CN111137925A - Method for preparing water purifying agent by using industrial waste sulfuric acid and waste cutter head - Google Patents
Method for preparing water purifying agent by using industrial waste sulfuric acid and waste cutter head Download PDFInfo
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- CN111137925A CN111137925A CN202010008967.XA CN202010008967A CN111137925A CN 111137925 A CN111137925 A CN 111137925A CN 202010008967 A CN202010008967 A CN 202010008967A CN 111137925 A CN111137925 A CN 111137925A
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- sulfuric acid
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- industrial waste
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method for preparing a water purifying agent by using industrial waste sulfuric acid and waste cutter bits, belonging to the field of resource recycling. Based on the analysis of the valuable components of the waste cutter head and the industrial waste sulfuric acid, the industrial waste sulfuric acid is used for dissolving iron in the waste cutter head to produce the iron-based water purifying agent, the iron-based water purifying agent is used for treating various kinds of waste water, the resource utilization of the industrial waste sulfuric acid and the waste cutter head is realized, a new mode of cooperative treatment of two kinds of waste materials is provided, the resource waste is overcome, the waste is changed into the valuable, and the huge social, economic and environmental benefits are exerted; the treatment cost is low, and the economic benefit generated by the produced water purifying agent can make up the cost of waste treatment; no secondary pollution is generated, and secondary pollutants of calcium sulfate slag can be generated by the conventional method.
Description
Technical Field
The invention relates to the technical field of resource recycling, in particular to a method for preparing a water purifying agent by using industrial waste sulfuric acid and waste cutter bits.
Background
The waste cutter head mainly comes from various large stone factories, the waste amount of more than 5000 tons is generated every year, if the waste is discarded at will, not only is the resource waste caused, but also water sources, soil and the like are polluted, and huge economic benefit and social benefit can be generated by recycling the waste cutter head.
China is also a large country for producing sulfuric acid and a large country for consuming sulfuric acid, the sulfuric acid production generates about 1 hundred million tons of waste sulfuric acid every year, the waste sulfuric acid can cause great harm to underground water, soil and atmosphere, but the disposal problem is not well solved all the time. At present, lime, carbide slag and slaked lime are adopted by common enterprises to carry out neutralization treatment on waste sulfuric acid, the pH value of the treated waste liquid can meet the requirement, but other indexes are difficult to reach the standard, secondary pollution is serious, a large amount of pollutants such as sulfuric acid slag and the like can still be generated, and the treatment cost is far higher than the product price due to the lower price of the sulfuric acid at present.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a water purifying agent by using industrial waste sulfuric acid and waste cutter bits. The invention is based on the analysis of the valuable components of the waste cutter head and the waste sulfuric acid, dissolves iron in the waste cutter head by the industrial waste sulfuric acid to produce the iron-based water purifying agent, and realizes the resource utilization of the waste sulfuric acid and the waste cutter head.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing a water purifying agent by using industrial waste sulfuric acid and waste cutter heads, which comprises the following steps:
removing solid impurities in the industrial waste sulfuric acid to obtain pretreated industrial waste sulfuric acid;
mixing the pretreated industrial waste sulfuric acid with the waste cutter head to perform double decomposition reaction to obtain a hot ferrous sulfate solution;
and introducing liquid oxygen into the hot ferrous sulfate solution, and then carrying out polymerization reaction to obtain the liquid polymeric ferric sulfate water purifying agent.
Preferably, the mass content of the sulfuric acid in the industrial waste sulfuric acid is 30-95%.
Preferably, the waste cutter head comprises the following components in parts by weight: fe 70-80%, Cu 15-20%, Sn 1-2%, Zn 2-4% and diamond 2-3%, wherein the sum of the weight contents of the components is 100%.
Preferably, the mass ratio of the waste cutter head to the industrial waste sulfuric acid is 1: 4-1: 6.
Preferably, the temperature of the double decomposition reaction is 50-80 ℃.
Preferably, the dosage ratio of the liquid oxygen to the hot ferrous sulfate solution is 15-18 kg: 1m3。
Preferably, the pressure of the polymerization reaction is 300-500N, the temperature is 50-80 ℃, and the time is 2-4 h.
Preferably, the metathesis reaction also produces a copper-tin-zinc mixture that enters a metal recovery system to extract copper, tin, and zinc.
The invention provides a method for preparing a water purifying agent by using industrial waste sulfuric acid and waste cutter heads, which comprises the following steps: removing solid impurities in the industrial waste sulfuric acid to obtain pretreated industrial waste sulfuric acid; mixing the pretreated industrial waste sulfuric acid with the waste cutter head to perform double decomposition reaction to obtain a hot ferrous sulfate solution; and introducing liquid oxygen into the hot ferrous sulfate solution, and then carrying out polymerization reaction to obtain the liquid polymeric ferric sulfate water purifying agent. Based on the analysis of the valuable components of the waste cutter head and the industrial waste sulfuric acid, the industrial waste sulfuric acid is used for dissolving iron in the waste cutter head to produce the iron-based water purifying agent, the iron-based water purifying agent is used for treating various kinds of waste water, the resource utilization of the industrial waste sulfuric acid and the waste cutter head is realized, a new mode of cooperative treatment of two kinds of waste materials is provided, the resource waste is overcome, the waste is changed into the valuable, and the huge social, economic and environmental benefits are exerted; the treatment cost is low, and the economic benefit generated by the produced water purifying agent can make up the cost of waste treatment; no secondary pollution is generated, and secondary pollutants of calcium sulfate slag can be generated by the conventional method. The data of the examples show that the water purifying agent prepared by the invention has excellent water purifying effect.
Detailed Description
The invention provides a method for preparing a water purifying agent by using industrial waste sulfuric acid and waste cutter heads, which comprises the following steps:
removing solid impurities in the industrial waste sulfuric acid to obtain pretreated industrial waste sulfuric acid;
mixing the pretreated industrial waste sulfuric acid with the waste cutter head to perform double decomposition reaction to obtain a hot ferrous sulfate solution;
and introducing liquid oxygen into the hot ferrous sulfate solution, and then carrying out polymerization reaction to obtain the liquid polymeric ferric sulfate water purifying agent.
The invention removes solid impurities in the industrial waste sulfuric acid to obtain the pretreated industrial waste sulfuric acid. In the invention, the mass content of sulfuric acid in the industrial waste sulfuric acid is preferably 30-95%, and the industrial waste sulfuric acid also preferably comprises organic matters. The method for removing the solid impurities in the present invention is not particularly limited, and may be a method known to those skilled in the art. The source of the industrial waste sulfuric acid is not particularly limited in the present invention.
After the pre-treated industrial waste sulfuric acid is obtained, the pre-treated industrial waste sulfuric acid is mixed with a waste cutter head to carry out double decomposition reaction, and a hot ferrous sulfate solution is obtained.
In the present invention, the waste cutter head preferably comprises the following components by weight: fe 70-75%, Cu 15-20%, Sn 1-2%, Zn 2-4% and diamond 2-3%, wherein the sum of the weight contents of the components is 100%. The present invention is not particularly limited as to the source of the waste cutter head.
In the invention, the mass ratio of the waste cutter head to the industrial waste sulfuric acid is preferably 1: 4-1: 6.
In the invention, the temperature of the double decomposition reaction is preferably 50-80 ℃, and the time is preferably until the waste cutter head is completely dissolved. In the present invention, the metathesis reaction preferably also produces a copper-tin-zinc mixture that is preferably passed to a metal recovery system for extraction of copper, tin and zinc. The metal recovery system is not particularly limited, and copper, tin and zinc can be extracted.
After the hot ferrous sulfate solution is obtained, the invention leads the hot ferrous sulfate solution into liquid oxygen to carry out polymerization reaction, thus obtaining the liquid polymeric ferric sulfate water purifying agent.
In the invention, the dosage ratio of the liquid oxygen to the hot ferrous sulfate solution is preferably 15-18 kg: 1m3More preferably 16 kg: 1m3。
In the invention, the pressure of the polymerization reaction is preferably 300-500N, more preferably 400-450N, the temperature is preferably 50-80 ℃, more preferably 60 ℃, and the time is preferably 2-4 h. In the present invention, the polymerization reaction is preferably carried out in a polymerization reactor.
In order to further illustrate the present invention, the method for preparing a water purifying agent using industrial waste sulfuric acid and waste bits according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Industrial waste sulfuric acid (the sulfuric acid content is 90%) is filtered through a filter screen to remove impurities, and then is put into a waste cutter head (the Fe weight content is 70%) to be dissolved, wherein the weight ratio of the waste cutter head to the industrial waste sulfuric acid is 1:4, reacting at 80 ℃ for 1 hour, then intercepting solid matters such as copper-tin-zinc slag and diamond by filtering through a filter screen, injecting the filtered hot ferrous sulfate into a polymerization reaction kettle, controlling the temperature to be 60 ℃, introducing liquid oxygen, and leading the liquid oxygen with the dosage of 16kg/m3The pressure is 450N, and the water purifying agent can be prepared after reaction for 3h and is used for treating and purifying wastewater.
The prepared water purifying agent is applied to treating wastewater:
1. antimony gold ore dressing wastewater: the main pollution indexes of arsenic and antimony are that the concentration of raw water arsenic is 0.5-5 mg/L and the concentration of antimony is 2-15 mg/L, and the treated water quality reaches the pollutant discharge index of the tin-antimony-mercury industry (GB 30770-2014).
2. Antimony-gold ore smelting wastewater: the main pollution indexes of arsenic and antimony are that the concentration of raw water arsenic is 1-10 mg/L and the concentration of antimony is 10-30 mg/L, and the treated water quality reaches the pollutant discharge index of the mercury-antimony-tin industry (GB 30770-2014).
3. Lead-zinc beneficiation wastewater: the main pollution indexes of lead, zinc, cadmium, arsenic and thallium, the raw water indexes of lead are less than 5mg/L, zinc is less than 20mg/L, cadmium is less than 2mg/L, arsenic is less than 3mg/L and thallium is less than 1mg/L, and the treated effluent reaches the lead-zinc industrial pollutant discharge standard (GB 25466-2010).
4. Lead-zinc smelting wastewater: the main pollution indexes of lead, zinc, cadmium, arsenic and thallium, the raw water indexes of lead are less than 20mg/L, zinc is less than 100mg/L, cadmium is less than 5mg/L, arsenic is less than 8mg/L and thallium is less than 3mg/L, and the treated effluent reaches the lead-zinc industrial pollutant discharge standard (GB 25466-2010).
Example 2
The industrial waste sulfuric acid (the sulfuric acid content is 95%) is filtered by a filter screen to remove impurities and then is put into a waste cutter head (the Fe weight content is 80%) for dissolution, and the weight ratio of the waste cutter head to the industrial waste sulfuric acid is 1:6, reacting for 3 hours at 50 ℃, then intercepting solid matters such as copper-tin-zinc slag and diamond by filtering through a filter screen, injecting the filtered hot ferrous sulfate into a polymerization reaction kettle, controlling the temperature to be 80 ℃, introducing liquid oxygen, wherein the dosage of the liquid oxygen is 18kg/m3The pressure is 400N, and the water purifying agent can be prepared after reaction for 2 hours and is used for treating and purifying wastewater.
The prepared water purifying agent is applied to treating wastewater:
1. antimony gold ore dressing wastewater: the main pollution indexes of arsenic and antimony are that the concentration of raw water arsenic is 0.5-5 mg/L and the concentration of antimony is 2-15 mg/L, and the treated water quality reaches the pollutant discharge index of the tin-antimony-mercury industry (GB 30770-2014).
2. Antimony-gold ore smelting wastewater: the main pollution indexes of arsenic and antimony are that the concentration of raw water arsenic is 1-10 mg/L and the concentration of antimony is 10-30 mg/L, and the treated water quality reaches the pollutant discharge index of the mercury-antimony-tin industry (GB 30770-2014).
3. Lead-zinc beneficiation wastewater: the main pollution indexes of lead, zinc, cadmium, arsenic and thallium, the raw water indexes of lead are less than 5mg/L, zinc is less than 20mg/L, cadmium is less than 2mg/L, arsenic is less than 3mg/L and thallium is less than 1mg/L, and the treated effluent reaches the lead-zinc industrial pollutant discharge standard (GB 25466-2010).
4. Lead-zinc smelting wastewater: the main pollution indexes of lead, zinc, cadmium, arsenic and thallium, the raw water indexes of lead are less than 20mg/L, zinc is less than 100mg/L, cadmium is less than 5mg/L, arsenic is less than 8mg/L and thallium is less than 3mg/L, and the treated effluent reaches the lead-zinc industrial pollutant discharge standard (GB 25466-2010).
Example 3
The industrial waste sulfuric acid (the sulfuric acid content is 85%) is filtered by a filter screen to remove impurities and then is put into a waste cutter head (the Fe weight content is 75%) for dissolution, and the weight ratio of the waste cutter head to the industrial waste sulfuric acid is 1: 5, reacting at 80 ℃ for 0.5 hour, then intercepting solid matters such as copper-tin-zinc slag and diamond by filtering through a filter screen, injecting the filtered hot ferrous sulfate into a polymerization reaction kettle, controlling the temperature to be 50 ℃, introducing liquid oxygen, wherein the dosage of the liquid oxygen is 15kg/m3The pressure is 500N, and the water purifying agent can be prepared after 4 hours of reaction and is used for treating and purifying wastewater.
The prepared water purifying agent is applied to treating wastewater:
1. antimony gold ore dressing wastewater: the main pollution indexes of arsenic and antimony are that the concentration of raw water arsenic is 0.5-5 mg/L and the concentration of antimony is 2-15 mg/L, and the treated water quality reaches the pollutant discharge index of the tin-antimony-mercury industry (GB 30770-2014).
2. Antimony-gold ore smelting wastewater: the main pollution indexes of arsenic and antimony are that the concentration of raw water arsenic is 1-10 mg/L and the concentration of antimony is 10-30 mg/L, and the treated water quality reaches the pollutant discharge index of the mercury-antimony-tin industry (GB 30770-2014).
3. Lead-zinc beneficiation wastewater: the main pollution indexes of lead, zinc, cadmium, arsenic and thallium, the raw water indexes of lead are less than 5mg/L, zinc is less than 20mg/L, cadmium is less than 2mg/L, arsenic is less than 3mg/L and thallium is less than 1mg/L, and the treated effluent reaches the lead-zinc industrial pollutant discharge standard (GB 25466-2010).
4. Lead-zinc smelting wastewater: the main pollution indexes of lead, zinc, cadmium, arsenic and thallium, the raw water indexes of lead are less than 20mg/L, zinc is less than 100mg/L, cadmium is less than 5mg/L, arsenic is less than 8mg/L and thallium is less than 3mg/L, and the treated effluent reaches the lead-zinc industrial pollutant discharge standard (GB 25466-2010).
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. A method for preparing a water purifying agent by using industrial waste sulfuric acid and waste cutter bits is characterized by comprising the following steps:
removing solid impurities in the industrial waste sulfuric acid to obtain pretreated industrial waste sulfuric acid;
mixing the pretreated industrial waste sulfuric acid with the waste cutter head to perform double decomposition reaction to obtain a hot ferrous sulfate solution;
and introducing liquid oxygen into the hot ferrous sulfate solution, and then carrying out polymerization reaction to obtain the liquid polymeric ferric sulfate water purifying agent.
2. The preparation method according to claim 1, wherein the mass content of sulfuric acid in the industrial waste sulfuric acid is 30 to 95%.
3. The manufacturing method according to claim 1 or 2, wherein the waste cutter head comprises the following components in weight content: fe 70-80%, Cu 15-20%, Sn 1-2%, Zn 2-4% and diamond 2-3%, wherein the sum of the weight contents of the components is 100%.
4. The preparation method according to claim 1, wherein the mass ratio of the waste cutter head to the industrial waste sulfuric acid is 1:4 to 1: 6.
5. The method according to claim 1, wherein the temperature of the metathesis reaction is 50 to 80 ℃.
6. The preparation method according to claim 1, wherein the ratio of the amount of the liquid oxygen to the amount of the hot ferrous sulfate solution is 15-18 kg/1m3。
7. The method according to claim 1, wherein the polymerization reaction is carried out at a pressure of 300 to 500N and a temperature of 50 to 80 ℃ for 2 to 4 hours.
8. The method of claim 1, wherein the metathesis reaction further produces a copper-tin-zinc mixture that enters a metal recovery system to extract copper, tin, and zinc.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076914A (en) * | 1992-08-31 | 1993-10-06 | 山东建筑工程学院 | The production technique of bodied ferric sulfate and device |
| CN105776354A (en) * | 2014-12-22 | 2016-07-20 | 祐鼎（福建）光电材料有限公司 | Preparation method of polymeric ferric sulfate |
| CN105948210A (en) * | 2016-07-11 | 2016-09-21 | 哈尔滨辰能工大环保科技股份有限公司 | Method for producing polymeric ferric sulfate from raw materials industrial waste acid and scrap iron |
| CN108046335A (en) * | 2017-11-29 | 2018-05-18 | 兰州理工大学白银新材料研究院 | A kind of solid ferric polysulfate preparation method |
| CN108557901A (en) * | 2018-05-10 | 2018-09-21 | 湘潭湘钢瑞兴公司 | A kind of production technology of steel mill's spent acid production bodied ferric sulfate |
-
2020
- 2020-01-06 CN CN202010008967.XA patent/CN111137925A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076914A (en) * | 1992-08-31 | 1993-10-06 | 山东建筑工程学院 | The production technique of bodied ferric sulfate and device |
| CN105776354A (en) * | 2014-12-22 | 2016-07-20 | 祐鼎（福建）光电材料有限公司 | Preparation method of polymeric ferric sulfate |
| CN105948210A (en) * | 2016-07-11 | 2016-09-21 | 哈尔滨辰能工大环保科技股份有限公司 | Method for producing polymeric ferric sulfate from raw materials industrial waste acid and scrap iron |
| CN108046335A (en) * | 2017-11-29 | 2018-05-18 | 兰州理工大学白银新材料研究院 | A kind of solid ferric polysulfate preparation method |
| CN108557901A (en) * | 2018-05-10 | 2018-09-21 | 湘潭湘钢瑞兴公司 | A kind of production technology of steel mill's spent acid production bodied ferric sulfate |
Non-Patent Citations (1)
| Title |
|---|
| 刘伟仁等: "利用铁氧化皮制备聚合硫酸铁", 《中国资源综合利用》 * |
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