CN111672276A - Resource utilization process of waste gas in production process of polymeric ferric sulfate - Google Patents
Resource utilization process of waste gas in production process of polymeric ferric sulfate Download PDFInfo
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- CN111672276A CN111672276A CN202010482700.4A CN202010482700A CN111672276A CN 111672276 A CN111672276 A CN 111672276A CN 202010482700 A CN202010482700 A CN 202010482700A CN 111672276 A CN111672276 A CN 111672276A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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Abstract
The invention discloses a resource utilization process of waste gas in the production process of polyferric sulfate, which comprises the steps of introducing waste gas containing nitrogen oxides (NOx) generated in the production process of the polyferric sulfate into a raw material liquid, transferring the nitrogen oxides in the waste gas into the raw material liquid through spraying and circulating absorption for producing the polyferric sulfate, and enabling the content of the nitrogen oxides in the absorbed tail gas to reach the emission standard. Factors such as temperature, flow, air adding amount, ferrous sulfate content in raw material liquid, circulation time and the like of a system need to be controlled in the processes of spraying and circulating absorption. The raw material liquid which has absorbed the nitrogen oxides is called absorption liquid, and then the absorption liquid is reused as a raw material. The absorbed nitrogen oxides can be used as a catalyst in the production process of the polyferric sulfate to participate in the subsequent production of the polyferric sulfate. The method can utilize the pollutants in the waste gas generated in the production of the polymeric ferric sulfate as resources, reduce the usage amount of the catalyst in the production process, save the cost and improve the production efficiency and the product quality; meanwhile, the problem of the emission of harmful components in tail gas in the production process of polymeric ferric sulfate is solved, and the method is beneficial to environmental protection.
Description
Technical Field
The invention relates to a resource utilization process of waste gas in a polymeric ferric sulfate production process.
Background
Polyferric sulfate is an inorganic polymeric flocculant developed in recent years, and has superior performance compared with traditional flocculants such as ferric trichloride and aluminum sulfate. The polyferric sulfate has the advantages of low production cost, small usage amount, wide applicable pH range, high pollutant removal rate, low residual concentration, good decolorization effect and the like, and can be widely applied to purification treatment of drinking water, industrial wastewater, municipal sewage, sludge dehydration and the like. The main production method of the polymeric ferric sulfate comprises the following steps: direct oxidation processes and catalytic oxidation processes. In the actual production, the catalytic oxidation method is mostly used, and the catalyst mainly comprises nitric acid, sodium nitrite and the like.
In the catalytic oxidation stage of polymeric ferric sulfate, ferrous iron and a catalyst firstly undergo an oxidation-reduction reaction to obtain ferric sulfate and generate Nitric Oxide (NO), and at the moment, introduced oxygen reacts with NO to generate NO2，NO2Dissolving in water to generate nitric acid and NO, reacting nitric acid with ferrous iron to generate NO, and continuously circulating. However, this technique has a process drawback: toxic gases NO and NO are generated in the reaction process2When the intermittent reaction is finished, NO which does not participate in the reaction is discharged out of the reaction kettle along with the product, enters the storage tank and overflows out of the storage tank along with hot water vapor, and reacts with air to generate yellow nitrogen dioxide, so that the air is polluted and the environment is damaged.
Disclosure of Invention
The invention aims to provide a resource utilization process of waste gas in a polymeric ferric sulfate production process, which solves the problem of resource utilization of useful components in the waste gas and the problem of emission of nitrogen oxides in the waste gas in the existing production process.
The technical scheme of the invention is as follows.
A resource utilization process of waste gas in the production process of polymeric ferric sulfate is characterized in that: the raw material in the production process of the polyferric sulfate is used as a waste gas absorption liquid to absorb waste gas generated in the production process of the polyferric sulfate, and nitrogen oxides in the waste gas are absorbed and recycled as a catalyst in the production process of the polyferric sulfate. The absorption process of waste gas in the production process of the polymeric ferric sulfate is as follows:
mixing the byproduct ferrous sulfate heptahydrate in the titanium dioxide industry and the waste sulfuric acid according to a certain weight ratio of 1: (1-10) stirring, heating and dissolving to obtain a raw material liquid, and conveying the raw material liquid to an absorption tower. By adjusting the gas flow (0.1-2 times of the waste gas flow) in the system, the waste gas containing nitrogen oxides generated in the production process of the polyferric sulfate is blown into the raw material liquid containing gold sulfate and ferrous sulfate, the temperature of the raw material liquid is controlled to be 0-100 ℃, the absorption cycle time is 0-60min, the waste gas is fully absorbed in the absorption equipment, and certain air is added to promote the conversion absorption of the waste gas. Fully absorbing in an absorption bottle to obtain absorption liquid, and directly discharging tail gas. Then collecting the absorption liquid, placing the absorption liquid in a reactor, adding a catalyst and introducing oxygen, and reacting for a period of time to obtain a polymeric ferric sulfate product
The ferrous sulfate heptahydrate is a byproduct in the titanium dioxide industry and is one of production raw materials of polymeric ferric sulfate.
The waste sulfuric acid is a byproduct in the titanium dioxide industry and is one of production raw materials of polymeric ferric sulfate, and contains a certain amount of sulfuric acid and ferrous sulfate.
The raw material liquid is titanium white waste acid solution dissolved with certain ferrous sulfate, and is a raw material used in the production of polymeric ferric sulfate.
The absorption tower is a gas absorption device with a spray header and a filler.
The tail gas is generated in the production process of polymeric ferric sulfate, and contains nitrogen oxides (NOx).
The air flow rate of the feeding air and the waste gas flow rate in the system have a certain relation, and are generally 0.1-2 times.
The control temperature is that the temperature of the absorption liquid is 0-100 ℃ when the tail gas is absorbed.
The air is added in an amount to oxidize NO in the exhaust gas and promote absorption of the exhaust gas by the solution.
The circulation is that the waste gas continuously contacts with the raw material liquid in the absorption tower through a branch, and the circulation time is 0-60 min.
The tail gas is gas containing nitrogen oxides generated in the production process of polymeric ferric sulfate.
The absorption liquid is a raw material liquid which absorbs the waste gas and is reused as a raw material for the production of the polyferric sulfate.
The invention has the beneficial effects that: the production raw material of the polymeric ferric sulfate is used as the absorption liquid to treat the waste gas, so that the treatment cost is low; harmful components NOx in the waste gas are absorbed, so that the emission of the waste gas is reduced, and the pollution to the environment is also reduced; the absorbed tail gas is recycled as a catalyst, so that the production cost is reduced.
Drawings
Embodiments of the present invention are described in further detail below with reference to the accompanying drawings.
FIG. 1 is a schematic flow chart of a resource utilization process of waste gas in a polymeric ferric sulfate production process.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be described in further detail with reference to the accompanying drawings and examples, which are not intended to limit the scope of the present invention.
FIG. 1 is a schematic process flow diagram of the present invention. As shown in figure 1, in the invention, ferrous sulfate and waste sulfuric acid are mixed to obtain a raw material solution, polymeric ferrous sulfate is prepared under the action of a catalyst and oxygen, waste gas is generated in the production process, the waste gas is introduced into the prepared raw material solution, absorption liquid is obtained after the waste gas is fully absorbed, the absorption liquid is recycled, and the dissolved waste gas is used as the catalyst for the production of polymeric ferric sulfate, so that the resource utilization of the waste gas is realized.
Example 1
Mixing ferrous sulfate heptahydrate and waste sulfuric acid according to the weight ratio of 1:1.8, and adding the mixture into a gas absorption bottle; adding the prepared raw material liquid into a three-neck flask, adding 20mL of sodium nitrite solution with the concentration of 1mol/L as a catalyst, controlling the reaction temperature to be 65 ℃, controlling the adding amount of air to be 0.1L/min, controlling the gas circulation flow of a system to be 0.6L/min, and circulating for 60 min. The measured nitrogen oxide concentration of the outlet tail gas is 115mg/m3, and the requirement of nitrogen oxide (other) in the standard DB 44/27-2001 is met. The absorption liquid is used for producing polymeric ferric sulfate, a proper amount of ferrous sulfate is supplemented into the polymeric ferric sulfate, the polymeric ferric sulfate is heated to 60-80 ℃, 19.5mL of sodium nitrite solution is added, and after the absorption liquid is finished, the mass fraction of total iron in the polymeric ferric sulfate is measured to be 11.2%, and the ferrous content is measured to be 0.09% (mass fraction), so that the requirement in the national standard GB/T14591-2016 is met.
Example 2
Mixing ferrous sulfate heptahydrate and titanium white waste acid according to the weight ratio of 1:2.4, and adding the mixture into a gas absorption bottle; adding the prepared raw material liquid into a three-neck flask, adding 20mL of sodium nitrite solution with the concentration of 1mol/L as a catalyst, controlling the reaction temperature to be 65 ℃, controlling the adding amount of air to be 0.1L/min, controlling the gas circulation flow of a system to be 0.6L/min, and circulating for 60 min. The measured concentration of nitrogen oxides in the outlet tail gas is 85mg/m3, and the requirement of nitrogen oxides (other) in the standard DB 44/27-2001 is met. The absorption liquid is used for producing polymeric ferric sulfate, a proper amount of ferrous sulfate is supplemented into the polymeric ferric sulfate, the polymeric ferric sulfate is heated to 60-80 ℃, 18.6mL of sodium nitrite solution is added, and after the absorption liquid is finished, the mass fraction of total iron in the polymeric ferric sulfate is measured to be 11.5%, and the ferrous content is 0.05% (mass fraction), so that the requirement in the national standard GB/T14591-2016 is met.
Example 3
Mixing ferrous sulfate heptahydrate and titanium white waste acid according to the weight ratio of 1:2.2, and adding the mixture into a gas absorption bottle; adding the prepared raw material liquid into a three-neck flask, adding 20mL of sodium nitrite solution with the concentration of 1mol/L as a catalyst, controlling the reaction temperature to be 65 ℃, controlling the adding amount of air to be 0.1L/min, controlling the gas circulation flow of a system to be 0.6L/min, and circulating for 60 min. The measured nitrogen oxide concentration of the outlet tail gas is 87mg/m3, and meets the requirements of nitrogen oxide (other) in the standard DB 44/27-2001. The absorption liquid is used for producing the polymeric ferric sulfate, a proper amount of ferrous sulfate is supplemented into the polymeric ferric sulfate, the polymeric ferric sulfate is heated to 60-80 ℃, 19mL of sodium nitrite solution is added, and after the absorption liquid is finished, the mass fraction of the total iron in the polymeric ferric sulfate is measured to be 11.7 percent, and the ferrous content is 0.03 percent (mass fraction), so that the requirement in the national standard GB/T14591-2016 is met.
Example 4
Mixing ferrous sulfate heptahydrate and titanium white waste acid according to the weight ratio of 1:2, and adding the mixture into a gas absorption bottle; adding the prepared raw material liquid into a three-neck flask, adding 20mL of sodium nitrite solution with the concentration of 1mol/L as a catalyst, controlling the reaction temperature to be 65 ℃, controlling the adding amount of air to be 0.1L/min, controlling the gas circulation flow of a system to be 0.6L/min, and circulating for 60 min. The measured nitrogen oxide concentration of the outlet tail gas is 109mg/m3, and meets the requirements of nitrogen oxide (other) in the standard DB 44/27-2001. The absorption liquid is used for producing polymeric ferric sulfate, a proper amount of ferrous sulfate is supplemented into the polymeric ferric sulfate, the polymeric ferric sulfate is heated to 60-80 ℃, 19.3mL of sodium nitrite solution is added, and after the absorption liquid is finished, the mass fraction of total iron in the polymeric ferric sulfate is measured to be 11.4%, and the ferrous content is measured to be 0.06% (mass fraction), so that the requirement in the national standard GB/T14591-2016 is met.
Claims (10)
1. The utility model provides a resource utilization technology of waste gas in polyferric sulfate production process which characterized in that, utilizes polyferric sulfate's raw materials for production, absorbs harmful gas nitrogen oxide (NOx) that produces in the polyferric sulfate production process, and the nitrogen oxide that absorbs is used for polyferric sulfate's catalytic oxidation to realize the resource utilization of waste gas, the flow of tail gas resource utilization is: mixing ferrous sulfate heptahydrate which is a production raw material of polymeric ferric sulfate and waste sulfuric acid according to a certain mass ratio, heating, stirring and dissolving to obtain a raw material liquid, conveying the raw material liquid to an absorption tower, blowing nitrogen oxide-containing waste gas generated in the production process of the polymeric ferric sulfate into the raw material liquid containing the ferrous sulfate, adjusting the gas flow in a treatment system, controlling the temperature of the raw material liquid, absorbing the circulation time, introducing a certain amount of air, fully absorbing in an absorption bottle to obtain an absorption liquid, directly discharging tail gas, collecting the absorption liquid, placing in a reactor, adding a catalyst, introducing oxygen, and reacting for a period of time to obtain a polymeric ferric sulfate product.
2. The resource utilization process of tail gas in the production process of polymeric ferric sulfate according to claim 1, characterized in that: the ferrous sulfate heptahydrate is a byproduct generated in the titanium dioxide industry together with waste sulfuric acid, and is one of raw materials used in the production of polymeric ferric sulfate.
3. The resource utilization process of tail gas in the production process of polymeric ferric sulfate according to claim 1, characterized in that: the waste sulfuric acid is a byproduct generated in the titanium dioxide industry, is one of raw materials used in the production of polymeric ferric sulfate, and contains a certain amount of sulfuric acid and ferrous sulfate, wherein the sulfuric acid content is 0-30%, and the ferrous sulfate content is 0-15%.
4. The resource utilization process of tail gas in the production process of polymeric ferric sulfate according to claim 1, characterized in that: the raw material liquid is a waste sulfuric acid solution in which a certain amount of ferrous sulfate heptahydrate is dissolved, and is a raw material for producing polymeric ferric sulfate, wherein the content of sulfuric acid is 0-30%, the content of ferrous sulfate is 0-30%, and the mass ratio of ferrous sulfate heptahydrate to waste sulfuric acid is 1: (1-10).
5. The resource utilization process of tail gas in the production process of polymeric ferric sulfate according to claim 1, characterized in that: the heating temperature when the ferrous sulfate heptahydrate is mixed with the waste acid is 100-200 ℃.
6. The resource utilization process of waste gas in the production process of polymeric ferric sulfate according to claim 1, characterized in that: the ratio of the flow rate of the air added to the system to the flow rate of the exhaust gas is 0.1-2 times.
7. The resource utilization process of tail gas in the production process of polymeric ferric sulfate according to claim 1, characterized in that: and controlling the temperature of the raw material liquid to be 0-100 ℃ when the raw material liquid absorbs the waste gas.
8. The resource utilization process of tail gas in the production process of polymeric ferric sulfate according to claim 1, characterized in that: the circulation is that the waste gas continuously contacts with the raw material liquid in the absorption tower through a branch, and the circulation time is 0-60 min.
9. The resource utilization process of tail gas in the production process of polymeric ferric sulfate according to claim 1, characterized in that: the absorption liquid is a raw material liquid which absorbs the waste gas and is reused as a raw material for the production of the polyferric sulfate.
10. The resource utilization process of tail gas in the production process of polymeric ferric sulfate according to claim 1, characterized in that: the waste gas of resource utilization is gas containing components such as nitrogen oxide, water vapor and the like generated in the production process of the polyferric sulfate, wherein the nitrogen oxide realizes resource utilization and is reused as a catalyst for the production of the polyferric sulfate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707446A (en) * | 2021-02-07 | 2021-04-27 | 杭州金丰环保科技有限公司 | Preparation method of polymeric ferric sulfate |
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Application publication date: 20200918 |