CN103920458A - Preparation method for water body eutrophication treatment rare earth composite material - Google Patents
Preparation method for water body eutrophication treatment rare earth composite material Download PDFInfo
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- CN103920458A CN103920458A CN201410100835.4A CN201410100835A CN103920458A CN 103920458 A CN103920458 A CN 103920458A CN 201410100835 A CN201410100835 A CN 201410100835A CN 103920458 A CN103920458 A CN 103920458A
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Abstract
The present invention discloses a preparation method for a water body eutrophication treatment rare earth composite material. The preparation method comprises: mixing a metal alkali solution and fly ash according to a certain ratio, and carrying out a reaction in a closed or opening system; after completing the reaction, cooling to a room temperature to obtain a zeolite and waste alkali solution mixture; under a stirring condition, continuously adding a soluble rare earth salt solution in a dropwise manner until achieve the pH value of less than 7.5; and carrying out solid-liquid separation, wherein the solid is subjected to a heat treatment to obtain the fly ash base zeolite/rare earth composite material. According to the present invention, the waste alkali solution produced during zeolite synthesis through fly ash is neutralized so as to provide possibility for waste alkali solution recycling, obtain the rare earth component providing strong affinity for the anion contaminants, effectively solve the problem of the too high nutrient concentration in the eutrophication water body, and achieve long term water body control; and the method has characteristics of waste treatment with waste, simple synthesis process, low cost and the like, and the composite material has characteristics of strong nutrient removing and eutrophication degree reducing.
Description
Technical field
The invention belongs to Environmental Technology field, relate to the preparation method of sorbing material, be specifically related to a kind of preparation method who administers body eutrophication rare earth composite material.
Background technology
Body eutrophication is called again wawter bloom, refers to the too much caused water pollution phenomenons of plant nutrient substance content such as Water phosphorus such as lake, river, reservoir, it has been generally acknowledged that phosphorus is the key factor that causes this environmental problem.The source form endogenous phosphorus of phosphorus and exogenous phosphorus in water body.Exogenous phosphorus, mainly from the sewage that enters water body, can be controlled effectively by pollution control measures; Endogenous phosphorus is the phosphorus from water body inside, and sewage enters, rainwash collects and aquatile remains deposit and cause in water body.The continuous accumulation of endogenous phosphorus and release have caused great difficulty for the improvement of body eutrophication.Just because of this, countries in the world are all extremely paid attention to for the control of water body endogenous phosphorus.Iron, aluminium medicament be owing to having the good affinity of phosphorus, and easy and simple to handle, therefore becomes at present the most general for water body dephosphorized material.Due to the concentration of endogenous phosphorus, to compare industrial wastewater much lower, and eutrophication water is alkalescence more, and iron, aluminum are often easily subject to water environment condition to the removal of phosphorus, as the impact of the factors such as phosphorus concentration, pH value, oxidation-reduction potential, lose even dephosphorization ability.Want to administer eutrophication problem, just in the urgent need to finding one to there is powerful removal effect to low phosphorus, and can be applicable to compared with the material of Complex water body environment.
Chinese patent (patent No.: CN101134615B) proposes to use sour modified coal ash to be used for flocculating and removes Measures of Algae in Water Body and nutritive salt, and reaches the object except algae by adding magnetic material.Although the method has proposed a kind of approach that effectively utilizes solid waste, the dephosphorization mechanism of the method remains utilizes iron oxide in flyash, aluminium oxide and calcium oxide etc. except phosphorus composition, therefore has equally the intrinsic problem of above-mentioned dephosphorization material.
Summary of the invention
The object of the invention is to the deficiency for above-mentioned existing dephosphorization medicament and material, a kind of preparation method who administers body eutrophication rare earth composite material is provided.Utilize the strong affine performance of rare earth to phosphorus, and be fixed in fly ash base synthetic zeolite surface, thereby obtain a kind of multifunctional and composite type dephosphorization material, for cutting down storehouse, lake Endogenous Phosphorus load, control storehouse, lake eutrophication problem.Particularly, prepare zeolite taking flyash as raw material by the hydro-thermal reaction under alkali condition exactly, and in preparation technology, introduce soluble rare-earth salt with in and spent lye, thereby make rare earth composite adsorbent capable.The advantages such as it is high that rare earth oxide has affinity for dephosphorization, and dephosphorization speed is fast, and dephosphorization ability is strong, and also there is good control effect for low concentration phosphorus in water body.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of preparation method who administers body eutrophication rare earth composite material, said method comprising the steps of:
Step 1, metal base solution mixes in proportion with flyash, in airtight or open system, reacts; Reaction finishes rear cool to room temperature, obtains the mixture of zeolite and spent lye;
Step 2, adopts the mode dripping continuously, in the zeolite obtaining and the mixture of spent lye, adds soluble ree salting liquid under stirring condition to step 1, to pH be below 7.5; By Separation of Solid and Liquid, solid obtains fly ash base zeolite/rare earth composite adsorbing material through heat treatment.
In step 1, described metal base solution is potassium hydroxide or NaOH, and molar concentration is 1～5M.
In step 1, the liquid-solid ratio 1.5～20 (L/kg) of described metal base solution and flyash.
In step 1, the temperature of described reaction is 80～200 DEG C, and the time is 3～24 hours.
In step 2, the speed of described continuous dropping is 10～100ml/min.Dropping to pH is 5.5～7.5 o'clock, enters solid-liquid separation process.
In step 2, described soluble rare-earth salt is the rare-earth salts soluble in water such as lanthanum chloride or cerium chloride, and molar concentration is 0.5～5M.
In step 2, described Separation of Solid and Liquid is filtration or centrifugal.
In step 2, described heat treated atmosphere is air, and temperature is 65～500 DEG C.
In step 2, the liquid of described Separation of Solid and Liquid gained continues on for preparing described metal base solution.The metal base solution configuring and obtain is as the preparation of follow-up zeolite/rare earth composite material.
Compared with prior art, the present invention has following beneficial effect:
1) comprehensive utilization solid waste is prepared novel environment friendly material and is met state incentives completely.
2) production technology is simple and easy to implement, and meets cleaner production requirement, does not substantially produce environment bazardous waste.
3) zeolite/rare earth material being prepared by flyash has very strong phosphorus crystallized ability, can effectively reduce phosphorus concentration in water body.The shortcoming that has overcome iron, aluminium dephosphorization material, has an application prospect widely.
4) therefore the zeolite component being obtained by water of coal ash thermal synthesis has high-cation exchange capacity can also fix the ammonia nitrogen in water body outside dephosphorization effectively.
5) rare earth that this patent adopts is lanthanum or cerium, and they are that in 17 kinds of rare earth elements, reserves are the abundantest the most cheap with price.
6) zeolite/rare earth material is fine particle, and after being sprayed in water body, natural subsidence, to sediment layer, can be controlled the release of nutritive salt in bed mud at short notice, and can not impact the living environment of water body biology.
7) zeolite/rare earth material has good stability, and in water body, long-term placement can not discharge noxious material yet.
Brief description of the drawings
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is process flow diagram of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
In embodiment, water body is an experiment pond waters of Minxing, Shanghai, and pond water is derived from river, and phosphorus concentration is 1500ug/L, pond area 15m
2, the about 1.5m of mean depth.
The main physical and chemical of the flyash adopting in embodiment is as following table 1.Carry out each embodiment by technological process shown in diagram 1.
Table 1 flyash chief component
| 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 |
comparative example 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), control 100 DEG C of temperature of reaction kettle, mixing speed is 120rpm, after hydro-thermal reaction 24 hours, cooling suspension is to room temperature.
Step 2, gets aluminium chloride and is dissolved in the water, and preparation concentration is 0.5M (molar concentration) aluminum chloride aqueous solution.Liquor alumini chloridi is joined in glass reaction still in the mode of Continuous Titration, and rate of titration is 10ml/min, and mixing speed is 60rpm, and reaction temperature is 20 DEG C, and terminal pH is 6.0.After having reacted, centrifugation, the liquid collection obtaining gets up to continue on for follow-up sodium hydroxide solution preparation; The solid obtaining is placed in the dry 24h of baking oven, and 65 DEG C of oven temperatures, obtain Zeolite/alumina composite adsorbing material.
Step 3,, measures after 5 hours and in water sample, remains nutrient concentration to direct Zeolite Addition/alumina composite sorbing material the water sample of fetching from pond by 0.2g/L dosage.
Implementation result: the cation exchange capacity of the Zeolite/alumina composite adsorbing material that the present embodiment prepares is 120cmol/kg, it is 14mg/g that maximum is removed phosphate capacity; Test result for eutrophication water sample shows, this composite reaches 50.47% to tp removal rate.
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), control 100 DEG C of temperature of reaction kettle, mixing speed is 120rpm, after hydro-thermal reaction 24 hours, cooling suspension is to room temperature.
Step 2, gets Lanthanum trichloride hexahydrate and is dissolved in the water, and preparation concentration is 0.5M (molar concentration) lanthanum chloride solution.Lanthanum chloride solution is joined in glass reaction still in the mode of Continuous Titration, and rate of titration is 10ml/min, and mixing speed is 60rpm, and reaction temperature is 20 DEG C, and terminal pH is 6.0.After having reacted, centrifugation, the liquid collection obtaining gets up to continue on for follow-up sodium hydroxide solution preparation; The solid obtaining is placed in the dry 24h of baking oven, and 65 DEG C of oven temperatures, obtain zeolite/lanthana composite adsorbing material.
Step 3,, measures after 5 hours and in water sample, remains nutrient concentration to direct Zeolite Addition/lanthana composite adsorbing material the water sample of fetching from pond by 0.2g/L dosage.
Implementation result: the cation exchange capacity of zeolite/lanthana composite adsorbing material that the present embodiment prepares is 114cmol/kg, it is 68mg/g that maximum is removed phosphate capacity; Test result for eutrophication water sample shows, this composite reaches 90.47% to tp removal rate.
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 2: 1 (L/kg), control 100 DEG C of temperature of reaction kettle, mixing speed is 120rpm, after hydro-thermal reaction 12 hours, cooling suspension is to room temperature.
Step 2, gets Cerium trichloride hexahydrate and is dissolved in the water, and preparation concentration is 2.5M (molar concentration) the cerium chloride aqueous solution.Solution of cerium chloride by oxidation is joined in glass reaction still in the mode of Continuous Titration, and rate of titration is 50ml/min, and mixing speed is 60rpm, and reaction temperature is 20 DEG C, and terminal pH is 7.5.After having reacted, centrifugation, the liquid collection obtaining gets up to continue on for follow-up potassium hydroxide solution preparation; The solid obtaining after dry 4 hours, obtains zeolite/cerium oxide composite adsorbing material in 105 DEG C.
Step 3,, measures after 5 hours and in water sample, remains nutrient concentration to direct Zeolite Addition/cerium oxide composite adsorbing material the water sample of fetching from pond by 0.2g/L dosage.
Implementation result: the cation exchange capacity of zeolite/cerium oxide composite adsorbing material that the present embodiment prepares is 133cmol/kg, it is 74mg/g that maximum is removed phosphate capacity; Test result for eutrophication water sample shows, this composite reaches 91.99% to tp removal rate.
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), control 200 DEG C of temperature of reaction kettle, mixing speed is 80rpm, after hydro-thermal reaction 4 hours, cooling suspension is to room temperature.
Step 2, gets Lanthanum trichloride hexahydrate and is dissolved in the water, and preparation concentration is 5M (molar concentration) lanthanum chloride solution.Lanthanum chloride solution is joined in stainless steel cauldron in the mode of Continuous Titration, and rate of titration is 80ml/min, and mixing speed is 60rpm, and reaction temperature is 25 DEG C, and terminal pH is 5.5.After having reacted, centrifugation, the liquid collection obtaining gets up to continue on for follow-up sodium hydroxide solution preparation; The solid obtaining is placed in Muffle furnace and calcines 2 hours, and 450 DEG C of calcining heats obtain zeolite/lanthana composite adsorbing material.
Step 3,, measures after 5 hours and in water sample, remains nutrient concentration to direct Zeolite Addition/lanthana composite adsorbing material in experiment pond by 0.2g/L dosage.
Implementation result: the cation exchange capacity of zeolite/lanthana composite adsorbing material that the present embodiment prepares is 133cmol/kg, it is 94mg/g that maximum is removed phosphate capacity; Result of the test for eutrophication water sample shows, this composite reaches 94.58% to tp removal rate.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. a preparation method who administers body eutrophication rare earth composite material, is characterized in that, said method comprising the steps of:
Step 1, metal base solution mixes in proportion with flyash, in airtight or open system, reacts; Reaction finishes rear cool to room temperature, obtains the mixture of zeolite and spent lye;
Step 2, under stirring condition to dripping continuously soluble ree salting liquid in the mixture of described zeolite and spent lye, to pH be below 7.5; Separation of Solid and Liquid, solid obtains described improvement body eutrophication rare earth composite material through heat treatment.
2. the preparation method of improvement body eutrophication rare earth composite material according to claim 1, is characterized in that, in step 1, described metal base solution is that molar concentration is NaOH or the potassium hydroxide solution of 1～5M.
3. the preparation method of improvement body eutrophication rare earth composite material according to claim 1, is characterized in that, in step 1, and the liquid-solid ratio 1.5～20L/kg of described metal base solution and flyash.
4. the preparation method of improvement body eutrophication rare earth composite material according to claim 1, is characterized in that, in step 1, the temperature of described reaction is 80～200 DEG C, and the time is 3～24 hours.
5. the preparation method of improvement body eutrophication rare earth composite material according to claim 1, is characterized by, and in step 2, described soluble rare-earth salt is that molar concentration is lanthanum chloride or the cerium chloride of 0.5～5M.
6. the preparation method of improvement body eutrophication rare earth composite material according to claim 1, is characterized in that, in step 2, the speed of described continuous dropping is 10～100ml/min.
7. the preparation method of improvement body eutrophication rare earth composite material according to claim 1, is characterized in that, in step 2, described Separation of Solid and Liquid is filtration or centrifugal.
8. the preparation method of improvement body eutrophication rare earth composite material according to claim 1, is characterized in that, in step 2, described heat treated atmosphere is air, and temperature is 65～500 DEG C.
9. the preparation method of improvement body eutrophication rare earth composite material according to claim 1, is characterized in that, in step 2, the liquid of described Separation of Solid and Liquid gained continues on for preparing described metal base solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104353411A (en) * | 2014-11-19 | 2015-02-18 | 上海电力学院 | Preparation method of water treatment strong adsorbent |
| CN110394165A (en) * | 2019-08-12 | 2019-11-01 | 中国科学院烟台海岸带研究所 | A kind of preparation method and application of dephosphorization zeolite |
| CN114751483A (en) * | 2022-05-20 | 2022-07-15 | 山东禹清环境科技有限公司 | Endogenous phosphorus passivation material for eutrophic water body and preparation method thereof |
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| JPS58109133A (en) * | 1981-12-19 | 1983-06-29 | Toyo Soda Mfg Co Ltd | Removing method for silicic acid in water |
| CN102380343A (en) * | 2011-08-31 | 2012-03-21 | 环境保护部华南环境科学研究所 | Simultaneous nitrogen and phosphorus removal modified artificial zeolite for micro-polluted water, and preparation method thereof |
| CN102671623A (en) * | 2012-05-23 | 2012-09-19 | 上海交通大学 | Preparation method of fly ash based zeolite / alumina composite adsorbing material |
-
2014
- 2014-03-18 CN CN201410100835.4A patent/CN103920458A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58109133A (en) * | 1981-12-19 | 1983-06-29 | Toyo Soda Mfg Co Ltd | Removing method for silicic acid in water |
| CN102380343A (en) * | 2011-08-31 | 2012-03-21 | 环境保护部华南环境科学研究所 | Simultaneous nitrogen and phosphorus removal modified artificial zeolite for micro-polluted water, and preparation method thereof |
| CN102671623A (en) * | 2012-05-23 | 2012-09-19 | 上海交通大学 | Preparation method of fly ash based zeolite / alumina composite adsorbing material |
Non-Patent Citations (1)
| Title |
|---|
| JIE XIE ET AL.: ""Green synthesis of a novel hybrid sorbent of zeolite/lanthanum hydroxide and its application in the removal and recovery of phosphate from water"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 423, 22 February 2014 (2014-02-22) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104353411A (en) * | 2014-11-19 | 2015-02-18 | 上海电力学院 | Preparation method of water treatment strong adsorbent |
| CN110394165A (en) * | 2019-08-12 | 2019-11-01 | 中国科学院烟台海岸带研究所 | A kind of preparation method and application of dephosphorization zeolite |
| CN114751483A (en) * | 2022-05-20 | 2022-07-15 | 山东禹清环境科技有限公司 | Endogenous phosphorus passivation material for eutrophic water body and preparation method thereof |
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