CN1105684C - Technology of applying 13x zeolite in treating heavy metal-containing waste water and recovering metal - Google Patents
Technology of applying 13x zeolite in treating heavy metal-containing waste water and recovering metal Download PDFInfo
- Publication number
- CN1105684C CN1105684C CN 99102984 CN99102984A CN1105684C CN 1105684 C CN1105684 C CN 1105684C CN 99102984 CN99102984 CN 99102984 CN 99102984 A CN99102984 A CN 99102984A CN 1105684 C CN1105684 C CN 1105684C
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- zeolite
- wastewater
- containing wastewater
- treating
- 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.)
- Expired - Fee Related
Links
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention relates to a technology for purifying wastewater containing heavy metal and recovering the metal by 13x zeolite. The 13x zeolite is adopted to remove heavy metal ions of Cu<2+>, Pb<2+>, Cd<2+> and Hg<2+> in the wastewater under the action of adsorption-ion exchange, and the purpose of purifying the wastewater is achieved. Then, saturated NaCl solution is used for eluting the heavy metal ions adsorbed by the 13x zeolite, and the 13x zeolite can be recycled. Finally, Na2S is used for precipitating the heavy metal ions in eluent. Precipitation and filtration are carried out, the main component of filtered solution is the saturated NaCl solution, and the filtered solution can be recycled. Heavy metal elements in precipitates are recovered through high temperature melting, purified wastewater completely reaches the water discharge standards, and simultaneously, the heavy metals can be recovered.
Description
Technical Field
The invention relates to a method for treating heavy metal-containing wastewater and recovering metals by using 13x zeolite.
Background
The wastewater containing heavy metals comes from the industries of electroplating, mining, smelting, chemical engineering and the like, and is the industrial wastewater which has the most serious harm to the environment and the most harm to human. The treatment of waste water containing heavy metals usually mainly adopts a physical and chemical method. The methods often generate new pollutants such as waste residues and the like while treating the wastewater, the water quality after treatment is usually difficult to reach the discharge standard, and the heavy metals removed from the wastewater are often difficult to recycle.
Technical content
The invention aims to provide a method for treating heavy metal-containing wastewater and recovering metals by using 13x zeolite, wherein the method for treating the heavy metal-containing wastewater by using the 13x zeolite is simple in operation, low in investment cost, large in wastewater treatment amount and high in operation speed, the wastewater after purification treatment completely reaches the discharge water standard, and simultaneously the heavy metals can be recovered, so that secondary recycling of the wastewater and the heavy metals is realized.
In order to achieve the purpose, the invention adopts the following technical scheme: the application of the 13x zeolite in treating the wastewater containing heavy metals is to add the 13x zeolite into the wastewater containing heavy metals, and obtain purified water after stirring, precipitation and filtration. The 13x zeolite is an inorganic microporous material, has excellent adsorption, ion exchange and catalytic performances, and has wide application and huge application potential in many fields such as industry and agriculture. The invention adopts 13x zeolite synthesized by using natural rock as raw material, and the production method of 13x zeolite is described in detail in patent application No. 96120734.5 entitled "Process for preparing zeolite molecular sieve from potassium feldspar. Heavy metal ions Cu in the wastewater are treated by adsorption-ion exchange2+、Pb2+、Zn2+、Cd2+、Hg2+And removing to achieve the purpose of purifying the wastewater. Then using saturated NaCl solution as eluent to elute the heavy metal ions adsorbed by the 13X zeolite, so that the 13X zeolite can be repeatedly used for many times. Finally using Na2S is used for precipitating heavy metal ions in the eluent, the heavy metal ions are precipitated and filtered, and the main component of the filtrate is saturated NaCl solution which can be continuously used as the eluent for recycling. The precipitate is metal sulfide which is a raw material for smelting heavy metal, and heavy metal elements can be recovered through high-temperature smelting. The method has the advantages of simple operation, low investment cost, large wastewater treatmentamount and high operation speed, the wastewater after purification treatment completely reaches the discharge water standard, and simultaneously the heavy metal can be recovered, so that secondary recycling of the wastewater and the heavy metal is realized.
The method for treating the heavy metal-containing wastewater and recovering metals by using the 13x zeolite mainly comprises the following steps:
(1) removing heavy metal ions in the wastewater by using 13x zeolite:
adding 13x zeolite into heavy metal-containing wastewater, stirring at normal temperature for 10-15min, standing for 5-10min, precipitating, filtering to obtain filtrate which is purified water meeting national discharge standard, directly discharging, collecting residue which is 13x zeolite saturated by adsorbing heavy metal ions,
(2) and (3) eluting heavy metal ions adsorbed by the 13x zeolite by using a saturated NaCl solution:
washing the filter residue obtained in the step with a saturated NaCl solution at 90-100 ℃, wherein the volume ratio of the saturated NaCl solution to the treated wastewater containing heavy metal is 0.8-1.2: 8-12, washing the filter residue in a small amount mode for multiple times, wherein the washing time is 10-15min, and after washing, resolving 13x zeolite is obtained, and the filtrate after washing is a concentrated solution rich in heavy metal ions.
(3) With Na2S, heavy metal ions in the concentrated solution are precipitated:
measuring the concentration of heavy metal ions in the concentrated solution obtained in the above step, and calculating the addition of Na2Total amount of S, andadding Na in an amount of more than 5 mol% of the theoretical calculation value2And S, adding the S into the concentrated solution, standing for 1.5-2h, then precipitating and filtering to obtain a filtrate which is mainly a saturated NaCl solution, and the filter residue is a heavy metal sulfide. The heavy metal sulfide enriches more than 90% of the total heavy metal in the concentrated solution, and is a raw material for recovering and smelting heavy metal.
The method of the invention also comprises the following steps:
(4) smelting heavy metal sulfide:
will be on the surface with Na2S, precipitating the filter residue obtained in the heavy metal ion step in the concentrated solution, drying at 105 +/-5 ℃, taking the dried filter residue as a raw material for recovering and refining heavy metals, and smelting to obtain the heavy metals. Smelting processes are well established techniques in the metallurgical industry and therefore will not be discussed in detail.
In the method, the 13x zeolite is resolved, dried, burned and activated, and continuously recycled, wherein the 13x zeolite is obtained in the step of eluting the heavy metal ions adsorbed by the 13x zeolite by using a saturated NaCl solution. Wherein the drying temperature is 105 +/-5 ℃, and the drying time is 1-1.2 h; the temperature of the burning activation is 550 +/-5 ℃, and the time of the burning activation is 1-1.2 h. The 13x zeolite can be recycled for multiple times.
In the step of precipitating heavy metal ions in the concentrated solution by using NaS in the method of the invention, the obtained filtrate is mainly a saturated NaCl solution, wherein the concentration of the heavy metal ions is reduced to be less than 10% of the original concentration, therefore, the filtrate can be continuously used as eluent and returned to the step 2 for recycling.
In the method, the heavy metal in the heavy metal-containing wastewater is one or more of Cu, Pb, Zn, Cd and Hg.
In the method of the invention, the heavy metal in the heavy metal-containing wastewater is Cu, and the dosage of 13x zeolite is calculated according to the following data: the initial concentration of the heavy metal wastewater is [ Cu]2+]The volume of the treated wastewater of 13x zeolite was 1471.3mL/g and the adsorption amount of 13x zeolite was 43.40mg/g, 30 mg/L.
In the method of the invention, the heavy metal in the heavy metal-containing wastewater is Pb, 13x zeoliteThe amount was calculated from the following data: the initial concentration of the heavy metal wastewater is [ Pb]2+]The volume of the treated wastewater of 13x zeolite was 1078.3mL/g and the adsorption amount of 13x zeolite was 20.48mg/g, which were 20 mg/L.
In the method of the invention, the heavy metal in the heavy metal-containing wastewater is Zn, and the dosage of the 13x zeolite is as followsAnd (3) data calculation: the initial concentration of the heavy metal wastewater is [ Zn]2+]The volume of the treated wastewater of 13x zeolite was 1334.1mL/g and the adsorption amount of 13x zeolite was 50.70mg/g, 40 mg/L.
In the method, the heavy metal in the heavy metal-containing wastewater is Cd, and the dosage of 13x zeolite is calculated according to the following data: the initial concentration of heavy metal wastewater is [ Cd]2+]The volume of the treated wastewater of 13x zeolite was 622.6mL/g and the adsorption amount of 13x zeolite was 6.16mg/g, which were 10 mg/L.
In the method of the invention, the heavy metal in the heavy metal-containing wastewater is Hg, and the dosage of 13x zeolite is calculated according to the following data: the initial concentration of the heavy metal wastewater is [ Hg]2+]The volume of the treated wastewater of 13x zeolite was 632.8mL/g and the adsorption amount of13x zeolite was 0.60mg/g, which were 1 mg/L.
The invention will be further explained with reference to the drawings.
Drawings
FIG. 1 is a process flow diagram for treating heavy metal-containing wastewater and recovering metals by using 13X zeolite
Detailed Description
The adsorption-ion exchange action of 13x zeolite is utilized to remove heavy metal ions in the wastewater, thereby achieving the purpose of purifying the wastewater. The specific operation is as follows: according to the actual concentration of the wastewater, the zeolite dosage of the wastewater to be treated is calculated by referring to the data in the table 1,
TABLE 1 adsorption capacity of 13X zeolite to meet wastewater discharge standards
| Name of heavy metal | Cu | Pb | Zn | Cd | Hg |
| Treatment volume (mL/g) | 1471.3 | 1078.3 | 1334.1 | 622.6 | 632.8 |
| Adsorption Capacity (mg/g) | 43.40 | 20.48 | 50.70 | 6.16 | 0.60 |
Note: the initial concentrations of the heavy metal wastewater are respectively as follows:
[Cu2+]＝30mg/L，[Pb2+]＝20mg/L，[Zn2+]＝40mg/L，[Cd2+]＝10mg/L，[Hg2+]＝1mg/L
the heavy metal in the heavy metal-containing wastewater marked by the block diagram in FIG. 1 is one of Cu, Pb, Zn, Cd and Hg
The following only takes the treatment of wastewater containing heavy metal Cu as an example, andthe process flow of treating wastewater containing other heavy metals is the same.
Examples
As shown in FIG. 1, the main sources of copper in industrial wastewater are cleaning metals, electroplating baths and rinse water, typically Cu2+The concentration of (A) is 20-40 mg/L. With CuSO4·5H2Preparing Cu from O and deionized water2+The pH value of the wastewater with the ion concentration of 30mg/L is kept from weak acidity to neutrality, and the treatment process is as follows:
1. 1g of 13x zeolite was charged into 1471mL of Cu-containing zeolite2+In the wastewater, the pH value of the wastewater is 5-7. Stirring for 10min, and standing for 5 min. After precipitation and filtration, the filtrate is purified water which meets the discharge standard and can be directly discharged.
2. And washing the filter residue by using 120mL of saturated NaCl solution at the temperature of 90-100 ℃ in a small quantity and multiple times for 10-15 min. The resolved 13x zeolite is obtained by cleaning, and can be continuously recycled after drying, burning and activating.
3. Cu in the eluate obtained in the second step2+Has a mass of 29.67mg according to the following chemical reaction formula
Calculating to add Na2S·9H2The amount of O is 113.02mg, the actual addition of more than 5 mol% of theory, i.e. 118.67mg, immediately produces a black precipitate. Drying the precipitate at 105 deg.C for 1 hr, analyzing by X-ray powder diffraction to obtain CuS, analyzing by GGX-2 type atomic absorption spectrophotometer, and filtering with Cu2+The concentration of (b) is 0.55mg/L, and the eluate can be continuously recycled.
4. And (4) smelting the CuS precipitate obtained in the third step at high temperature, and recovering to obtain the metal copper.
Claims (9)
1. A method for treating heavy metal-containing wastewater and recovering metals by 13x zeolite is characterized by comprising the following steps: the method comprises the following steps:
(1) removing heavy metal ions in the wastewater by using 13x zeolite:
adding 13x zeolite into the wastewater containing heavy metal, stirring, standing, precipitating, filtering to obtain filtrate which is purified water meeting national discharge standard, directly discharging, collecting residue which is 13x zeolite saturated by adsorbing heavy metal ions,
(2) and (3) eluting heavy metal ions adsorbed by the 13x zeolite by using a saturated NaCl solution:
washing the filter residue obtained in the above step with saturated NaCl solution at 90-100 deg.C at volume ratio of 0.8-1.2: 8-12, washing the filter residue with small amount of water for 10-15min for several times to obtain 13x zeolite, collecting the filtrate as concentrated solution rich in heavy metal ions,
(3) with Na2S, heavy metal ions in the concentrated solution are precipitated:
measuring the concentration of heavy metal ions in the concentrated solution obtained in the above step, and calculating the addition of Na2The total amount of S and Na in an amount of 5 mol% which exceeds the theoretical calculation value2And S, adding the S into the concentrated solution, standing for 1.5-2h, then precipitating and filtering to obtain a filtrate which is mainly a saturated NaCl solution, and the filter residue is a heavy metal sulfide.
2. The method of claim 1 for treating heavy metal-containing wastewater with 13x zeolite and recovering metals, characterized in that: the method further comprises the steps of:
(4) smelting heavy metal sulfide:
will be on the surface with Na2S, precipitating the filter residue obtained in the heavy metal ion step in the concentrated solution, drying at 105 +/-5 ℃, taking the dried filter residue as a raw material for recovering and refining heavy metals, and smelting to obtain the heavy metals.
3. The method of treating heavy metal-containing wastewater with 13x zeolite and recovering metals according to claim 1 or 2, characterized in that: and (3) eluting the 13x zeolite adsorbed heavy metal ions by using a saturated NaCl solution to obtain the resolved 13x zeolite, drying, burning and activating, and continuously recycling.
4. The method of claim 3 for treating heavy metal-containing wastewater and recovering metals with 13x zeolite, characterized in that: the heavy metal in the heavy metal-containing wastewater is one or more of Cu, Pb, Zn, Cd and Hg.
5. The method of claim 4 for treating heavy metal-containing wastewater with 13x zeolite and recovering metals, characterized in that: the heavy metal in the heavy metal-containing wastewater is Cu, and the dosage of 13x zeolite is calculated according to the following data: the initial concentration of the heavy metal wastewater is [ Cu]2+]The volume of the treated wastewater of 13x zeolite was 1471.3mL/g and the adsorption amount of 13x zeolite was 43.40mg/g, 30 mg/L.
6. The method of claim 4 for treating heavy metal-containing wastewater with 13x zeolite and recovering metals, characterized in that: the heavy metal in the heavy metal-containing wastewater is pb, and the dosage of the 13x zeolite is calculated according to the following data: the initial concentration of the heavy metal wastewater is [ Pb]2+]The volume of the treated wastewater of 13x zeolite was 1078.3mL/g and the adsorption amount of 13x zeolite was 20.48mg/g, which were 20 mg/L.
7. According toThe method for treating heavy metal-containing wastewater and recovering metals using 13x zeolite according to claim 4, wherein: the heavy metal in the heavy metal-containing wastewater is Zn, and the dosage of 13x zeolite is calculated according to the following data: the initial concentration of the heavy metal wastewater is [ Zn]2+]The volume of the treated wastewater of 13x zeolite was 1334.1mL/g and the adsorption amount of 13x zeolite was 50.70mg/g, 40 mg/L.
8. The method of claim 4 for treating heavy metal-containing wastewater with 13x zeolite and recovering metals, characterized in that: the heavy metal in the heavy metal-containing wastewater is Cd, and the dosage of 13x zeolite is calculated according to the following data: the initial concentration of heavy metal wastewater is [ Cd]2+]The volume of the treated wastewater of 13x zeolite was 622.6mL/g and the adsorption amount of 13x zeolite was 6.16mg/g, which were 10 mg/L.
9. The method of claim 4 for treating heavy metal-containing wastewater with 13x zeolite and recovering metals, characterized in that: the heavy metal in the heavy metal-containing wastewater is Hg, and the dosage of 13x zeolite is calculated according to the followingdata: the initial concentration of the heavy metal wastewater is [ Hg]2+]The volume of the treated wastewater of 13x zeolite was 632.8mL/g and the adsorption amount of 13x zeolite was 0.60mg/g, which were 1 mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99102984 CN1105684C (en) | 1999-03-15 | 1999-03-15 | Technology of applying 13x zeolite in treating heavy metal-containing waste water and recovering metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99102984 CN1105684C (en) | 1999-03-15 | 1999-03-15 | Technology of applying 13x zeolite in treating heavy metal-containing waste water and recovering metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1267641A CN1267641A (en) | 2000-09-27 |
| CN1105684C true CN1105684C (en) | 2003-04-16 |
Family
ID=5271078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99102984 Expired - Fee Related CN1105684C (en) | 1999-03-15 | 1999-03-15 | Technology of applying 13x zeolite in treating heavy metal-containing waste water and recovering metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1105684C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826674A (en) * | 2011-06-15 | 2012-12-19 | 上海丰信环保科技有限公司 | Method for processing lead and chromium in wastewater |
| CN102424489A (en) * | 2011-09-28 | 2012-04-25 | 界首市骏马工贸有限公司 | Desulfurized lead-containing wastewater recycling processing method |
| CN102689938A (en) * | 2012-05-23 | 2012-09-26 | 北京佳康尔水处理技术有限公司 | 13x molecular sieve water purifying device for purifying heavy metal in drinking water |
| CN103723786B (en) * | 2013-12-18 | 2015-06-03 | 同济大学 | Self-repairing method for anti-seepage wall body of heavy metal pollutant place |
| CN103864472B (en) * | 2014-02-26 | 2016-03-09 | 化工部长沙设计研究院 | A kind of absorption method prepares the technique of potash fertilizer by potassium feldspar decomposition mother liquor |
| CN105271297A (en) * | 2015-10-22 | 2016-01-27 | 北京科技大学 | Method for preparing 4A molecular sieves by using tailings and application of 4A molecular sieves |
| CN106495363A (en) * | 2016-12-07 | 2017-03-15 | 云南大地绿坤环保科技有限公司 | A kind of processing method of mercurous waste liquid |
| CN106862252A (en) * | 2017-03-24 | 2017-06-20 | 中国科学院广州能源研究所 | The processing system and method for a kind of heavy metal in soil |
| CN109607908A (en) * | 2018-11-13 | 2019-04-12 | 长沙埃比林环保科技有限公司 | A kind of processing method of chromate waste water |
| CN113398890A (en) * | 2021-06-21 | 2021-09-17 | 中国矿业大学(北京) | Method for preparing heavy metal composite adsorbent from coal-based sodium humate/zeolite |
-
1999
- 1999-03-15 CN CN 99102984 patent/CN1105684C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1267641A (en) | 2000-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1105684C (en) | Technology of applying 13x zeolite in treating heavy metal-containing waste water and recovering metal | |
| CN106824113B (en) | Preparation and application of imidazole ionic liquid modified chitosan adsorbent | |
| CN107902855B (en) | Recovery process of waste zinc ions in viscose fiber production | |
| CN103449623B (en) | Method for preparing metal nanometer material by recovering from industrial waste water | |
| CN1123843A (en) | Recovery of platinum family elements from waste catalysts | |
| CN115652114A (en) | Recycling process of thallium in thallium-containing solution | |
| CN115007116A (en) | Shaddock peel adsorbent and method for adsorbing and removing heavy metals in industrial wastewater | |
| CN110732311A (en) | crosslinked chitosan coated MoS2Adsorbent, preparation method and application thereof | |
| KR100269160B1 (en) | Method for purification of soils contaminated with heavy metals | |
| CN110846510B (en) | Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid | |
| CN109811129B (en) | Method for recovering thallium, mercury and chromium from smelting acid wastewater | |
| CN109012571B (en) | Modified electrolytic manganese waste residue, preparation method thereof and industrial wastewater treatment method | |
| US4744825A (en) | Removal and recovery of silver from waste stream | |
| CN103170313A (en) | Heavy metal modified bioadsorbent and preparation method thereof as well as application of heavy metal modified bioadsorbent in tungsten-containing waste water treatment | |
| CN112569913B (en) | Fiber-based adsorption material, preparation method thereof and removal of organic copper complex | |
| CN1091469C (en) | Antimony and impurity removing method for copper electrolyte | |
| CN109811130B (en) | Method for recovering thallium and mercury from smelting acid wastewater | |
| CN109081777B (en) | Method for recovering and treating tetrafluorobenzoic acid wastewater | |
| CN1648066A (en) | Method and device for treating multiple form heavy metal waste water by multiphase transfer method | |
| CN109626430B (en) | Method for preparing thallium chromate from smelting acid wastewater by recovering thallium | |
| CN111717954A (en) | Heavy metal wastewater treating agent and treating method thereof | |
| CN1297067A (en) | Method for purifying copper electrolyte by solvent extraction | |
| CN1611451A (en) | Method for biochemical treatment of discharged water | |
| CN1253385C (en) | Processing method of cupric ion of phthalocyanine green waste water using 335 type alkalescence anion resin | |
| CN113526724B (en) | Low-concentration ammonia nitrogen manganese wastewater treatment system and method using manganese tailings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |