CN111229252A - Novel iron matrix high-efficiency catalytic carrier with autotrophic and heterotrophic coupling effects - Google Patents
Novel iron matrix high-efficiency catalytic carrier with autotrophic and heterotrophic coupling effects Download PDFInfo
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- CN111229252A CN111229252A CN202010161285.2A CN202010161285A CN111229252A CN 111229252 A CN111229252 A CN 111229252A CN 202010161285 A CN202010161285 A CN 202010161285A CN 111229252 A CN111229252 A CN 111229252A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/166—Nitrites
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/16—Total nitrogen (tkN-N)
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Abstract
The invention provides a novel iron matrix high-efficiency catalytic carrier with autotrophic and heterotrophic coupling effects, which comprises the following raw materials in parts by weight: 40.000 to 98.000 parts of zero-valent iron, 5.000 to 28.000 parts of activated carbon powder, 4.500 to 17.500 parts of water glass, 1.000 to 6.000 parts of Portland cement and 0.500 to 6.000 parts of multi-element metal catalyst; the invention provides a method for increasing NO in sewage3 ‑The reduction efficiency of N is reduced, the inhibition of the pH of the water body on the reduction reaction is reduced, and NO in the reduction process can be reduced2 –-N and NH4 +A novel iron substrate high-efficiency catalytic denitrification carrier generated by N and has good treatment effect within the pH value of 6-9And the TN removal is realized in the true sense, and the purification effect on the phosphorus in the sewage is good.
Description
Technical Field
The invention relates to sewage treatment, in particular to a novel iron matrix high-efficiency catalytic carrier with autotrophic and heterotrophic coupling effects.
Background
NO in environmental water of China3 -The pollution of-N is continuously increased, and the sewage plant drainage is NO in the environmental water body3 -One of the main sources of-N. Domestic sewage treatment plant drainageIn the nitrogen as NO3 -the-N is mainly 28-68% of the Total Nitrogen (TN), and if the-N is directly discharged into an environmental water body, the eutrophication of the water body is caused, and the black and smelly water body can be caused. Thus, NO3 -The removal of-N has become an important issue for sewage plant drainage TN emission control.
It is generally considered that when BOD is contained in the wastewater5And when the/TN is less than 3-5, the sewage is low in carbon-nitrogen ratio. However, after the domestic sewage is subjected to secondary treatment in a sewage plant, BOD is consumed in large quantities, resulting in BOD of the discharged water5the/TN is only 0.3-0.8, belonging to typical sewage with low carbon-nitrogen ratio, and the sewage is difficult to realize deep denitrification by utilizing the traditional biological denitrification process. If a physicochemical method such as reverse osmosis, ion exchange, electrodialysis and the like is adopted, a certain denitrification effect can be achieved in sewage treatment, but the method has the defects of high investment, high energy consumption, generation of concentrated water and the like, and is not suitable for deep denitrification treatment of sewage plant drainage.
The working principle of the domestic iron matrix carrier is that zero-valent iron can be used for rapidly reducing NO3 -N, although having a certain purifying effect, is seriously affected by the pH of the water, and it is often necessary to adjust the pH to 4 to 5 or less and reduce the product with NH4 +predominantly-N, TN removal is difficult to achieve. Reduction of NO to increase zero-valent iron3 -Efficiency of N, reduction of NO with nano zero valent iron (nZVI)3 --N, greatly increasing the reduction of NO by zero-valent iron3 -The efficiency of N while reducing the influence of pH on the rate of the reduction reaction. However, the passivation rate of nZVI in the reaction is fast, and the reduction product is still NH4+N is dominant, and the production cost of nZVI is much higher than that of ordinary zero-valent iron (ZVI), so the technology is not yet put into practical use. Therefore, the development of a novel deep denitrification technology with high efficiency, low consumption and no secondary pollution is of great significance.
Disclosure of Invention
The invention aims to provide a novel iron matrix high-efficiency catalytic carrier with autotrophic and heterotrophic coupling effects, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a novel iron matrix high-efficiency catalytic carrier with autotrophic and heterotrophic coupling effects comprises the following raw materials in parts by weight: 40.000 to 98.000 parts of zero-valent iron, 5.000 to 28.000 parts of activated carbon powder, 4.500 to 17.500 parts of water glass, 1.000 to 6.000 parts of Portland cement and 0.500 to 6.000 parts of multi-element metal catalyst.
As a further scheme of the invention: the composite material comprises the following raw materials in parts by weight: 55.000-83.000 parts of zero-valent iron, 8.000-25.000 parts of activated carbon powder, 7.500-14.500 parts of water glass, 2.000-5.000 parts of Portland cement and 1.500-5.000 parts of multi-original metal catalyst.
As a further scheme of the invention: the multi-element metal catalyst comprises the following raw materials in parts by weight: 0.300-2.100 parts of manganese, 0.010-0.100 part of vanadium, 0.010-0.120 part of zinc, 0.010-0.800 part of titanium, 0.100-0.850 part of copper, 0.001-0.100 part of cobalt, 0.0010.050 parts of nickel, 0.010-0.100 part of chromium, 0.001-0.150 part of gallium, 0.010-0.120 part of strontium, 0.005-0.100 part of zirconium, 0.002-0.080 part of rubidium, 0.001-0.050 part of niobium, 0.001-0.050 part of yttrium, 0.001-0.050 part of molybdenum, 0.010-0.800 part of barium, 0.001-0.020 part of cerium, 0.001-0.020 part of cesium and 0.001-0.020 part of platinum.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for increasing NO in sewage3 -The reduction efficiency of N is reduced, the inhibition of the pH of the water body on the reduction reaction is reduced, and NO in the reduction process can be reduced2 –-N and NH4 +The novel iron substrate high-efficiency catalytic denitrification carrier generated by the N has a good treatment effect within the pH value range of 6-9, realizes TN removal in the true sense, and has a good purification effect on phosphorus in sewage. Iron-based high-efficiency catalytic denitrification carrier added with multi-metal catalyst for raw water NO with different pH values3 -The removal rate of-N is 90-95%, and the method can be used for removing nitrate Nitrogen (NO) in sewage water3 --N) the removal efficiency is greatly increased; nitrite (NO) during reduction2 –-N) and ammonium (NH)4 +-N) the generation rate is low, and no secondary pollution is caused to the water body; has low passivation rate, can maintain activity for a long time in the use process, and further reducesThe cost is low, and the carrier is not hardened; the device is not influenced by the carbon-nitrogen ratio of water, the use temperature and the application range; the investment is low, the energy consumption is low, and no waste water or sludge is generated; meanwhile, the method also has high purification efficiency on phosphorus, and the efficiency can reach 85-95%.
Detailed Description
The technical solution of the present patent will be described in further detail with reference to the following embodiments.
A novel iron matrix high-efficiency catalytic carrier with autotrophic and heterotrophic coupling effects comprises the following raw materials in parts by weight: 40.000 to 98.000 parts of zero-valent iron, 5.000 to 28.000 parts of activated carbon powder, 4.500 to 17.500 parts of water glass, 1.000 to 6.000 parts of Portland cement and 0.500 to 6.000 parts of multi-element metal catalyst. The main raw material of the iron-based high-efficiency catalytic denitrification carrier is zero-valent iron, and the zero-valent iron is mixed with a multi-element metal catalyst, a foaming agent and an adhesive to prepare a carrier with the diameter of 5-50mm, and the carrier is placed into a roasting furnace and roasted at the high temperature of 900-1100 ℃; wherein, the zero-valent iron is iron powder; one part of the activated carbon powder reacts to produce gas in the roasting process and plays the role of a foaming agent, and the other part of the activated carbon powder does not participate in the reaction and is left in the iron-matrix carrier finished product; the adhesive is mainly water glass and common Portland cement, and mainly plays a role in bonding and forming raw materials. The multi-element metal catalyst is prepared by mixing a fourth period transition metal element (manganese, vanadium, zinc, titanium, copper, cobalt, nickel, chromium and gallium), a fifth period transition metal element (strontium, zirconium, rubidium, niobium, molybdenum and yttrium), a sixth period transition metal element (barium, cesium and platinum) and cerium according to a certain proportion.
Specifically, the feed comprises the following raw materials in parts by weight: 55.000-83.000 parts of zero-valent iron, 8.000-25.000 parts of activated carbon powder, 7.500-14.500 parts of water glass, 2.000-5.000 parts of Portland cement and 1.500-5.000 parts of multi-original metal catalyst.
Specifically, the multi-element metal catalyst comprises the following raw materials in parts by weight: 0.300-2.100 parts of manganese, 0.010-0.100 part of vanadium, 0.010-0.120 part of zinc, 0.010-0.800 part of titanium, 0.100-0.850 part of copper, 0.001-0.100 part of cobalt, 0.0010.050 parts of nickel, 0.010-0.100 part of chromium, 0.001-0.150 part of gallium, 0.010-0.120 part of strontium, 0.005-0.100 part of zirconium, 0.002-0.080 part of rubidium, 0.001-0.050 part of niobium, 0.001-0.050 part of yttrium, 0.001-0.050 part of molybdenum, 0.010-0.800 part of barium, 0.001-0.020 part of cerium, 0.001-0.020 part of cesium and 0.001-0.020 part of platinum.
The iron substrate high-efficiency catalytic denitrification carrier added with the multi-metal catalyst is used for carrying out NO treatment on raw water with different pH values3 -The removal rate of-N is 90-95%, and the method can be used for removing nitrate Nitrogen (NO) in sewage water3 --N) the removal efficiency is greatly increased; nitrite (NO) during reduction2 –-N) and ammonium (NH)4 +-N) the generation rate is low, and no secondary pollution is caused to the water body; the passivation rate is low, the activity can be maintained for a long time in the use process, the cost is further reduced, and the carrier is not hardened; the device is not influenced by the carbon-nitrogen ratio of water, the use temperature and the application range; the investment is low, the energy consumption is low, and no waste water or sludge is generated; meanwhile, the method also has high purification efficiency on phosphorus, and the efficiency can reach 85-95%.
Although the preferred embodiments of the present patent have been described in detail, the present patent is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present patent within the knowledge of those skilled in the art.
Claims (3)
1. A novel iron matrix high-efficiency catalytic carrier with autotrophic and heterotrophic coupling effects is characterized by comprising the following raw materials in parts by weight: 40.000 to 98.000 parts of zero-valent iron, 5.000 to 28.000 parts of activated carbon powder, 4.500 to 17.500 parts of water glass, 1.000 to 6.000 parts of Portland cement and 0.500 to 6.000 parts of multi-element metal catalyst.
2. The novel iron matrix high-efficiency catalytic carrier with the autotrophic and heterotrophic coupling effect according to claim 1 is characterized by comprising the following raw materials in parts by weight: 55.000-83.000 parts of zero-valent iron, 8.000-25.000 parts of activated carbon powder, 7.500-14.500 parts of water glass, 2.000-5.000 parts of Portland cement and 1.500-5.000 parts of multi-original metal catalyst.
3. The novel iron matrix high-efficiency catalytic carrier with the autotrophic and heterotrophic coupling effect according to claim 1, wherein the multi-element metal catalyst comprises the following raw materials in parts by weight: 0.300-2.100 parts of manganese, 0.010-0.100 part of vanadium, 0.010-0.120 part of zinc, 0.010-0.800 part of titanium, 0.100-0.850 part of copper, 0.001-0.100 part of cobalt, 0.0010.050 parts of nickel, 0.010-0.100 part of chromium, 0.001-0.150 part of gallium, 0.010-0.120 part of strontium, 0.005-0.100 part of zirconium, 0.002-0.080 part of rubidium, 0.001-0.050 part of niobium, 0.001-0.050 part of yttrium, 0.001-0.050 part of molybdenum, 0.010-0.800 part of barium, 0.001-0.020 part of cerium, 0.001-0.020 part of cesium and 0.001-0.020 part of platinum.
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| CN202010161285.2A CN111229252A (en) | 2020-03-10 | 2020-03-10 | Novel iron matrix high-efficiency catalytic carrier with autotrophic and heterotrophic coupling effects |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602521A (en) * | 2022-02-22 | 2022-06-10 | 北京和众大成环保科技有限公司 | Multi-element catalytic composite carrier based on cementite-carbon system |
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| CN102951708A (en) * | 2012-09-24 | 2013-03-06 | 潍坊海洁环保设备有限公司 | Multielement catalysis iron-carbon micro-electrolysis filler and preparation method thereof |
| CN103145234A (en) * | 2013-03-22 | 2013-06-12 | 北京交通大学 | Aerobic bio-particle carrier for directly removing ammonia nitrogen from sewage with low carbon nitrogen ratio and preparation method thereof |
| WO2015109899A1 (en) * | 2014-01-21 | 2015-07-30 | 北京师范大学 | Method for quickly and effectively removing heavy metals in water body |
| CN109110862A (en) * | 2018-09-20 | 2019-01-01 | 北京师范大学 | A kind of denitrogenation dephosphorizing material and preparation method thereof |
| CN109650561A (en) * | 2019-02-26 | 2019-04-19 | 清华大学 | A kind of denitrification functions filler and its preparation and application |
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- 2020-03-10 CN CN202010161285.2A patent/CN111229252A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951708A (en) * | 2012-09-24 | 2013-03-06 | 潍坊海洁环保设备有限公司 | Multielement catalysis iron-carbon micro-electrolysis filler and preparation method thereof |
| CN103145234A (en) * | 2013-03-22 | 2013-06-12 | 北京交通大学 | Aerobic bio-particle carrier for directly removing ammonia nitrogen from sewage with low carbon nitrogen ratio and preparation method thereof |
| WO2015109899A1 (en) * | 2014-01-21 | 2015-07-30 | 北京师范大学 | Method for quickly and effectively removing heavy metals in water body |
| CN109110862A (en) * | 2018-09-20 | 2019-01-01 | 北京师范大学 | A kind of denitrogenation dephosphorizing material and preparation method thereof |
| CN109650561A (en) * | 2019-02-26 | 2019-04-19 | 清华大学 | A kind of denitrification functions filler and its preparation and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602521A (en) * | 2022-02-22 | 2022-06-10 | 北京和众大成环保科技有限公司 | Multi-element catalytic composite carrier based on cementite-carbon system |
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Application publication date: 20200605 |