CN108722345B - Zeolite synthesized by using fly ash and method for treating high-concentration ammonia nitrogen wastewater by using zeolite - Google Patents
Zeolite synthesized by using fly ash and method for treating high-concentration ammonia nitrogen wastewater by using zeolite Download PDFInfo
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Abstract
The invention relates to the field of sewage treatment, in particular to zeolite synthesized by using fly ash and a method for treating high-concentration ammonia nitrogen wastewater by using the zeolite, wherein the preparation method of the zeolite comprises pretreatment, and the pretreatment is to obtain washing-acid washing fly ash by sequentially using washing and acid washing fly ash; washing refers to uniformly mixing the fly ash and pure water, stirring for 48 hours at 15-30 ℃, and carrying out solid-liquid separation to obtain washed fly ash; acid washing refers to mixing the washed fly ash with 2mol/L HCl solution in a ratio of 1: 9, stirring for 1h at 80 ℃, then carrying out solid-liquid separation, washing with water, washing with alcohol, and drying to obtain the washing-acid washing fly ash. The zeolite adopts a pretreatment mode combining acid washing and water washing, so that the ammonia nitrogen removal rate of the zeolite is higher than that of the zeolite only subjected to acid washing pretreatment and is far higher than that of the zeolite only subjected to water washing pretreatment; compared with direct pickling, the use amount of hydrochloric acid is reduced by 18.18%, and the preparation cost is reduced.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to zeolite synthesized by using fly ash and a method for treating high-concentration ammonia nitrogen wastewater by using the zeolite.
Background
Ammonia nitrogen is one of the important reasons for eutrophication of water, so that the control of nitrogen load in wastewater treatment, particularly high-concentration ammonia nitrogen wastewater, is particularly critical. The high-concentration ammonia nitrogen wastewater mainly comes from industrial wastewater and aquaculture wastewater. According to the first national pollution source census bulletin (2010), the discharge amount of ammonia nitrogen in various source water pollutants is 172.91 ten thousand tons, and the total nitrogen is 472.89 ten thousand tons. Wherein the ammonia nitrogen production amount of the industrial wastewater is 201.67 ten thousand tons every year, and the ammonia nitrogen in the pollutants which are actually discharged into the environmental water body after being discharged from a factory area and reduced by town sewage treatment and industrial wastewater centralized treatment facilities is 20.76 ten thousand tons. The total nitrogen emission of agricultural sources is 270.46 ten thousand tons, wherein the total nitrogen emission of the livestock and poultry industry is 102.48 ten thousand tons, which accounts for 37.89 percent of the total nitrogen emission of all agricultural gardens, and the method is one of the main approaches for the pollution of agricultural nitrogen sources. In addition, with the stricter emission limit values of ammonia nitrogen and total nitrogen of effluent of water treatment in China, high ammonia nitrogen wastewater in industry, livestock and poultry industry and the like becomes the key point of ammonia nitrogen load control of water environment.
At present, ammonia nitrogen in wastewater is higher than 500mg/L, and a stripping method and a steam stripping method are generally adopted. Aiming at high-concentration special industry wastewater containing ammonia nitrogen (50-500mg/L) and livestock and poultry breeding industry wastewater, two treatment methods adopted at home and abroad are mainly as follows: firstly, denitrification is carried out by a physical and chemical method, wherein the denitrification comprises an ammonium magnesium phosphate precipitation method, a breakpoint chlorination method, an ion exchange method, a zeolite adsorption method and the like; ② a biological denitrification method, including A/O method and A2The O method, SBR method, BAF method and the like. The physicochemical method is limited by different degrees in engineering application due to the limitations of high investment, large energy consumption, high operating cost, complex management, secondary pollution and the like. The biological nitrification and denitrification nitrogen removal method is widely applied to the field of wastewater treatment, and is the most common technical method adopted in domestic wastewater nitrogen removal treatment at present.
When the high-concentration ammonia nitrogen industrial wastewater is treated by a biochemical method, on one hand, the high ammonia nitrogen is usedThe wastewater has poor buffering capacity, a large amount of alkalinity needs to be supplemented to maintain the pH value of the system, and on the other hand, the activity of microorganisms is inhibited by high-concentration free ammonia, so that the biological treatment efficiency is low, and the method is a great difficulty in industrial wastewater treatment. In addition, the denitrification process is further limited due to insufficient carbon source, so that the denitrification effect of the traditional biological deamination process for treating the high-ammonia nitrogen wastewater is poor, the condition that the ammonia nitrogen concentration of effluent is high or the treatment efficiency is unstable generally exists in the industrial wastewater treatment process, and the high-ammonia nitrogen wastewater hardly reaches the standard and is discharged by singly using a biochemical treatment method. When the high-concentration ammonia nitrogen industrial wastewater is biochemically treated, the wastewater is generally subjected to physicochemical pretreatment such as dilution to make the ammonia nitrogen concentration of the wastewater be 300 mg.L-1The following or even lower is followed by a subsequent biological treatment, which considerably increases the total amount of waste water.
Disclosure of Invention
The invention provides a zeolite synthesized by using fly ash, which can adsorb N in high-concentration ammonia nitrogen wastewater at high speed, has small influence of phosphate radicals in the wastewater on ammonia nitrogen absorption, and ensures that ammonia nitrogen in the wastewater is adsorbed at high efficiency.
The zeolite synthesized by using the fly ash is characterized in that the preparation method of the zeolite comprises pretreatment, wherein the pretreatment is to obtain the washing-acid washing fly ash by sequentially using washing and acid washing fly ash.
Further, the washing refers to uniformly mixing the fly ash and pure water, stirring for 48 hours at 25 ℃, and then carrying out solid-liquid separation to obtain the washed fly ash.
Further, the acid washing refers to mixing the washed fly ash with 2mol/L HCl solution in a volume ratio of 9:1, stirring for 1h at 80 ℃, then carrying out solid-liquid separation, washing with water, washing with alcohol, and drying to obtain the washed-acid washed fly ash.
Further, the preparation method of the zeolite further comprises a crystallization step and a hydrothermal synthesis step, wherein the crystallization step is to stir and crystallize the washing-pickling fly ash and 2M NaOH solution for 12 hours at normal temperature and normal pressure, and then carry out ultrasonic treatment on the crystallized mixed solution for 30-40 min. Preferably, the amount of 2M NaOH solution added is 6 mL/g.
Further, the stirring speed of the stirring is 180 r/min.
Further, the hydrothermal synthesis step is to react the mixed solution after the ultrasonic treatment at 95 ℃ for 48 hours to obtain synthetic zeolite, and the synthetic zeolite is washed with water, washed with alcohol, dried and sieved to obtain a finished zeolite product.
The invention also provides a method for treating high-concentration ammonia nitrogen wastewater by using the zeolite, which is characterized by comprising two steps of physical adsorption and biochemical treatment, wherein the physical adsorption is to add the zeolite into the wastewater and perform adsorption reaction after uniform mixing.
Furthermore, the wastewater inlet water quality index is pH6-8, ammonia nitrogen concentration 100-.
Further, the adding amount of the zeolite is 10g/L and 30g/L respectively.
Further, the time of the adsorption reaction is 20 minutes.
The invention has the beneficial effects that:
1. the zeolite of the invention is prepared by adopting a pretreatment mode of combining water washing and acid washing to pretreat the fly ash and then synthesizing the zeolite. The ammonia nitrogen removal rate of the zeolite is higher than that of zeolite synthesized by only using acid washing pretreatment fly ash and is far higher than that of zeolite synthesized by only using water washing pretreatment fly ash; meanwhile, compared with direct pickling, the pretreatment mode of water washing-pickling combination reduces the use amount of 18.18 percent of hydrochloric acid and reduces the preparation cost;
2. the zeolite provided by the invention has a high adsorption rate, can complete adsorption reaction in the first 20 minutes, and is favorable for improving the wastewater treatment efficiency, and t is obtained by the zeolite in a quasi-second-order kinetic model0.5The values are 12.01min, 8.83min, 6.75min and 5.87min respectively.
3. In the zeolite provided by the invention, in the treatment process, the coexisting ions such as phosphate and the like have no obvious influence on the ammonia nitrogen removal effect, when the initial concentration of the wastewater is 20-500mg/L and the P/N is increased from 0.1 to 1, the adsorption capacity of the synthetic zeolite on the ammonia nitrogen is weakened by the presence of the phosphate, but the influence is weak, and the highest nitrogen removal rate is only reduced by 6.87%; when the zeolite is used for treating the high ammonia nitrogen wastewater, the ammonia nitrogen adsorption efficiency of the zeolite is slightly influenced by other ions, so that the rapid removal of ammonia nitrogen is facilitated, and the next biochemical treatment can be conveniently carried out.
4. The invention adopts the fly ash to synthesize the zeolite, thereby not only realizing the resource utilization of the fly ash, but also removing the ammonia nitrogen in the wastewater, treating the wastewater by using the waste, and having great significance for the biochemical treatment of the high ammonia nitrogen wastewater and the alleviation of the eutrophication of the water body
5. Aiming at the comprehensive water inflow of a pig farm with the ammonia nitrogen concentration of 584mg/L, the actual ammonia nitrogen removal rate is 21.64-64.34% when the adding amount is 10-60 g/L. When the adding amount of the fly ash synthetic zeolite is 60g/L, the ammonia nitrogen adsorption removal rate is as high as 64.34%, and the inhibition of high-concentration ammonia nitrogen on the microbial activity in the follow-up biochemical treatment of the wastewater of the pig farm can be greatly reduced.
6. Aiming at biochemical unit effluent with the ammonia nitrogen concentration of 189mg/L, when the adding amount of zeolite is 10-30 g/L, the removal rate is 61.88-75.61%. The concentration of the ammonia nitrogen in the effluent is 46.10-72.0 mg/L, which is lower than that of the NH in the effluent in GB18596-2001 discharge Standard of pollutants for livestock and poultry Breeding4 +Concentration limit (80 mg/L). The optimally prepared fly ash synthetic wastewater is adopted to treat the high ammonia nitrogen wastewater in the pig farm, so that the feasibility is good, the increase of the energy consumption cost of directly carrying out aerobic treatment aeration can be avoided, and the standard discharge of the effluent is ensured.
Drawings
FIG. 1 is a diagram showing the ammonia nitrogen removal effect of pretreated fly ash synthetic zeolite. In fig. 1, the abscissa is time (min) and the ordinate is ammonia nitrogen removal efficiency (%);
FIG. 2 is an X-ray diffraction pattern of a fly ash synthetic zeolite. In fig. 1, the abscissa is 2Theta (°), and the ordinate is the peak intensity;
FIG. 3 is a diagram of ammonia nitrogen adsorption effect of simulated wastewater from fly ash zeolite treatment, wherein in FIG. 3, the abscissa is ammonia nitrogen concentration (mg/L) in wastewater at equilibrium, and the ordinate is ammonia nitrogen removal load (mg-N/g);
FIG. 4 shows the effect of P/N ratio on ammonia nitrogen adsorption effect of simulated wastewater from synthetic zeolite treatment. In FIG. 4, the abscissa is different initial ammonia nitrogen concentrations (mg/L) and the ordinate is ammonia nitrogen removal efficiency (%);
FIG. 5 is a kinetic diagram of adsorption of high-concentration ammonia nitrogen in pretreatment of fly ash zeolite, wherein the abscissa in FIG. 5 is reaction time (min), and the abscissa is qe(mg-N/g)；
FIG. 6 is a simulated diagram of quasi-secondary dynamics of high-concentration ammonia nitrogen in pretreatment of fly ash zeolite, wherein the abscissa in FIG. 6 is reaction time (min), and the abscissa is t/qe(min.g/mg)；
FIG. 7 is a graph showing the adsorption effect of ammonia nitrogen in the supernatant of the fly ash zeolite-treated pig farm water intake and ammonia nitrogen pretreatment; in FIG. 7, (a) a comprehensive influent ammonia nitrogen adsorption effect diagram of a zeolite-treated pig farm and (b) an effluent ammonia nitrogen adsorption effect diagram of a biochemical unit of the zeolite-treated pig farm.
Detailed Description
The present invention will be further described with reference to the following specific embodiments
Example 1: a method for pretreating high-concentration ammonia nitrogen wastewater by utilizing fly ash zeolite comprises the following steps of:
(1) pretreatment of fly ash
The fly ash and deionized water are uniformly mixed in a beaker according to a proper volume ratio, and then the mixture is placed in a magnetic stirrer in a constant-temperature water area and stirred for 48 hours at the temperature of 25 ℃ and the speed of 1800r/min for water washing pretreatment. After the washing, the mixture was centrifuged to separate the solid and liquid, and the supernatant was discarded. And washing the centrifugal washing fly ash with absolute ethyl alcohol, and repeating the operation for 3 times. And taking the dried fly ash, and sieving in a 200-mesh standard sieve. The screened material is the washing fly ash prepared by the experiment, and the washing fly ash is stored in a dryer for standby.
(2) Preparation of zeolites
Pretreating fly ash and 2M NaOH solution by a reaction of 1: the mixture is uniformly mixed in a high-pressure reaction kettle according to the ratio of 6 (W/V). Crystallizing at room temperature and normal pressure for 12h under the condition of magnetic stirring. And (3) placing the crystallized mixed solution in an ultrasonic device, carrying out ultrasonic treatment for 30-40 min, transferring the mixed solution into an oven, reacting for 48h at 95 ℃ under the condition of standard atmospheric pressure, and carrying out hydrothermal synthesis on the zeolite.
The synthetic zeolite was washed with deionized water 6 times and 95% ethanol 3 times, respectively. The cleaned zeolite is dried in a constant temperature oven. And (4) sieving the dried zeolite with a 200-mesh sieve, and storing in a dryer for later use.
Example 2: a method for pretreating high-concentration ammonia nitrogen wastewater by utilizing fly ash zeolite comprises the following steps of:
(1) pretreatment of fly ash
Mixing fly ash with 2mol/L HCL solution, mixing the fly ash with the solution at a ratio of 11: 1(V/W) volume ratio in a beaker, then placing the mixture in a magnetic stirrer in a constant temperature water area, stirring the mixture for 1 hour at 80 ℃ and 1800r/min, and carrying out acid cleaning pretreatment. After the acid washing is finished, performing solid-liquid separation by centrifugation, and discarding the supernatant. Deionized water is adopted to clean residual Cl-in the acid-washed fly ash, and 0.1mol/L AgNO is adopted after centrifugation3Solution detection of Cl in supernatant-And (4) content. The above operation was repeated until no Cl could be detected in the supernatant-Is present.
Then, 95% absolute ethyl alcohol and the acid-washed fly ash are evenly mixed and then centrifuged to carry out solid-liquid separation, and the operation is repeated for 3 times. The obtained fly ash is dried for 24 hours at 105 ℃. And taking the dried fly ash, and sieving in a 200-mesh standard sieve. The screened material is the acid-washed fly ash prepared by the experiment, and the acid-washed fly ash is stored in a dryer for standby.
The subsequent fly ash zeolite preparation method was the same as in example 1.
Example 3: a method for pretreating high-concentration ammonia nitrogen wastewater by utilizing fly ash zeolite comprises the following steps of:
the fly ash and deionized water are uniformly mixed in a beaker according to a proper volume ratio, and then the mixture is placed in a constant-temperature water magnetic stirrer and stirred for 48 hours at the temperature of 25 ℃ and under the condition of 180r/min for water washing pretreatment. After the washing, the mixture is centrifuged for 30min at 5000r/min, solid-liquid separation is carried out, and the supernatant is discarded. And washing the centrifugal washing fly ash with absolute ethyl alcohol, and repeating the operation for 3 times. And taking the dried fly ash, and sieving in a 200-mesh standard sieve. The screened material is the washing fly ash prepared by the experiment, and the washing fly ash is stored in a dryer for standby.
Mixing the washed fly ash with 2mol/L HCL solution according to the weight ratio of 9: 1(V/W) volume ratio, then placing the mixture into a magnetic stirrer in a constant temperature water area, and stirring the mixture for 1 hour at 80 ℃ and 180r/min for acid cleaning pretreatment. After the acid washing is finished, performing solid-liquid separation by centrifugation, and discarding the supernatant. Deionized water is adopted to clean residual Cl-in the acid-washed fly ash, and 0.1mol/L AgNO is adopted after centrifugation3Solution detection of Cl in supernatant-And (4) content. The above operation was repeated until no Cl could be detected in the supernatant-Is present.
Then, 95% absolute ethyl alcohol and the acid-washed fly ash are uniformly mixed, and the mixture is centrifuged to carry out solid-liquid separation, and the operation is repeated for 3 times. And taking the dried fly ash, and sieving in a 200-mesh standard sieve. The screened material is the washing-pickling fly ash prepared by the experiment, and the washing-pickling fly ash is stored in a dryer for later use.
The subsequent preparation method is the same as example 1.
Example 4: the application of the method for pretreating high-concentration ammonia nitrogen wastewater by using fly ash zeolite in high ammonia nitrogen simulation wastewater comprises the following steps:
weighing 1g of optimally prepared zeolite into a 250mL reactor, adding 100mL of simulated wastewater with initial ammonia nitrogen concentration of 10-2000 mg/L respectively, placing the wastewater on a constant-speed shaking table, and carrying out isothermal adsorption thermodynamic experiments on the synthesized zeolite. And (4) measuring the ammonia nitrogen equilibrium concentration, and calculating the ammonia nitrogen equilibrium adsorption quantity. According to the ammonia nitrogen equilibrium concentration and the equilibrium adsorption quantity, fitting and analysis discussion of an isothermal adsorption model for adsorbing ammonia nitrogen by synthetic zeolite are carried out, the result is shown in an attached figure 3, and the kinetic parameters are shown in a table 1.
TABLE 1 synthetic zeolite isothermal adsorption Ammonia Nitrogen parameters
The initial ammonia nitrogen concentration of the simulated wastewater in each reactor is 20-500mg/L, and the phosphate concentration is adjusted to ensure that the initial P/N ratio is respectively as follows: 0.1,0.5,1. The prepared zeolite is used for treating ammonia nitrogen simulation wastewater with the dosage of 10g/L, and after reacting for 2 hours, the ammonia nitrogen concentration of the wastewater under each initial P/N ratio condition is measured. And calculating the ammonia nitrogen removal efficiency. The results are shown in FIG. 4.
Example 5: the application of the method for pretreating high-concentration ammonia nitrogen wastewater by using fly ash zeolite in high ammonia nitrogen simulation wastewater comprises the following steps:
weighing 1g of optimally prepared zeolite into a 250mL reactor, adding 100mL of simulated wastewater with initial ammonia nitrogen concentration of 20-500mg/L respectively, placing the wastewater on a constant-speed shaking table, and carrying out an ammonia nitrogen adsorption kinetic experiment of the synthetic zeolite. And measuring the ammonia nitrogen equilibrium concentration in the reactor, and calculating the equilibrium adsorption quantity of the ammonia nitrogen. According to the change relationship between the adsorption quantity and the adsorption time, an ammonia nitrogen adsorption kinetic curve is drawn and shown in the attached figure 5 and the attached figure 6, and kinetic parameters are shown in a table 2.
TABLE 2 synthetic zeolite adsorption ammonia nitrogen quasi-second order kinetic parameters
Example 6: an application of a method for pretreating high-concentration ammonia nitrogen wastewater by using fly ash zeolite in pretreatment of aquaculture wastewater:
the water quality indexes in the aquaculture wastewater are as follows: the pH value is 6-8, the ammonia nitrogen concentration is 100-600mg/L, the TN is 100-700, the COD is 200-4000mg/L, the orthophosphoric acid is 10-60mg/L, and the TP is 60-200 mg/L.
The prepared fly ash zeolite is respectively put into a pig farm comprehensive water inlet and a biochemical unit water outlet in an adding amount of 5-60g/L, and a sample is taken to determine the ammonia nitrogen concentration in the wastewater after continuous operation for 2 hours. The results are shown in FIG. 7.
The comprehensive water inflow of the pig farm with the ammonia nitrogen concentration of 584mg/L is realized, and when the adding amount is 10-60 g/L, the actual ammonia nitrogen removal rate is 21.64-64.34%. When the adding amount of the fly ash synthetic zeolite is 60g/L, the ammonia nitrogen adsorption removal rate is as high as 64.34%, and the inhibition of high-concentration ammonia nitrogen on the microbial activity in the follow-up biochemical treatment of the wastewater of the pig farm can be greatly reduced.
The ammonia nitrogen concentration of the biochemical unit effluent is 189mg/L, and when the adding amount of the zeolite is 10-30 g/L, the removal rate is 61.88-75.61%. The concentration of the ammonia nitrogen in the effluent is 46.10-72.0 mg/L, which is lower than GB18596-2001 discharge Standard of pollutants for livestock and poultry BreedingMiddle effluent NH4 +Concentration limit (80 mg/L). The optimally prepared fly ash synthetic wastewater is adopted to treat the high ammonia nitrogen wastewater in the pig farm, so that the feasibility is good, the increase of the energy consumption cost of directly carrying out aerobic treatment aeration can be avoided, and the standard discharge of the effluent is ensured.
Claims (6)
1. A method for treating high-concentration ammonia nitrogen wastewater by using fly ash synthetic zeolite is characterized by comprising two steps of physical adsorption and biochemical treatment, wherein the physical adsorption is to add zeolite into wastewater and uniformly mix the zeolite for adsorption reaction;
the preparation method of the zeolite comprises pretreatment, wherein the pretreatment is to obtain washing-acid washing fly ash by sequentially utilizing washing and acid washing fly ash; the washing is to uniformly mix the fly ash and pure water, stir the mixture for 48 hours at the temperature of 15-30 ℃, and then carry out solid-liquid separation to obtain washed fly ash; the acid washing is to mix the washed fly ash with 2mol/L HCl solution in a volume ratio of 9:1, stir for 1h at 80 ℃, then carry out solid-liquid separation, wash with water, wash with alcohol and dry to obtain washed-acid washed fly ash;
the preparation method of the zeolite further comprises a crystallization step and a hydrothermal synthesis step, wherein the crystallization step is to stir the washed-acid-washed fly ash and 2M NaOH solution for 12 hours at normal temperature and normal pressure, and then carry out ultrasonic treatment for 30-40 min; and the hydrothermal synthesis step is to react the mixed solution after the ultrasonic treatment for 48 hours at the temperature of 95 ℃ to obtain synthetic zeolite, and the synthetic zeolite is washed with water, washed with alcohol, dried and sieved to obtain a finished zeolite product.
2. The method of claim 1, wherein the amount of 2M NaOH solution added in the crystallization step is 6 mL/g.
3. The method of claim 2, wherein the stirring is performed at a rotational speed of 180 r/min.
4. The method of claim 3, wherein the wastewater influent water quality index is pH6-8, ammonia nitrogen concentration 100
600mg/L, TN 100-700, COD 200-4000mg/L, orthophosphoric acid 10-60mg/L, TP60-200 mg/L.
5. The method of claim 4, wherein the zeolite is added in an amount of 10g/L or 30g/L to the wastewater.
6. The method of claim 5, wherein the adsorption reaction is for a period of 20 minutes.
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| CN112195029B (en) * | 2020-10-28 | 2021-07-27 | 东北大学 | Method and device for preparing soil conditioner by using coal ash synthetic zeolite to treat wastewater |
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| CN113072122A (en) * | 2021-03-16 | 2021-07-06 | 南昌大学 | Treatment scheme and device for ammonia nitrogen adsorption of acid modified fly ash |
| CN113371783A (en) * | 2021-06-11 | 2021-09-10 | 东北大学 | Method for treating nitrogen and phosphorus wastewater by using water-quenched slag-fly ash-based 4A zeolite |
| CN113477213A (en) * | 2021-07-09 | 2021-10-08 | 武汉工程大学 | Preparation method of composite nanocrystalline adsorption material |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798124A (en) * | 2010-04-10 | 2010-08-11 | 太原理工大学 | Method for treating ammonia and nitrogen in coking wastewater |
| CN102764671A (en) * | 2012-08-03 | 2012-11-07 | 东北石油大学 | Method for preparing denitration catalyst by coal ash |
| JP2015004655A (en) * | 2013-05-24 | 2015-01-08 | アタカ大機株式会社 | Method for highly concentrating radioactive cesium separated from drain water |
| CN104437354A (en) * | 2014-12-01 | 2015-03-25 | 浙江大学 | Method for preparing improved coal ash-zeolite composite particles |
| CN106082267A (en) * | 2016-06-16 | 2016-11-09 | 中国华能集团公司 | A kind of use microwave hydrothermal coupling process by coal ash for manufacturing for the method for SAPO 34 molecular sieve |
| KR20170000372A (en) * | 2016-12-18 | 2017-01-02 | 서희동 | Method of manufacturing kalium type artificial zeolite from coal fly ash |
| CN106865565A (en) * | 2017-03-26 | 2017-06-20 | 天津大学 | A kind of flyash synthesizes the method for X-type zeolite |
-
2018
- 2018-05-24 CN CN201810508635.0A patent/CN108722345B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798124A (en) * | 2010-04-10 | 2010-08-11 | 太原理工大学 | Method for treating ammonia and nitrogen in coking wastewater |
| CN102764671A (en) * | 2012-08-03 | 2012-11-07 | 东北石油大学 | Method for preparing denitration catalyst by coal ash |
| JP2015004655A (en) * | 2013-05-24 | 2015-01-08 | アタカ大機株式会社 | Method for highly concentrating radioactive cesium separated from drain water |
| CN104437354A (en) * | 2014-12-01 | 2015-03-25 | 浙江大学 | Method for preparing improved coal ash-zeolite composite particles |
| CN106082267A (en) * | 2016-06-16 | 2016-11-09 | 中国华能集团公司 | A kind of use microwave hydrothermal coupling process by coal ash for manufacturing for the method for SAPO 34 molecular sieve |
| KR20170000372A (en) * | 2016-12-18 | 2017-01-02 | 서희동 | Method of manufacturing kalium type artificial zeolite from coal fly ash |
| CN106865565A (en) * | 2017-03-26 | 2017-06-20 | 天津大学 | A kind of flyash synthesizes the method for X-type zeolite |
Non-Patent Citations (3)
| Title |
|---|
| Conversion of waste incineration fly ash into zeolite A and zeolite P by hydrothermal treatment;Tamura, C. et al.;《JOURNAL OF THE CERAMIC SOCIETY OF JAPAN》;20060228;第114卷(第1326期);205-209 * |
| Study on Washing Method of Hydrothermal Synthesis Zeolite from Coal Fly Ash;Hongmei Cui et al.;《Advanced Materials Research》;20131231;2687-2691 * |
| 粉煤灰制备分子筛研究现状;林伟等;《安徽化工》;20170228;9-11 * |
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| CN108722345A (en) | 2018-11-02 |
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