CN104437354A - Method for preparing improved coal ash-zeolite composite particles - Google Patents
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/14—Base exchange silicates, e.g. zeolites
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
Abstract
The invention discloses a method for preparing improved coal ash-zeolite composite particles. The method comprises the following steps: firstly, carrying out acid pickling pretreatment to remove metal impurity components affecting zeolite formation in coal ash, then adding a mineral raw material rich in Si and Al to compensate the effectiveness defect of Si and Al, synthesizing zeolite composite particles under an alkaline hydrothermal condition, and improving the adsorption and exchange properties of the composite particles by using a calcium or magnesium salt to obtain the improved coal ash-zeolite composite particles. The method disclosed by the invention is simple in equipment, simple and convenient to operate, cheap and easy to obtain the used raw materials and is suitable for industrialized production. The prepared improved coal ash-zeolite composite particles have an obvious adsorption coprecipitation effect on nitrogen and phosphorus in waste water and are suitable for synchronous removal and recovery of nitrogen and phosphorus in high-concentration waste water.
Description
Technical field
The present invention relates to a kind of preparation method of modified coal ash zeolite composite particles.
Background technology
Flyash is the accessory substance in thermal power plant, has become one of Chinese key industry solid waste, has threaten the sustainable development of national economy and ecological environment, and the process of flyash is disposed and comprehensive utilization becomes problem demanding prompt solution.The comprehensive utilization of flyash accounts for 80% in building, building materials, traffic, but ratio is less than 5% in the high added value such as environmental protection and new material Application and Development, thus need the dynamics strengthening the high-new application technology research and development of flyash, improve resource and the comprehensive utilization ratio thereof of flyash.
Water pollutions and environmental disruption have become one of key factor of restriction Chinese national economy sustainable development, and wherein body eutrophication has become an outstanding water environmental problems of China.The input controlling exogenous nitrogen phosphorus is one of control strategy of body eutrophication, especially auxotype high concentration Nitrogen-and Phosphorus-containing waste water, as livestock breeding wastewater.Although this type of waste water reduces severe pollution industry by conventional anaerobic fermentation process, anaerobic fermentation water outlet N, P concentration still very high (NH
4 +-N 500 ~ 1000mg/L, total phosphorus-TP 60 ~ 500mg/L).In addition, food industrial wastewater (COD 3000 ~ 41000mg/L, total nitrogen-TN 100 ~ 1000mg/L, TP20 ~ 300mg/L), percolate from garbage filling field (NH
4 +-N is up to more than 2000mg/L), chemical fertilizer factory waste water (NH
4 +-N is up to 3000mg/L) etc. nitrogen and phosphorus load high, though the technological means such as existing biology, chemistry and physics can realize removal or the recovery of waste water N, P to a certain extent, processing cost is high and technical requirement harsh.Therefore, the nitrogen phosphorus ligands of exploitation efficient, low cost, auxotype high-concentration waste water easy and simple to handle and recovery technology seem very necessary.
Absorption method is the physical chemistry method of removal waste water N, P of a kind of relative ease, a kind of nitrogen phosphorus sorbing material efficiently of research and development is also competent in auxotype high-concentration waste water nitrogen phosphorus ligands and recovery, and this is significant for realizing the reduction of discharging of waste water nitrogen phosphorus and controlling body eutrophication.Alkalescence hydro-thermal method is by flyash Fast back-projection algorithm zeolite composite particles, and the specific area of its product improves greatly, and absorption property also obviously strengthens, and has the ability of N, P nutriment in good removal waste water, can be applied to the process of high concentration of nitrogen and phosphorus waste water.But the fire coal of each thermal power plant, electrification technique as well as are different, its fly ash form, component etc. produced is each variant, cause the effective silicon of flyash: aluminum ratio (Si:Al) does not match with skeleton Si:Al needed for synthetic zeolite composite particles, directly affects synthetic zeolite composite particles crystal structure and performance.In addition, the foreign metal ion of flyash itself easily occupies the active site position of synthetic zeolite composite particles, causes obligate to be adsorbed and declines with ion-exchange performance, weakening ammonia nitrogen in waste water and phosphaticly to remove and recovery capacity.Thus, supplemented by external source be rich in effective Si, Al natural mineral raw to improve synthetic zeolite composite particles crystal structure and performance, auxiliary impurity element elution technique, be coupled calcium magnesium salts modification technology to strengthen obligate absorption and the ion-exchange performance of synthetic zeolite composite particles simultaneously, produce the composite that more high-quality and absorption property are superior, to the raising nutraceutical removal of waste water N, P and the ability of recovery significant, also raising total utilization of PCA is had important practical significance simultaneously.
Summary of the invention
The object of the invention is to the technological deficiencies such as low for existing synthetic zeolite from flyash composite particles relevant Si, Al validity, impurity element disturbs, obligate absorption/exchange capacity is not enough, a kind of preparation method of modified coal ash zeolite composite particles is provided.
For achieving the above object, first the present invention takes off pretreatment by pickling and removes in flyash the metal impurity components affecting zeolite and formed, thereafter itself Si and Al validity defect is made up by adding the raw mineral materials being rich in Si and Al, synthetic zeolite composite particles under alkaline water heat condition, recycling calcium salt or magnesium salts modification technology improve absorption and the switching performance of composite particles, the type that is finally improved coal ash zeolite composite particles.
The technical solution used in the present invention is: the preparation method of described modified coal ash zeolite composite particles, comprises the steps:
(1) by after flyash oven dry, ground 60 mesh sieves, the acid solution being 1 ~ 3mol/L with concentration is uniformly mixed by solid-to-liquid ratio 1g:3mL, acid etch reaction 0.5 ~ 2h at 60 ~ 100 DEG C of temperature, and cooled and filtered is separated, it is dry at 6 ~ 7,90 DEG C that gained solid water is washed till pH value;
(2) mixed with the raw mineral materials being rich in Si and Al by the flyash through step (1) low-kappa number, obtain grey-ore deposit solid mixture, in ash-ore deposit solid mixture, Si:Al mol ratio is 1 ~ 3:1;
(3) aqueous slkali being 1 ~ 6mol/L by ash-ore deposit solid mixture and concentration mixes in the ratio of solid-to-liquid ratio 1g:2 ~ 8mL, hydro-thermal reaction 24 ~ 72h at 80 ~ 120 DEG C of temperature, obtains coal ash zeolite composite particles primary product;
(4) coal ash zeolite composite particles primary product mixed by solid-to-liquid ratio 1g:10mL with calcium salt soln or magnesium salt solution, the concentration of calcium salt soln or magnesium salt solution is 0.5 ~ 2mol/L, normal temperature vibration 24h;
(5) product step (4) obtained after filtration, deionized water washing, until detect cleaning solution without Ca
2+or Mg
2+, then particle is dry, the type that is improved coal ash zeolite composite particles.
Further, the raw mineral materials of the Si of being rich in of the present invention and Al is diatomite, kaolin or both mixtures.
Further, acid solution of the present invention is hydrochloric acid, sulfuric acid or both mixtures.
Further, of the present invention is NaOH, potassium hydroxide or both mixed solutions containing aqueous slkali.
Further, calcium salt of the present invention is one or more in calcium chloride, calcium nitrate and calcium bicarbonate.Described magnesium salts is a kind of in magnesium chloride and magnesium nitrate or both mixtures.
Compared with prior art, the invention has the beneficial effects as follows:
1. the inventive method equipment is simple, easy and simple to handle, and raw material used are industrial solid castoff cheap and easy to get and raw mineral materials, is applicable to suitability for industrialized production.
2. first the inventive method is removed with pickling and is unfavorable for the metal impurity components that zeolite is formed, then add Si, Al validity defect that mineral make up original fly ash, after synthesizing elementary composite particles, adopt calcium salt or magnesium salt solution modification technology to promote absorption and the exchange capacity of composite particles again.For conventional method, the cation exchange capacity (CEC) (CEC) of the modified coal ash zeolite composite particles that the present invention obtains adds 20 ~ 85%, phosphorus adsorption capacity (PIC) improves 60 ~ 120%, nitrogen removal efficiency improves 50 ~ 95%, and tp removal rate improves 150 ~ 260%.
3. adding sial chemicals with tradition regulates compared with synthetic zeolite from flyash composite particles, and the inventive method regulates Si, Al validity in flyash by the raw mineral materials (diatomite, kaolin or both mixtures) of the natural Si of being rich in of interpolation, Al.What the inventive method was selected is a kind of relative sial salt chemical reagent material more cheap and easy to get containing Si, Al raw mineral materials, and from the residue Al synthetic zeolite that also can utilize under alkali lye condition in flyash, it adds the effective rate of utilization that improve Si, Al composition in flyash.
4. the inventive method improves coal ash zeolite composite particles performance by calcium salt or magnesium salt solution modification technology, the sodium ion in zeolitic frameworks is made to be replaced into calcium, magnesium ion, calcium, magnesium ion have the effects such as exchange, absorption and co-precipitation to ammonia nitrogen, phosphate, this modified coal ash zeolite composite particles CEC is 240 ~ 320cmol/kg and PIC is 50 ~ 85g/kg, it, to nitrogen phosphorus adsorption coprecipitation successful in waste water, is applicable to synchronous removal and the recovery of nitrogen phosphorus in high-concentration waste water.
Accompanying drawing explanation
Fig. 1 is the modified coal ash zeolite composite particles of embodiment 1 and X-ray diffraction (XRD) comparison diagram (angle of diffraction is 10 ~ 60 °, M=mullite, Q=quartz, P1=NaP1 zeolite) adopting conventional method coal ash zeolite particle.
Fig. 2 is the electron-microscope scanning figure of coal ash zeolite composite particles, and wherein a) figure is the modified coal ash zeolite composite particles of embodiment 1, and b) figure is the coal ash zeolite particle of conventional method.
Fig. 3 is the modified coal ash zeolite composite particles of embodiment 2 and X-ray diffraction (XRD) comparison diagram (angle of diffraction is 10 ~ 60 °, M=mullite, Q=quartz, P1=NaP1 zeolite) of the coal ash zeolite particle of employing conventional method.
Fig. 4 is the modified coal ash zeolite composite particles electron-microscope scanning figure of embodiment 2.
Fig. 5 is the modified coal ash zeolite composite particles of embodiment 3 and X-ray diffraction (XRD) comparison diagram (angle of diffraction is 10 ~ 60 °, M=mullite, Q=quartz, P1=NaP1 zeolite) of the coal ash zeolite particle of employing conventional method.
Fig. 6 is the modified coal ash zeolite composite particles electron-microscope scanning figure of embodiment 3.
Detailed description of the invention
The preparation method of modified coal ash zeolite composite particles of the present invention: the metal impurity components first being taken off powdered coal ash by pickling, thereafter add the raw mineral materials being rich in Si, Al and improve Si:Al when validity, then alkaline water thermal synthesis is carried out to ash-ore deposit solid mixture and form coal ash zeolite particle primary product, finally recycle the Nitrogen and phosphorus exchange of calcium salt or magnesium salt solution modification technology enhancing final products, absorption and co-precipitation performance.Wherein, carrying out the pretreated main purpose of pickling to flyash is remove the metal oxide Fe in powdered coal ash
2o
3, CaO, MgO etc., these metal oxides generate precipitation in the basic conditions and are attached to flyash precursor granule surface and can affect the stripping of Si, Al in flyash and the zeolite crystallization at particle surface.Regulating Si, Al validity of original fly ash to improve Si:Al ratio by adding raw mineral materials, improving zeolite crystal productive rate.Containing silicon, aluminium component in the flyash that the present invention is used, its type, the place of production, composition are not limit; Raw mineral materials containing Si, Al is preferably diatomite, kaolin or both mixtures; Acid solution used is preferably hydrochloric acid, sulfuric acid or both mixed liquors; Alkali lye used is preferably NaOH, potassium hydroxide or both mixed solutions; Calcium used, magnesium salts are preferably calcium chloride, magnesium chloride or both salt-mixtures.Preparation method of the present invention is further illustrated below with specific embodiment.
Embodiment 1
Getting 20g pulverizing is that No. 1,60 object flyash sample (composition Si:Al mol ratio is 1.82:1) mixes by solid-to-liquid ratio 1g:3mL with hydrochloric acid solution (3mol/L), be heated to 95 DEG C, mixing speed is stop after 200r/min, 1h adding thermal agitation.Dry at the washing of cooled and filtered, deionized water is 7,90 DEG C to pH value, obtain low-kappa number flyash.
In low-kappa number flyash, add diatomite 1.68g, obtain ash-ore deposit solid mixture that Si:Al mol ratio is 2.5:1.Ash-ore deposit solid mixture is mixed by solid-to-liquid ratio 1g:6mL with sodium hydroxide solution (2mol/L), under temperature 95 DEG C, mixing speed 200r/min, reacts 48h.Reactant mixture obtains coal ash zeolite composite particles primary product after filtration, and spending deionized water to pH value is 7.5, subsequently dry 24h at 90 DEG C.Carry out saturated replacement Treatment to composite particles calcium chloride solution (0.5mol/L) again, after filtration, deionized water washing is to without Ca
2+, final acquisition modified coal ash zeolite composite particles (ZFA-1) after dry.
Adopt the technical process of conventional method synthesis coal ash zeolite as follows: directly to be mixed by solid-to-liquid ratio 1g:6mL with sodium hydroxide solution (2mol/L) by 60 order flyash, 48h is reacted under temperature 95 DEG C, mixing speed 200r/min, reactant mixture after filtration, washing, dry, obtain coal ash zeolite composite particles (ZFA
cK).
As shown in Figure 1, comparative analysis finds the mineral composition XRD diffraction analysis of modified coal ash zeolite composite particles: the peak intensity comparatively ZFA of the zeolite of ZFA-1
cKhigher.Particle surface shape is as shown in Fig. 2 ESEM (SEM) analysis, and a large amount of synthetic zeolite crystal grain is attached to flyash surface.Its physicochemical character is as shown in table 1, and relative to Traditional preparation, CEC, the PIC of modified coal ash zeolite composite particles, specific area (BET) respectively synergy reach 48.6%, 78.3% and 59.3%.Natural pond, the pig farm liquid waste water that ammonia nitrogen concentration is 1105mg/L, phosphorus concentration is 285mg/L is contained for process, by solid-to-liquid ratio 1g:100ml, vibrate after 24h under 25 DEG C of conditions, the nitrogen of modified coal ash zeolite composite particles (ZFA-1), the more traditional coal ash zeolite composite particles of tp removal rate (ZFA
cK) synergy 52.7% and 259.1% respectively.
Embodiment 2
Getting 20g pulverizing is that No. 2,60 order flyash sample (composition Si:Al mol ratio is 1.51:1) mixes by solid-to-liquid ratio 1g:3mL with hydrochloric acid solution (3mol/L), and be heated to 95 DEG C, mixing speed is stop after 200r/min, 1h adding thermal agitation.Dry at the washing of cooled and filtered, deionized water is 7,90 DEG C to pH value, obtain low-kappa number flyash.
In low-kappa number flyash, add kaolin 1.5g, obtain ash-ore deposit solid mixture that Si:Al mol ratio is 1.72:1.Ash-ore deposit solid mixture is mixed by solid-to-liquid ratio 1g:6mL with sodium hydroxide solution (2mol/L), under temperature 95 DEG C, mixing speed 200r/min, reacts 48h.Reactant mixture obtains coal ash zeolite composite particles primary product after filtration, and spending deionized water to pH value is 7.5, subsequently dry 24h at 90 DEG C.Carry out saturated replacement Treatment to composite particles magnesium chloride solution (0.5mol/L) again, after filtration, deionized water washing is to without Mg
2+, drying is improved type coal ash zeolite composite particles (ZFA-2).
Adopt the technical process of conventional method synthesis coal ash zeolite as follows: directly to be mixed by solid-to-liquid ratio 1g:6mL with sodium hydroxide solution (2mol/L) by 60 order flyash, 48h is reacted under temperature 95 DEG C, mixing speed 200r/min, reactant mixture after filtration, washing, dry, obtain coal ash zeolite composite particles (ZFA
cK).
The mineral composition XRD diffraction analysis of modified coal ash zeolite composite particles as shown in Figure 3, the peak intensity comparatively ZFA of ZFA-2 zeolite
cKhigher.Particle surface shape, as shown in Fig. 4 ESEM (SEM) analysis, is distributed in flyash surface to a large amount of zeolite tiny crystals uniform particles.Its physicochemical character is as shown in table 1.CEC, PIC, BET of modified coal ash zeolite composite particles improve 24.4%, 103.1%, 115.3% respectively relative to traditional coal ash zeolite composite particles.
Adopt the waste water of example 1 and techniqueflow to carry out nitrogen phosphorus and remove test, find nitrogen, the more traditional coal ash zeolite composite particles of the tp removal rate (ZFA of modified coal ash zeolite composite particles (ZFA-2)
cK) synergy 66.8% and 203.9% respectively.
Embodiment 3
Getting 20g pulverizing is 60 order sample 3 flyash (composition Si:Al mol ratio is 1.21:1), and mix by solid-to-liquid ratio 1g:3mL with sulfuric acid solution (3mol/L), be heated to 95 DEG C, mixing speed is stop after 200r/min, 1h adding thermal agitation.Dry at the washing of cooled and filtered, deionized water is 6,90 DEG C to pH value, obtain low-kappa number flyash.
In low-kappa number flyash, add diatomite and kaolinic mixture 3.66g, diatomite and kaolinic weight ratio are 1.8:1, obtain ash-ore deposit solid mixture that Si:Al mol ratio is 2.25:1.Ash-ore deposit solid mixture is mixed by solid-to-liquid ratio 1g:6mL with sodium hydroxide solution (2mol/L), under temperature 95 DEG C, mixing speed 200r/min, reacts 48h.Instead, answer mixture to obtain coal ash zeolite composite particles primary product after filtration, spending deionized water to pH value is 7.5, subsequently dry 24h at 90 DEG C.Carry out saturated replacement Treatment to composite particles calcium chloride solution (0.5mol/L) again, after filtration, deionized water washing is to without Ca
2+, drying is improved type coal ash zeolite composite particles (ZFA-3).
Adopt the technical process of conventional method synthesis coal ash zeolite as follows: directly to be mixed by solid-to-liquid ratio 1g:6mL with sodium hydroxide solution (2mol/L) by 60 order flyash, 48h is reacted under temperature 95 DEG C, mixing speed 200r/min, reactant mixture after filtration, washing, dry, obtain synthetic zeolite from flyash composite particles (ZFA
cK)
The mineral composition XRD diffraction analysis of modified coal ash zeolite composite particles as shown in Figure 5, ZFA-3 zeolite peak number amount and intensity all comparatively ZFA
cKhigher.Shown in Fig. 6 ESEM, particle surface has a large amount of zeolite crystal to be attached to flyash surface with presenting intersection composite-like.Its physicochemical character is as shown in table 1, and CEC, PIC, BET of modified coal ash zeolite composite particles improve 80.3%, 100.3%, 95.3% respectively relative to traditional coal ash zeolite composite particles.
Adopt the waste water of example 1 and techniqueflow to carry out nitrogen phosphorus and remove test, find nitrogen, the more traditional synthetic zeolite from flyash composite particles of the tp removal rate (ZFA of modified synthetic zeolite from flyash composite particles (ZFA-3)
cK) synergy 91.3% and 183.7% respectively.
The performance parameter of table 1 modified synthetic zeolite from flyash composite particles
Claims (6)
1. a preparation method for modified coal ash zeolite composite particles, is characterized in that comprising the steps:
(1) by after flyash oven dry, ground 60 mesh sieves, the acid solution being 1 ~ 3mol/L with concentration is uniformly mixed by solid-to-liquid ratio 1g:3mL, acid etch reaction 0.5 ~ 2h at 60 ~ 100 DEG C of temperature, and cooled and filtered is separated, it is dry at 6 ~ 7,90 DEG C that gained solid water is washed till pH value;
(2) mixed with the raw mineral materials being rich in Si and Al by the flyash through step (1) low-kappa number, obtain grey-ore deposit solid mixture, in ash-ore deposit solid mixture, Si:Al mol ratio is 1 ~ 3:1;
(3) aqueous slkali being 1 ~ 6 mol/L by ash-ore deposit solid mixture and concentration mixes in the ratio of solid-to-liquid ratio 1g:2 ~ 8mL, hydro-thermal reaction 24 ~ 72h at 80 ~ 120 DEG C of temperature, obtains coal ash zeolite composite particles primary product;
(4) coal ash zeolite composite particles primary product mixed by solid-to-liquid ratio 1g:10mL with calcium salt soln or magnesium salt solution, the concentration of calcium salt soln or magnesium salt solution is 0.5 ~ 2 mol/L, normal temperature vibration 24h;
(5) product step (4) obtained after filtration, deionized water washing, until detect cleaning solution without Ca
2+or Mg
2+, then particle is dry, the type that is improved coal ash zeolite composite particles.
2. the preparation method of modified coal ash zeolite composite particles according to claim 1, is characterized in that: the described raw mineral materials being rich in Si and Al is diatomite, kaolin or both mixtures.
3. the preparation method of modified coal ash zeolite composite particles according to claim 1, is characterized in that: described acid-containing solution is hydrochloric acid, sulfuric acid or both mixed liquors.
4. the preparation method of modified coal ash zeolite composite particles according to claim 1, is characterized in that: described is NaOH, potassium hydroxide or both mixed solutions containing aqueous slkali.
5. the preparation method of modified coal ash zeolite composite particles according to claim 1, is characterized in that: described calcium salt is one or more in calcium chloride, calcium nitrate and calcium bicarbonate.
6. the preparation method of modified coal ash zeolite composite particles according to claim 1, is characterized in that: described magnesium salts is a kind of in magnesium chloride and magnesium nitrate or both mixtures.
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