CN102671623A - Preparation method of fly ash based zeolite / alumina composite adsorbing material - Google Patents
Preparation method of fly ash based zeolite / alumina composite adsorbing material Download PDFInfo
- Publication number
- CN102671623A CN102671623A CN2012101633553A CN201210163355A CN102671623A CN 102671623 A CN102671623 A CN 102671623A CN 2012101633553 A CN2012101633553 A CN 2012101633553A CN 201210163355 A CN201210163355 A CN 201210163355A CN 102671623 A CN102671623 A CN 102671623A
- Authority
- CN
- China
- Prior art keywords
- zeolite
- preparation
- fly ash
- alumina composite
- adsorbing material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a preparation method of fly ash based zeolite / alumina composite adsorbing material, which comprises the following steps: metal lye solution and fly ash are mixed to be subjected to hydrothermal synthesis reaction; soluble aluminum stearate solution is continuously added in the mixture of the synthetic zeolite and waste lye liquor under stirring drop by drop, after solid-liquid separation, the solid phase is subjected to heat treatment to obtain zeolite / alumina composite adsorbent material, and the remaining solution is used to the preparation of lye solution in the subsequent synthesis process. According to the preparation method of the fly ash based zeolite / alumina composite adsorbing material, the waste lye liquor generated during the zeolite synthetizing with fly ash is changed into alumina, so that the long-standing unsolved problems that waste lye produced when the fly ash is used as raw material to produce zeolite cannot be treated, and the zeolite product has strong basicity can be solved, and the prepared zeolite / alumina composite adsorbing material has more efficient adsorption effect on nitrogen and phosphorus nutrients in the water, so the treatment of wastes with processes of waster against one another can be achieved; and the synthesis process is simple, and the cost is low.
Description
Technical field
The present invention relates to the method in a kind of Environmental Technology field, being specifically related to a kind of is the method that basic material prepares the Zeolite/alumina composite adsorbing material with flyash.
Background technology
Flyash is a kind of worldwide solid waste, is that it is handled and causes the scholar and the public's extensive concern already by the remaining ash that produces behind the coal burning.At present, aspect the utilizing again of flyash, mainly be batching as building materials such as cement and concrete.On the one hand, the amount of the used flyash of building trade is limited after all, on the other hand, sees from permanent continuable being used to again, also very be necessary to seek surcharge higher utilize method again.
Literature search through to prior art is found; Number of patent application is that to have proposed a kind of be the method for raw material synthetic zeolite with flyash for 200410084313.6 Chinese patent; The zeolite of this method preparation has good effect to the removal of nitrogen phosphorus nutrition element in the water; Therefore solve the high added value that fly-ash Preparation is become zeolite and is used for water treatment and utilized problem again, created a kind of novel approach that utilizes of flyash.
But spent lye problem and zeolite product that this method still exists building-up process to produce are alkaline problem.In Hydrothermal Preparation zeolite process, need to use a large amount of alkali lye, concentration of lye is generally 1～5M (molar concentration).The general liquid-solid ratio that adopts is 5～10 liters/kilogram, that is to say that 1 ton of zeolite of every production will produce 5～10 tons of spent lyes.Although the recycle of salkali waste fluid power is synthetic in zeolite in principle, the alkali concn of spent lye is lower than former alkali lye, if do not adjust concentration during recycle or the concentration adjustment is inaccurate, will make product quality obviously become bad or unstable; Except that alkali, also contain the alkali solubility composition in the flyash in the spent lye, and the recycle number of times is many more, these compositions accumulate manyly more, will the quality of synthetic zeolite be exerted an influence; In addition, even the zeolite product after the Separation of Solid and Liquid still generally presents strong basicity through repeatedly washing, limited its application, and also will produce low concentration spent lye problem in the washing process.But still be not directed against the good solution that spent lye problem and zeolite product are the strong basicity problem at present.
Summary of the invention
The objective of the invention is to deficiency, propose both to have solved the harm problem that spent lye causes environment in the prior art processes, simultaneously spent lye is carried out the preparation method of the fly ash base Zeolite/alumina composite adsorbing material of recycling to prior art.Specifically be that raw material prepares zeolite through the hydro-thermal reaction under the alkali condition with flyash; In same agitated reactor; And then spent lye is converted into hydrated alumina, the solid phase product that after Separation of Solid and Liquid, obtains is prepared into the Zeolite/alumina compound adsorbent through heat treatment; And the no alkali wasteliquid that after Separation of Solid and Liquid, obtains can be used for alkali lye preparation once more, and circulation is used for the synthetic zeolite technical process, thereby realizes the zero-emission of waste liquid.
The objective of the invention is to realize through following technical scheme:
The present invention relates to a kind of preparation method of fly ash base Zeolite/alumina composite adsorbing material, may further comprise the steps:
Step 1 is got metal base solution, mixes with flyash, and cool off the reaction back, obtains the mixture of zeolite and spent lye;
Step 2 adopts the mode that drips continuously, under stirring condition, in said mixture, adds the soluble aluminum salting liquid; Then carry out Separation of Solid and Liquid, solid phase obtains fly ash base Zeolite/alumina composite adsorbing material through heat treatment.
Preferably, the liquid phase in the step 2 after the Separation of Solid and Liquid is used for the preparing metal aqueous slkali, and the metal base solution of this preparation is used for the preparation of follow-up Zeolite/alumina composite adsorbing material.
Preferably, in the step 1, said soluble metal aqueous slkali is that molar concentration is NaOH or the potassium hydroxide solution of 1～5M.
Preferably, in the step 1, the said mixing with flyash is specially: the ratio that adds 1.5～10L metal base solution in every kilogram of flyash is mixed.
Preferably, in the step 1, the temperature of said reaction is 80～200 ° of C, and the time is 3～24 hours.
Preferably, in the step 2, the speed of said continuous dropping is 10～100ml/min.
Preferably, in the step 2, said aluminum soluble salt is that molar concentration is the aluminium chloride of 0.5～5M.
Preferably, in the step 2, said Separation of Solid and Liquid is filtration or centrifugal.
Preferably, in the step 2, the atmosphere that said heat treatment is adopted is air, and temperature is 105～500 ° of C.
It is raw material that the present invention adopts the flyash behind the coal burning, and through the improvement to synthetic zeolite technology, preparation Zeolite/alumina composite adsorbing material makes that the spent lye in the synthesis technique is rationally disposed and recycling.Compare with the flyash synthetic zeolite, the novel absorption material of preparation has stronger adsorption effect to the nitrogen and phosphorous nutrient in the water.
Compared with prior art, the present invention has the following advantages:
1, the spent lye in the fly ash base zeolite production process can be utilized fully, therefore can not cause secondary pollution to environment;
2, compare with the flyash synthetic zeolite, the Zeolite/alumina composite adsorbing material of preparation has higher deamination phosphor-removing effect.
3, zeolite preparation (step 1) and spent lye are converted into aluminium oxide (step 2) and can in same agitated reactor, carry out, so preparation technology is uncomplicated, helps realizing low cost movement;
4, using by pollutant in the compound adsorbent adsorption treatment sewage of fly-ash Preparation, is the engineering of a treatment of wastes with processes of wastes against one another;
5 so long as handle the nitrogen phosphorus waste water (the for example sanitary sewage after the biochemical treatment) that does not contain hazardous substance, and the synthetic compound adsorbent of the flyash that contains high concentration N-P after absorption reaches capacity can also be applied in the farmland; Can solve the environmental problem that nitrogen phosphorus nutrition pollutant causes in flyash solid discarded object and the sewage simultaneously, also can realize the resource of nitrogen phosphorus in resource and the sewage of flyash simultaneously.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.Following examples will help those skilled in the art further to understand the present invention, but not limit the present invention in any form.Should be pointed out that to those skilled in the art, under the prerequisite that does not break away from the present invention's design, can also make some adjustment and improvement.These all belong to protection scope of the present invention.
The main physical and chemical of the flyash that adopts among the embodiment such as following table 1.Carry out following each embodiment by technological process shown in the accompanying drawing 1.
Table 1 flyash is mainly formed
| Constituent | Content (%) |
| Na 2O | 0.49 |
| MgO | 0.69 |
| Al 2O 3 | 39.4 |
| SiO 2 | 49.7 |
| SO 3 | 0.60 |
| Cl | 0.04 |
| K 2O | 1.6 |
| CaO | 2.4 |
| TiO 2 | 1.7 |
| Fe 2O 3 | 3.0 |
| Other | 0.38 |
Embodiment 1
Step 1; In double-layer glass reaction kettle (open system), add 2M (molar concentration) sodium hydroxide solution and flyash by liquid-solid ratio 10:1 (L/kg), 80 ℃ of control temperature of reaction kettle, mixing speed is 120rpm; After the hydro-thermal reaction 24 hours, the cooling suspension is to room temperature.
Step 2 is got Aluminium chloride hexahydrate and is dissolved in the water, and preparation concentration is 0.5M (molar concentration) aluminum chloride aqueous solution.The mode of liquor alumini chloridi with Continuous Titration joined in the glass reaction still, and rate of titration is 10ml/min, and mixing speed is 60rpm, and reaction temperature is 20 ℃, and terminal point pH is 6.0.After reaction is accomplished, centrifugation, the liquid that obtains collects and continues on for follow-up sodium hydroxide solution preparation; The solid that obtains places Muffle furnace calcining 2 hours, and 250 ℃ of calcining heats promptly obtain the Zeolite/alumina composite adsorbing material.
Implementation result: the cation exchange capacity of the Zeolite/alumina composite adsorbing material that present embodiment prepares is 166cmol/kg, and removing phosphate capacity is 72mg/g; Behind this material processed sewage treatment plant secondary biochemical sewage (ammonia nitrogen 22mg/L before handling, phosphorus 4.5mg/L), purification efficiency is: ammonia nitrogen 64%, phosphorus 95%.
Embodiment 2
Step 1; In double-layer glass reaction kettle (open system), add 5M (molar concentration) potassium hydroxide solution and flyash by liquid-solid ratio 1.5:1 (L/kg), 100 ℃ of control temperature of reaction kettle, mixing speed is 120rpm; After the hydro-thermal reaction 12 hours, the cooling suspension is to room temperature.
Step 2 is got Aluminium chloride hexahydrate and is dissolved in the water, and preparation concentration is 2.5M (molar concentration) aluminum chloride aqueous solution.The mode of liquor alumini chloridi with Continuous Titration joined in the glass reaction still, and rate of titration is 50ml/min, and mixing speed is 60rpm, and reaction temperature is 20 ℃, and terminal point pH is 7.0.After reaction is accomplished, centrifugation, the liquid that obtains collects and continues on for follow-up potassium hydroxide solution preparation; The solid that obtains after 4 hours, promptly obtains the Zeolite/alumina composite adsorbing material in 105 ℃ of dryings.
Implementation result: the cation exchange capacity of the Zeolite/alumina composite adsorbing material that present embodiment prepares is 123cmol/kg, and removing phosphate capacity is 65mg/g; Behind this material processed sewage treatment plant secondary biochemical sewage (ammonia nitrogen 22mg/L before handling, phosphorus 4.5mg/L), purification efficiency is: ammonia nitrogen 68%, phosphorus 90%.
Embodiment 3
Step 1; In stainless steel cauldron (closed system), add 1M (molar concentration) sodium hydroxide solution and flyash by liquid-solid ratio 6:1 (L/kg), 200 ℃ of control temperature of reaction kettle, mixing speed is 80rpm; After the hydro-thermal reaction 3 hours, the cooling suspension is to room temperature.
Step 2 is got Aluminium chloride hexahydrate and is dissolved in the water, and preparation concentration is 5M (molar concentration) aluminum chloride aqueous solution.The mode of liquor alumini chloridi with Continuous Titration joined in the stainless steel cauldron, and rate of titration is 100ml/min, and mixing speed is 60rpm, and reaction temperature is 25 ℃, and terminal point pH is 5.5.After reaction is accomplished, isolated by filtration, the liquid that obtains collects and continues on for follow-up sodium hydroxide solution preparation; The solid that obtains places Muffle furnace calcining 2 hours, and 450 ℃ of calcining heats promptly obtain the Zeolite/alumina composite adsorbing material.
Implementation result: the cation exchange capacity of the Zeolite/alumina composite adsorbing material that present embodiment prepares is 195cmol/kg, and removing phosphate capacity is 85mg/g; Behind this material processed sewage treatment plant secondary biochemical sewage (ammonia nitrogen 22mg/L before handling, phosphorus 4.5mg/L), purification efficiency is: ammonia nitrogen 75%, phosphorus 99%.
Can know that by embodiment 1～3 the Zeolite/alumina composite adsorbing material of the present invention's preparation has higher deamination phosphor-removing effect.In addition, because the synthetic compound adsorbent mesolite of flyash itself has the effect of improvement agricultural land soil, especially promote the formation of soil aggregate and the improvement of fertilizer-preserving ability; Treated nitrogenous phosphorus waste water (the nitrogen phosphorus waste water that does not contain hazardous substance, for example: be applied to the farmland the sanitary sewage after the biochemical treatment) again, the nitrogen phosphorus of absorption can supply crops to utilize, thereby can save the fertilizer spending and alleviate the agricultural wastewater pollution problem; Therefore present technique can solve the environmental problem that nitrogen phosphorus nutrition pollutant causes in flyash solid discarded object and the sewage simultaneously, and can realize the resource of nitrogen phosphorus in resource and the sewage of flyash simultaneously.
Claims (9)
1. the preparation method of a fly ash base Zeolite/alumina composite adsorbing material is characterized in that, may further comprise the steps:
Step 1 is got metal base solution, mixes with flyash, and cool off the reaction back, obtains the mixture of zeolite and spent lye;
Step 2 adopts the mode that drips continuously, under stirring condition, in said mixture, adds the soluble aluminum salting liquid; Then carry out Separation of Solid and Liquid, solid phase obtains fly ash base Zeolite/alumina composite adsorbing material through heat treatment.
2. the preparation method of fly ash base Zeolite/alumina composite adsorbing material according to claim 1; It is characterized in that; Liquid phase in the step 2 after the Separation of Solid and Liquid is used for the preparing metal aqueous slkali, and the metal base solution of this preparation is used for the preparation of follow-up Zeolite/alumina composite adsorbing material.
3. the preparation method of fly ash base Zeolite/alumina composite adsorbing material according to claim 1 is characterized by, and in the step 1, said soluble metal aqueous slkali is that molar concentration is NaOH or the potassium hydroxide solution of 1～5M.
4. the preparation method of fly ash base Zeolite/alumina composite adsorbing material according to claim 1 is characterized by, and in the step 1, the said mixing with flyash is specially: the ratio that adds 1.5～10L metal base solution in every kilogram of flyash is mixed.
5. the preparation method of fly ash base Zeolite/alumina composite adsorbing material according to claim 1 is characterized by, and in the step 1, the temperature of said reaction is 80～200 ° of C, and the time is 3～24 hours.
6. the preparation method of fly ash base Zeolite/alumina composite adsorbing material according to claim 1 is characterized by, and in the step 2, the speed of said continuous dropping is 10～100ml/min.
7. the preparation method of fly ash base Zeolite/alumina composite adsorbing material according to claim 1 is characterized by, and in the step 2, said aluminum soluble salt is that molar concentration is the aluminium chloride of 0.5～5M.
8. the preparation method of fly ash base Zeolite/alumina composite adsorbing material according to claim 1 is characterized by, and in the step 2, said Separation of Solid and Liquid is filtration or centrifugal.
9. the preparation method of fly ash base Zeolite/alumina composite adsorbing material according to claim 1 is characterized by, and in the step 2, the atmosphere that said heat treatment is adopted is air, and temperature is 105～500 ° of C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101633553A CN102671623A (en) | 2012-05-23 | 2012-05-23 | Preparation method of fly ash based zeolite / alumina composite adsorbing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101633553A CN102671623A (en) | 2012-05-23 | 2012-05-23 | Preparation method of fly ash based zeolite / alumina composite adsorbing material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102671623A true CN102671623A (en) | 2012-09-19 |
Family
ID=46804563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101633553A Pending CN102671623A (en) | 2012-05-23 | 2012-05-23 | Preparation method of fly ash based zeolite / alumina composite adsorbing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102671623A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920458A (en) * | 2014-03-18 | 2014-07-16 | 上海交通大学 | Preparation method for water body eutrophication treatment rare earth composite material |
| CN110385104A (en) * | 2019-05-17 | 2019-10-29 | 北京化工大学 | A kind of modified zeolite flyash composite adsorbing material and preparation method thereof |
| CN111097374A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院生态环境研究中心 | Preparation method of oxygen-carrying and adsorption composite functional material and application of oxygen-carrying and adsorption composite functional material in water body remediation |
| CN111097373A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院生态环境研究中心 | Porous adsorption material, oxygen-carrying and adsorption composite functional material and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456612A (en) * | 2008-07-23 | 2009-06-17 | 刘转年 | Clean production novel process for preparing environment pollution treatment material by fly ash |
| CN102091593A (en) * | 2010-12-07 | 2011-06-15 | 浙江大学 | Preparation method of functionalized fly ash and zeolite composite particles |
-
2012
- 2012-05-23 CN CN2012101633553A patent/CN102671623A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456612A (en) * | 2008-07-23 | 2009-06-17 | 刘转年 | Clean production novel process for preparing environment pollution treatment material by fly ash |
| CN102091593A (en) * | 2010-12-07 | 2011-06-15 | 浙江大学 | Preparation method of functionalized fly ash and zeolite composite particles |
Non-Patent Citations (1)
| Title |
|---|
| 童军杰等: "粉煤灰制取沸石分子筛的新进展", 《太原科技》, no. 2, 26 April 2003 (2003-04-26), pages 7 - 3 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920458A (en) * | 2014-03-18 | 2014-07-16 | 上海交通大学 | Preparation method for water body eutrophication treatment rare earth composite material |
| CN111097374A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院生态环境研究中心 | Preparation method of oxygen-carrying and adsorption composite functional material and application of oxygen-carrying and adsorption composite functional material in water body remediation |
| CN111097373A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院生态环境研究中心 | Porous adsorption material, oxygen-carrying and adsorption composite functional material and application thereof |
| CN110385104A (en) * | 2019-05-17 | 2019-10-29 | 北京化工大学 | A kind of modified zeolite flyash composite adsorbing material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106282585B (en) | A kind of detoxification classification resource utilization method of domestic garbage incineration flyash | |
| CN103638744B (en) | A kind of method improving acid flyash slurry filtration performance | |
| CN102746023B (en) | Constructed wetland matrix filling material for simultaneous nitrogen and phosphorus removal and its preparation method | |
| CN107265470A (en) | Cinder from refuse incineration hydro-thermal method heavy metal antihunt means | |
| WO2013143335A1 (en) | Method for extracting aluminium oxide in fly ash by alkaline process | |
| CN114425549B (en) | Method for microwave hydrothermal detoxification and synchronous synthesis of tobermorite by using waste incineration fly ash | |
| CN105597668A (en) | Preparation method and application of modified zeolite | |
| CN102671623A (en) | Preparation method of fly ash based zeolite / alumina composite adsorbing material | |
| CN103349994B (en) | A kind of catalyst that reclaims from coal ash is also separated the method obtaining aluminum contained compound | |
| CN105198022A (en) | Multi-effect printing and dyeing wastewater purifying treatment pulvis and preparation method thereof | |
| CN113479920A (en) | Aluminum ash resource utilization method | |
| CN107628632A (en) | A kind of method using coal ash for manufacturing for flocculant poly aluminium chloride | |
| CN109678624A (en) | A kind of mineral water solution and the preparation method and application thereof | |
| CN103752261A (en) | Method for preparing uranium adsorbent and curing agent by using raw materials of white mud and oil shale ash | |
| CN104826597A (en) | Method for preparing adsorbent by attapulgite clay organic modification | |
| CN103253681B (en) | Method for preparing Na-A/X or Na-A/X/P cocrystal molecular sieve through lithium slag hydrothermal synthesis | |
| CN106219568A (en) | A kind of method utilizing gangue to prepare high-purity molecular sieve ZSM 5 | |
| CN108129516A (en) | A kind of benzyl arsenic acid synthetic method | |
| CN105126740B (en) | A kind of BIOLOGICAL CALCIUM type Phosphateadsorption porous material and preparation method thereof | |
| CN103936045A (en) | Method for extracting aluminum oxide from coal ash | |
| CN109824285B (en) | Cement flue gas desulfurizer and application thereof | |
| CN106629757A (en) | Method for removing nitrogen and phosphorus from water by using calcium silicate prepared from silicon recycled from red mud | |
| CN104016357B (en) | A kind of manganese slag for comprehensive utilizes the method for producing industrial chemicals | |
| CN101804322A (en) | High-strength dry type CO2 adsorbent for regeneration using river sediment as carrier and preparation method thereof | |
| CN103638745B (en) | A kind of method improving alkaline coal ash slurry filtration performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120919 |