CN112169825A - Ion induction catalyst for industrial circulating water treatment and preparation method thereof - Google Patents
Ion induction catalyst for industrial circulating water treatment and preparation method thereof Download PDFInfo
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- CN112169825A CN112169825A CN202010994081.7A CN202010994081A CN112169825A CN 112169825 A CN112169825 A CN 112169825A CN 202010994081 A CN202010994081 A CN 202010994081A CN 112169825 A CN112169825 A CN 112169825A
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- circulating water
- catalyst
- zeolite
- ion
- vacuum
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 10
- 230000006698 induction Effects 0.000 title claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 38
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 30
- 239000010457 zeolite Substances 0.000 claims abstract description 30
- 150000002500 ions Chemical class 0.000 claims abstract description 27
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 27
- 230000001939 inductive effect Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- UNYOJUYSNFGNDV-UHFFFAOYSA-M magnesium monohydroxide Chemical compound [Mg]O UNYOJUYSNFGNDV-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
-
- B01J35/40—
-
- B01J35/618—
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
-
- 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
- C02F2101/103—Arsenic compounds
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
Abstract
An ion-induced catalyst for treating industrial circulating water is prepared from natural zeolite through high-temp pore-forming, vacuum activating in the presence of sodium carbonate solution and sodium hydroxide solution, and drying. The invention has the beneficial effects that: the ion-induced catalyst after pore-forming and activating has greatly increased specific surface area, and makes the adsorption of embedded CO in and on the zeolite pore channel2‑ 3And OH‑The method can ensure that the metal ions are rapidly precipitated on the surface of the catalyst and gradually increased to form spherical crystals for discharge, and has good precipitation effect and higher removal rate of the metal ions.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to an ion induction catalyst for industrial circulating water treatment and a preparation method thereof.
Background
In the operation process of large-scale metallurgy, petrochemical industry and chemical industry production, a large amount of industrial circulating water is required to exchange heat generated in the production process so as to ensure productionAnd (5) normally running. A certain amount of Ca exists in the industrial circulating water2+、Mg2+、Fe2+、Mn2+、As3+And F-The plasma can cause great harm such as scaling, corrosion and the like to the equipment pipeline in the operation process, and aims to prevent and reduce Ca in the circulating water2+、Mg2+、Fe2+、Mn2+、As3+And F-The traditional method is to add sufficient antiscale and corrosion inhibitor into the circulating water, the method plays a certain role in antiscale and corrosion inhibition in the using process of the circulating water, but has great defects that firstly, a large amount of medicament needs to be added, which causes waste and increases the operating cost, and on the other hand, because of evaporation loss of water in the operating process of the circulating water, Ca in the circulating water can be caused to be evaporated and lost2+、Mg2+、Fe2+、Mn2+、As3+And F-Plasma constantly enriches, and the concentration increases, needs a large amount of strong brine waste water of discharging and constantly supplyes fresh water and be used for guaranteeing production normal operating, causes the very big waste of water resource, and the emission of strong brine also causes pressure to subsequent high salt waste water treatment simultaneously.
At present, there is also a method of inducing crystallization by adding seed crystal, the seed crystal is added to accelerate the speed of precipitation crystallization and sedimentation, the seed crystal material of the method is usually quartz sand, silicate and the like, but the method only adds seed crystal or adds seed crystal and precipitant, the seed crystal particle is taken as the conventional solid particle, the inducing effect is small, and therefore the speed of inducing crystallization is slow.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the ion-induced catalyst for industrial circulating water treatment and the preparation method thereof, which can quickly crystallize and precipitate metal ions in water, have good precipitation effect and higher removal rate of the metal ions.
An ion-induced catalyst for treating industrial circulating water is prepared from zeolite: sodium carbonate solution: the volume ratio of the sodium hydroxide solution is 1:2-50: 2-50;
the zeolite is natural zeolite with the diameter of 0.1-2.0mm, the mass concentration of a sodium carbonate solution is 10-30%, and the mass concentration of a sodium hydroxide solution is 3-15%.
A preparation method of an ion-induced catalyst for industrial circulating water treatment comprises the following steps:
step one, high-temperature pore forming, namely calcining natural zeolite in a high-temperature furnace, keeping the temperature at 650-850 ℃ for 4-12h, and cooling for later use;
step two, vacuum activation, namely adding calcined natural zeolite into a reaction bottle, vacuumizing the reaction bottle to a limit vacuum state by using a vacuum pump, sucking a sodium carbonate solution and a sodium hydroxide solution in a feeding funnel connected with the reaction bottle into the reaction bottle by using vacuum, opening an emptying valve to release vacuum, soaking for 6-24 hours at normal pressure, and filtering;
and step three, drying, filtering the soaked and activated zeolite, and drying for 4-10 hours at the temperature of 90-110 ℃.
The ratio of the sodium carbonate solution to the sodium hydroxide solution is controlled in a volume ratio of 1: 0.1-1.
The particle diameter D of the ion-induced catalyst50100-2G, density 1-3.5g/cm3。
The application and the principle of the invention are as follows:
the ion-induced catalyst is used in an industrial circulating water treatment device to remove Ca in water2+、Mg2+、Fe2+、Mn2+、As3+The ions are concentrated on the catalyst surface where they react with OH added to the system-And CO2Water insoluble precipitate generated by the reaction is attached to the inner hole and the surface of the catalyst and is continuously grown to form spherical particles to be discharged out of the system, thereby removing Ca in the water2+、Mg2+、Fe2 +、Mn2+、As3+The circulating water is purified, the evaporation rate of the circulating water is improved, and the scaling and corrosion hazards of harmful ions in water to the circulating system are reduced. Utilization of purified CO in boiler flue gas2CO as a system3 2-The source, on one hand, saves a large amount of cost, and on the other hand, can greatly reduce the temperatureThe room gas is discharged, and ecological protection and high-quality development are realized.
The ion inducing catalyst for industrial circulating water is prepared with natural zeolite as carrier and through high temperature calcination to modify the inner pore passage of zeolite and raise the specific surface area greatly, and soaking in sodium carbonate and sodium hydroxide solution under vacuum condition to adsorb and inlay CO onto the surface and inner pore passage of zeolite2- 3And OH-. Ca in water2+、Mg2+When the ions enter the interior and the surface of the catalyst to contact with CO2- 3And OH-Combined formation of CaCO3·MgCO3The MgOH precipitates grow inside and on the surface of the support and grow continuously into spherical particles. The spherical particles are dissolved by acid to remove precipitates, and then are activated to be used as the ion-induced catalyst again for recycling.
The invention has the beneficial effects that: the ion induced catalyst after pore forming and activation has greatly increased specific surface area and makes the adsorption of embedded CO in and on the zeolite pore channel2- 3And OH-The method can ensure that the metal ions are rapidly precipitated on the surface of the catalyst and gradually increased to form spherical crystals for discharge, has good precipitation effect and higher removal rate of the metal ions, and can achieve the removal rate of the metal ions reaching over 75 percent when being applied to industrial circulating water treatment; in addition, the ion-induced catalyst provided by the invention has the advantages of low raw material price, simple preparation method and low cost, and can be widely used for softening industrial circulating water in factories.
Detailed Description
Example 1, the present invention provides an ion-induced catalyst for industrial circulating water treatment and a method for preparing the same, which introduces CO using a zeolite porous framework by an impregnation method3 2-And OH-Forming the ion-induced catalyst with the anion-loaded active group.
The ion-induced catalyst is prepared from the following raw materials: sodium carbonate solution: the volume ratio of the sodium hydroxide solution is 1:2: 2; the zeolite is natural zeolite with the diameter of 0.1-2.0mm, the mass concentration of the sodium carbonate solution is 30%, and the mass concentration of the sodium hydroxide solution is 15%.
The preparation method of the ion-induced catalyst comprises the following steps:
step one, high-temperature pore forming, namely calcining 1L of natural zeolite in a high-temperature furnace, keeping the temperature at 650 ℃ for 12 hours, and cooling for later use;
step two, vacuum activation, namely adding calcined natural zeolite into a reaction bottle, vacuumizing the reaction bottle to a limit vacuum state by using a vacuum pump, sucking 2L of sodium carbonate solution (with the mass concentration of 30%) and 2L of sodium hydroxide solution (with the mass concentration of 15%) in a feeding funnel connected with the reaction bottle into the reaction bottle by using vacuum, opening an emptying valve to release vacuum, soaking for 6-24 hours at normal pressure, and filtering;
and step three, drying, filtering the soaked and activated zeolite, and drying for 4 hours at 110 ℃.
Example 2, an ion-inducing catalyst was prepared using the following starting materials, zeolite: sodium carbonate solution: the volume ratio of the sodium hydroxide solution is 1:50: 2; the zeolite is natural zeolite with the diameter of 0.1-2.0mm, the mass concentration of the sodium carbonate solution is 10%, and the mass concentration of the sodium hydroxide solution is 15%.
The preparation method of the ion-induced catalyst comprises the following steps:
step one, high-temperature pore forming, namely calcining 1L of natural zeolite in a high-temperature furnace, keeping the temperature at 850 ℃ for 4 hours, and cooling for later use;
step two, vacuum activation, namely adding calcined natural zeolite into a reaction bottle, vacuumizing the reaction bottle to a limit vacuum state by using a vacuum pump, sucking 50L of sodium carbonate solution (with the mass concentration of 10%) and 2L of sodium hydroxide solution (with the mass concentration of 15%) in a feeding funnel connected with the reaction bottle into the reaction bottle by using vacuum, opening an emptying valve to release vacuum, soaking for 6-24 hours at normal pressure, and filtering;
and step three, drying, filtering the soaked and activated zeolite, and drying at 90 ℃ for 10 h.
Example 3, an ion-inducing catalyst was prepared using the following starting materials, zeolite: sodium carbonate solution: the volume ratio of the sodium hydroxide solution is 1:50: 50; the zeolite is natural zeolite with the diameter of 0.1-2.0mm, the mass concentration of the sodium carbonate solution is 10%, and the mass concentration of the sodium hydroxide solution is 3%.
The preparation method of the ion-induced catalyst comprises the following steps:
step one, high-temperature pore forming, namely calcining 1L of natural zeolite in a high-temperature furnace, keeping the temperature at 700 ℃ for 8 hours, and cooling for later use;
step two, vacuum activation, namely adding calcined natural zeolite into a reaction bottle, vacuumizing the reaction bottle to a limit vacuum state by using a vacuum pump, sucking 50L of sodium carbonate solution (with the mass concentration of 10%) and 50L of sodium hydroxide solution (with the mass concentration of 3%) in a feeding funnel connected with the reaction bottle into the reaction bottle by using vacuum, opening an emptying valve to release vacuum, soaking for 6-24 hours at normal pressure, and filtering;
and step three, drying, filtering the soaked and activated zeolite, and drying for 7 hours at 100 ℃.
Claims (3)
1. An ion induction catalyst for industrial circulating water treatment is characterized by being prepared from the following raw materials: sodium carbonate solution: the volume ratio of the sodium hydroxide solution is 1:2-50: 2-50;
the zeolite is natural zeolite with the diameter of 0.1-2.0mm, the mass concentration of a sodium carbonate solution is 10-30%, and the mass concentration of a sodium hydroxide solution is 3-15%.
2. A preparation method of an ion induction catalyst for industrial circulating water treatment is characterized by comprising the following steps:
step one, high-temperature pore forming, namely calcining natural zeolite in a high-temperature furnace, keeping the temperature at 650-850 ℃ for 4-12h, and cooling for later use;
step two, vacuum activation, namely adding calcined natural zeolite into a reaction bottle, vacuumizing the reaction bottle to a limit vacuum state by using a vacuum pump, sucking a sodium carbonate solution and a sodium hydroxide solution in a feeding funnel connected with the reaction bottle into the reaction bottle by using vacuum, opening an emptying valve to release vacuum, soaking for 6-24 hours at normal pressure, and filtering;
and step three, drying, filtering the soaked and activated zeolite, and drying for 4-10 hours at the temperature of 90-110 ℃.
3. The method for preparing the ion-induced catalyst for industrial circulating water treatment according to claim 2, wherein the ratio of the sodium carbonate solution to the sodium hydroxide solution is controlled in a volume ratio of 1: 0.1-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010994081.7A CN112169825A (en) | 2020-09-21 | 2020-09-21 | Ion induction catalyst for industrial circulating water treatment and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010994081.7A CN112169825A (en) | 2020-09-21 | 2020-09-21 | Ion induction catalyst for industrial circulating water treatment and preparation method thereof |
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| CN112169825A true CN112169825A (en) | 2021-01-05 |
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| CN202010994081.7A Pending CN112169825A (en) | 2020-09-21 | 2020-09-21 | Ion induction catalyst for industrial circulating water treatment and preparation method thereof |
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Cited By (1)
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| CN114713185A (en) * | 2022-04-22 | 2022-07-08 | 重庆三峡学院 | Preparation method and application of spherical lanthanum carbonate loaded zeolite phosphate adsorbent |
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Inventor after: Cheng Lanxing Inventor after: Chen Bo Inventor after: Zhang Bing Inventor after: Feng Shengyue Inventor after: Chen Lei Inventor after: Yuan Lin Inventor after: Guo Huijun Inventor after: Zhao Zengbing Inventor after: Liu Limin Inventor after: Guan Sumin Inventor after: Zhao Yili Inventor after: Xu Aichun Inventor after: Yang Shucheng Inventor after: Luo Gang Inventor before: Cheng Lanxing Inventor before: Chen Bo Inventor before: Zhang Bing Inventor before: Feng Shengyue Inventor before: Chen Lei Inventor before: Yuan Lin Inventor before: Guan Sumin Inventor before: Zhao Zengbing Inventor before: Liu Limin Inventor before: Guo Huijun Inventor before: Zhao Yili Inventor before: Xu Aichun Inventor before: Yang Shucheng Inventor before: Luo Gang |