparation method of the present invention, with industrial solid castoff---circular fluid bed flyash and bottom ash, as renewable resource, need not be through any roasting, calcining pretreatment, normal pressure, low-temperature hydrothermal synthesis method; Regulate flyash and bottom ash ratio, can distinguish synthesis of high content A type, X type and P type zeolite, simplified zeolite synthesis technology, saved resource and the energy.Synthetic zeolite transformation efficiency height, crystal formation purity height has high using value.
Circular fluid bed flyash and bottom ash synthesize A type, X type, P type prepare zeolite technology, it is characterized in that adopting industrial solid castoff (circular fluid bed flyash and bottom ash) as main raw material, technical grade alkali lye is time main raw material, flyash need not be through any roasting, calcining pretreatment, directly with normal pressure, synthetic A type, X type, the P type zeolite produced of low-temperature hydrothermal synthesis method.Can be used as the main raw material of soil improvement amendment; Produce slowly-releasing controlledly synthesis zeolite chemical fertilizer main raw material; Can effectively improve water retention capacity and the exchange of particles performance of soil, make soil become more fluffy, plantation crop yield thereon increases.Also can provide comparatively cheap filtration main raw as environment protection sewage, off gas treatment.
Compared with prior art, beneficial effect of the present invention: the method that the present invention utilizes circular fluid bed flyash and bottom ash to synthesize A type, X type, P type zeolite, synthesis material flyash need not be through any roasting, calcining pretreatment; Synthesis technique is that normal pressure opens wide reaction system, the synthetic A type of low-temperature hydrothermal synthesis method, X type, P type zeolite, has saved the traditional processing technology method and has used pure chemistry raw material or natural mineral through complicated technology synthetic zeolite spent resource and the energy.
The zeolite product that the inventive method prepares has great cation exchange capacity, the result that test obtains according to relevant criterion shows, the cation exchange capacity of gained zeolite is that existing method makes hundreds of times of zeolite (prior art is generally 50～100cmol/kg, the inventive method 2.0～3.6mol/g).Higher cation exchange capacity can be strengthened the application of zeolite aspect the soil getting fat, and the zeolite of using isodose can improve the productivity ratio of farm crop on the soil greatly.
Embodiment
The present invention is described in further detail below in conjunction with testing example and embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology that realizes based on content of the present invention all belong to scope of the present invention.
The correlated performance test
Test particle diameter with absorption method, record synthetic zeolite particle diameter 0.001～0.004mm.
Measure the cation exchange capacity (CEC) of synthetic zeolite according to JIS K1478-2009 " measuring method of the cation exchange capacity of permutite ".Test result: the synthetic zeolite that obtains, the CEC cationic exchange is 2.0～3.6mol/g
Adopt the specific surface area of absorption method test synthetic zeolite, the zeolite external surface area that the present invention synthesizes is 800～1000m
2/ kg.
Embodiment 1
Select circulating sulfuration bed coal ash and the bottom ash in A power station for use, the flyash flying dust is taken off charcoal, bottom ash through the levigate operation processing of ball mill through the sieve apparatus screening, in dry-mixed machine, mix by a certain percentage then, make SiO in the compound
2+ Al
2O
380w%, SiO
2/ Al
2O
3=1.2(mass ratio), press flowing fluid ratio solid 5:1(weight ratio) and OH
-Ionic concn is that the alkali lye of 3.2mol/L mixes.Under 95 ℃ of temperature, stir with 50～70r/min rotating speed, react 1h in the synthesis under normal pressure system.Continue then to stir with 20～40r/min rotating speed, 95 ℃ of temperature are opened wide in the system and are reacted 4h.Dewatering and filtering, repetitive scrubbing are collected the solid phase composition to washing lotion pH=9, namely get A type zeolite product at 85 ℃ of dry 3h.It is formulated that described alkali lye usefulness NaOH and KOH press the 2:1 mol ratio.
Embodiment 2
Select circulating sulfuration bed coal ash and the bottom ash in A power station for use, the flyash flying dust is taken off charcoal, bottom ash through the levigate operation processing of ball mill through the sieve apparatus screening, in dry-mixed machine, mix by a certain percentage then, make SiO in the compound
2+ Al
2O
370w%, SiO
2/ Al
2O
3=1.4(mass ratio), press flowing fluid ratio solid 9:1(weight ratio) mix with the NaOH solution of 2.5mol/L.Under 100 ℃ of temperature, stir with 59～70r/min rotating speed, open wide in the system and react 2h.Continue then to stir with 20～40r/min rotating speed, 100 ℃ of temperature are reacted 6h in the system of opening wide.Dewatering and filtering, repetitive scrubbing are collected the solid phase composition to washing lotion pH=10, namely get X type zeolite product at 100 ℃ of dry 5h.
Embodiment 3
Select circulating sulfuration bed coal ash and the bottom ash in B power station for use, the flyash flying dust is taken off charcoal, bottom ash through the levigate operation processing of ball mill through the sieve apparatus screening, in dry-mixed machine, mix by a certain percentage then, make SiO in the compound
2+ Al
2O
370w%, SiO
2/ Al
2O
3=1.7(mass ratio), press flowing fluid ratio solid 6:1(weight ratio) mix with the NaOH solution of 2.8mol/L.Under 98 ℃ of temperature, stir with 50～70r/min rotating speed, open wide in the system and react 1.5h.Continue then to stir with 20～40r/min rotating speed, 98 ℃ of temperature are opened wide in the system and are reacted 5h.Dewatering and filtering, repetitive scrubbing are collected the solid phase composition to washing lotion pH=10, namely get P type zeolite product at 90 ℃ of dry 4h.
Embodiment 4
Select circulating sulfuration bed coal ash and the bottom ash in B power station for use, the flyash flying dust is taken off charcoal, bottom ash through the levigate operation processing of ball mill through the sieve apparatus screening, in dry-mixed machine, mix by a certain percentage then, make SiO in the compound
2+ Al
2O
370w%, SiO
2/ Al
2O
3=1.37(mass ratio), by liquid-solid ratio 8:1(weight ratio) mix with the NaOH solution of 3.0mol/L.Under 97 ℃ of temperature, stir with 50～70r/min rotating speed, open wide in the system and react 1.5h.Continue then to stir with 20～40r/min rotating speed, 99 ℃ of temperature are opened wide in the system and are reacted 5h.Dewatering and filtering, repetitive scrubbing are collected the solid phase composition to washing lotion pH=10, namely get X type zeolite product at 95 ℃ of dry 4h.
Embodiment 5
Select circulating sulfuration bed coal ash and the bottom ash in B power station for use, the flyash flying dust is taken off charcoal, bottom ash through the levigate operation processing of ball mill through the sieve apparatus screening, in dry-mixed machine, mix by a certain percentage then, make SiO in the compound
2+ Al
2O
370w%, SiO
2/ Al
2O
3=1.8(mass ratio), by liquid-solid mass ratio 8:1(weight ratio) and OH
-Ionic concn is that the alkali lye of 3.0mol/L mixes.Under 97 ℃ of temperature, stir with 50～70r/min rotating speed, open wide in the system and react 1.5h.Continue then to stir with 20～40r/min rotating speed, 99 ℃ of temperature are opened wide in the system and are reacted 5h.Dewatering and filtering, repetitive scrubbing are collected the solid phase composition to washing lotion pH=10, namely get P type zeolite product at 95 ℃ of dry 4h.It is formulated that described alkali lye usefulness NaOH and KOH press the 2:1 mol ratio.
Performance test
Get the zeolite that embodiment 1～5 synthesizes, test its physicochemical property according to relevant criterion or method, the results are shown in Table 1.
Table 1 physicochemical property test result
Annotate: the absorption method test is tested with nitrogen adsorption, each embodiment product repeated sampling test 5 times, result's SPSS 11.5 statistical study.
Claims (9)
1. the method for a circular fluid bed flyash and bottom ash synthetic zeolite is characterized in that, may further comprise the steps:
(1) flyash is taken off charcoal and handles with sieve apparatus after and mix through the levigate bottom ash of ball mill, the bottom ash add-on accounts for the 20w%～30w% of total amount;
(2) in the mixed powder that obtains to step (1), the weight ratio of pressing flowing fluid ratio pressed powder 5:1～9:1 adds alkali lye, obtains mixed solution;
(3) mixed solution that step (2) is obtained, with 50～70 rev/mins speed stirring reactions 1～2 hour, 95～100 ℃ of temperature;
(4) continue speed with 20～40 rev/mins, stir and made its crystallization, 95～100 ℃ of temperature in 4～6 hours;
(5) dewatering and filtering, wash crystallization thing are to pH=9～10, and dewatering and filtering discards washings again, collect crystallization, dry under 85～100 ℃ of conditions and namely get the zeolite product in 3～5 hours;
Step (1) is described takes off charcoal and handles and make that carbon content is 3w%～10w% in the flyash; The described alkali lye of step (3) is the NaOH solution of 2.5～3.2mol/L.
2. the method for circular fluid bed flyash according to claim 1 and bottom ash synthetic zeolite is characterized in that, described bottom ash particle diameter＜0.046mm.
3. the method for circular fluid bed flyash according to claim 1 and bottom ash synthetic zeolite is characterized in that, uses dry-mixed machine powder mix coal ash and bottom ash in the step (1).
4. the method for circular fluid bed flyash according to claim 1 and bottom ash synthetic zeolite is characterized in that, step (3) (4) is for opening wide reaction system.
5. the method for circular fluid bed flyash according to claim 1 and bottom ash synthetic zeolite is characterized in that, alkali lye is OH described in the step (2)
-Ionic concn is NaOH and the compound alkali lye of KOH of 2.5～3.2mol/L.
6. the method for circular fluid bed flyash according to claim 5 and bottom ash synthetic zeolite is characterized in that, described compound alkali lye is technical grade NaOH and KOH, and it is formulated to press the 1:0.4-0.6 mixed in molar ratio.
7. the method for circular fluid bed flyash according to claim 1 and bottom ash synthetic zeolite is characterized in that, the washings in the recycling step (5) is used for step (2) behind the adjusting pH.
8. the zeolite for preparing according to the method for the described circular fluid bed flyash of claim 1～8 and bottom ash synthetic zeolite.
9. the zeolite for preparing according to the method for the described circular fluid bed flyash of claim 1～8 and bottom ash synthetic zeolite is in the application of agromelioration, fertilizer and field of environment protection.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104787763A (en) * | 2015-04-10 | 2015-07-22 | 山西大学 | Preparation method for activated coke powder for carbon fuel cell |
| CN104843729A (en) * | 2015-05-04 | 2015-08-19 | 华中科技大学 | Zeolite preparation process at normal temperature and pressure and application thereof |
| CN105036150A (en) * | 2015-06-26 | 2015-11-11 | 中国矿业大学(北京) | Artificial zeolite prepared directionally by utilizing industrial solid waste and preparation method and application thereof |
| CN106281337A (en) * | 2016-08-05 | 2017-01-04 | 中国地质大学（北京） | One utilizes potassium-enriched rock to prepare farmland soil heavy metals Cd passivator and preparation method thereof |
| CN108190911A (en) * | 2018-02-08 | 2018-06-22 | 西安建筑科技大学 | A kind of synthetic method of multi-stage porous block phillipsite |
| CN110423174A (en) * | 2019-08-02 | 2019-11-08 | 温州科技职业学院 | A kind of soil acidity conditioner and preparation method thereof |
| CN112500864A (en) * | 2020-12-16 | 2021-03-16 | 华南理工大学 | Multi-element soil conditioner produced by using fly ash and preparation method thereof |
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| JPH10324518A (en) * | 1997-05-26 | 1998-12-08 | Akio Henmi | Continuous production of artificial zeolite by circulating fluidized-bed and device for continuously producing artificial zeolite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104787763A (en) * | 2015-04-10 | 2015-07-22 | 山西大学 | Preparation method for activated coke powder for carbon fuel cell |
| CN104843729A (en) * | 2015-05-04 | 2015-08-19 | 华中科技大学 | Zeolite preparation process at normal temperature and pressure and application thereof |
| CN104843729B (en) * | 2015-05-04 | 2017-08-01 | 华中科技大学 | Process and its application of zeolite are prepared under a kind of normal temperature and pressure |
| CN105036150A (en) * | 2015-06-26 | 2015-11-11 | 中国矿业大学(北京) | Artificial zeolite prepared directionally by utilizing industrial solid waste and preparation method and application thereof |
| CN106281337A (en) * | 2016-08-05 | 2017-01-04 | 中国地质大学（北京） | One utilizes potassium-enriched rock to prepare farmland soil heavy metals Cd passivator and preparation method thereof |
| CN108190911A (en) * | 2018-02-08 | 2018-06-22 | 西安建筑科技大学 | A kind of synthetic method of multi-stage porous block phillipsite |
| CN108190911B (en) * | 2018-02-08 | 2021-06-11 | 西安建筑科技大学 | Method for synthesizing multi-level pore block phillipsite |
| CN110423174A (en) * | 2019-08-02 | 2019-11-08 | 温州科技职业学院 | A kind of soil acidity conditioner and preparation method thereof |
| CN112500864A (en) * | 2020-12-16 | 2021-03-16 | 华南理工大学 | Multi-element soil conditioner produced by using fly ash and preparation method thereof |
| CN112500864B (en) * | 2020-12-16 | 2022-04-22 | 华南理工大学 | Multi-element soil conditioner produced by using fly ash and preparation method thereof |
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