CN107555678B - Method for treating waste liquid of silicon-aluminum molecular sieve - Google Patents
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Abstract
A method for treating waste liquid of a silicon-aluminum molecular sieve comprises the following steps: (1) adding aluminum salt into the waste liquid of the silicon-aluminum molecular sieve according to the silicon content, and adjusting the pH value to 6-8; (2) introducing the waste liquid treated in the step (1) into an electric flocculation device for flocculation and precipitation treatment; (3) performing solid-liquid separation to obtain filter residue and filtrate; (4) adjusting the pH value of the filtrate to 7-9, introducing the filtrate into a multidimensional electrocatalytic oxidation device, adding NaCl solution and hydrogen peroxide into the electrocatalytic oxidation device, controlling the concentration of NaCl in the filtrate to be 5-10 g/L and the concentration of hydrogen peroxide to be 0.05-0.5 wt%, starting the multidimensional electrocatalytic oxidation device for deep treatment, and reacting for 1-4 h to meet the requirements of discharging or next-stage treatment on water inflow. The invention can effectively treat the waste liquid of the silicon-aluminum molecular sieve, solves the problem of gelation of the silicon-containing waste water and accelerates the separation effect while recycling a useful silicon source in the waste liquid, and reduces the COD concentration of the waste water to meet the requirements of discharge or next-stage treatment of inlet water.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a method for treating a silicon-aluminum molecular sieve waste liquid.
Background
In the existing production process of the molecular sieve, when the alkaline silica-alumina gel is converted into the molecular sieve crystal, a part of SiO2 is converted into a liquid phase from a solid phase and cannot be utilized, so that the utilization rate of the raw material SiO2 is only about 60%, and meanwhile, a large amount of SiO2, Al2O3 raw materials and organic amine template agents enter production wastewater, so that the wastewater contains a large amount of COD and organic amine besides high-concentration SiO 2. Not only pollutes the environment, but also a large amount of superfine molecular sieve particles are lost along with the filtrate, so that the production cost of the molecular sieve is high. Therefore, from the perspective of recovering resources and reducing production cost, and from the perspective of environmental protection, it is of great significance to develop a process for recycling useful silicon sources in the waste liquid of the aluminosilicate molecular sieve and deeply degrading the COD concentration of the wastewater.
For such waste water, commonly used water treatment agents such as polyaluminium chloride (PAC), Polyacrylamide (PAM) and polyacrylic acid have no or poor effect on removing suspended substances in the waste water. The reports of the wastewater treatment are few, the domestic common treatment method is to neutralize acidic water generated in a deionized water workshop, a large amount of colloidal precipitates are easily generated in the neutralization process, the water content is high, the volume is large, the filter pressing is difficult to form cakes, and the suspended solid content of the neutralized wastewater (hereinafter referred to as neutralized water) is still high and needs to be treated. In order to recover useful components in the wastewater and enable the treated water quality to reach the national allowable discharge standard, the development of a process for recycling useful silicon sources in the waste liquid of the aluminosilicate molecular sieve and deeply degrading the COD concentration of the wastewater has great significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for treating the waste liquid of the silicon-aluminum molecular sieve, which can recycle useful silicon sources in the waste liquid of the silicon-aluminum molecular sieve and can also deeply degrade the COD concentration of the waste water.
The invention firstly adopts the electrocoagulation technology to recover useful silicon sources in the waste liquid, and then enters the multidimensional electrocatalytic oxidation device for advanced treatment to reduce the COD and ammonia nitrogen concentration in the waste water so as to meet the requirements of discharging or next-stage treatment of inlet water.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for treating waste liquid of a silicon-aluminum molecular sieve comprises the following steps:
(1) adding aluminum salt in a certain proportion into the waste liquid of the silicon-aluminum molecular sieve according to the silicon content, and adjusting the pH value to 6-8;
(2) introducing the waste liquid treated in the step (1) into an electric flocculation device for flocculation and precipitation treatment;
(3) carrying out solid-liquid separation on the waste liquid after the electric flocculation treatment to obtain filter residue and filtrate;
(4) adjusting the pH value of the filtrate obtained in the step (3) to 7-9, introducing the filtrate into a multidimensional electrocatalytic oxidation device, adding a NaCl solution and hydrogen peroxide into the electrocatalytic oxidation device, controlling the concentration of NaCl in the filtrate to be 5-10 g/L and the concentration of hydrogen peroxide to be 0.05-0.5 wt%, starting the multidimensional electrocatalytic oxidation device for deep treatment, and reacting for 1-4 h to meet the requirements of discharging or next-stage treatment on water inlet.
Further, in the step (1), the waste liquid of the silicon-aluminum molecular sieve is a waste liquid containing aluminosilicate and amine organic template. The amine organic template agent in the silicon-aluminum molecular sieve waste liquid is tetrapropylammonium hydroxide or hexamethylenediamine, n-butylamine and dibromohexamethylenediamine.
Further, in the step (1), the concentration of Silicate (SiO) in the waste liquid of the silicon-aluminum molecular sieve2Measured) is 0.3-20 g/L, the pH value is 5-14, and the COD (chemical oxygen demand) concentration is 500-20000 mg/L.
Further, in the step (1), the mass ratio of the addition amount of the aluminum salt to the silicon content in the waste liquid is 1: 10-3 (m)Al: mSi) The aluminum salt is aluminum sulfate, aluminum oxide or aluminum chloride.
Further, in the step (2), the electric flocculation device comprises a direct current power supply, a cathode plate and an anode plate, a reaction tank and an aeration system, inert polar plates are used as the cathode plate and the anode plate, the cathode plate and the anode plate are arranged at intervals to form a parallel loop, and the anode and the cathode of the electric flocculation device are connected with the anode and the cathode of the direct current power supply to carry out electric flocculation treatment.
Further, in the step (2), the reaction current density of the electric flocculation device is 20-60 mA/cm2The aeration rate is 20-80L/h, and the reaction time is 20-60 min.
Further, in the step (3), the filter residue is recycled as a raw material.
Further, in the step (4), the multi-dimensional electrocatalytic oxidation apparatus is composed of an anode (an insoluble transition metal or oxide-supported electrode plate thereof is used as the anode), a cathode (an inert electrode plate is used as the cathode), a particle electrode (a packed particle is used as the particle electrode), a direct current power supply, a circulation system, and an electrocatalytic oxidation reaction tank.
Further, in the step (4), the concrete steps are as follows:
(a) adjusting the pH value of the filtrate to 7-9, and introducing into a multidimensional electrocatalytic oxidation device;
(b) adding NaCl solution and hydrogen peroxide into the multidimensional electrocatalytic oxidation device, and controlling the concentration of NaCl in the filtrate to be 5-10 g/L and the concentration of hydrogen peroxide to be 0.05-0.5 wt%;
(c) starting the multidimensional electrocatalytic oxidation device, and controlling the reaction current density to be 100-300 mA/cm2And controlling the reaction time to be 2-4 h according to the COD concentration of the inlet water.
Further, in the step (1) and the step (4), the method for adjusting the pH value of the waste liquid comprises using an aqueous solution of an acid with a mass concentration of 10% -15% or an aqueous solution of a base with a mass concentration of 10% -20%, wherein the acid is sulfuric acid or hydrochloric acid, and the base is sodium hydroxide or aluminum hydroxide.
Further, in the step (4), the added NaCl is a NaCl solution with the mass concentration of 15-20%; the added hydrogen peroxide is H2O2The mass concentration of the hydrogen peroxide solution is 37 percent.
The invention has the beneficial effects that:
the invention can solve the problems of large amount of jelly produced in the process of treating the silicon-aluminum molecular sieve wastewater, high water content, large volume and difficult solid-liquid separation, and can effectively destroy the gel phenomenon, accelerate the solid-liquid separation speed and recover useful silicon sources by adding aluminum salt and carrying out electrocoagulation treatment after adjusting the pH value. The utilization rate of raw materials is improved to the maximum extent, pollution is avoided, and the production cost is reduced.
The invention carries out multidimensional electrocatalytic oxidation deep treatment on the electrocoagulation effluent, and can effectively solve COD and ammonia nitrogen pollution caused by the discharge of the waste liquid of the silicon-aluminum molecular sieve.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
The EU molecular sieve high-silicon wastewater is taken as a treatment object, the wastewater contains tetrapropylammonium hydroxide (TPAOH) template agent, the pH value of the wastewater is 11.78, and the concentration of Silicon (SiO) is contained2) 13047.52mg/L, and the COD concentration of the wastewater is 2076.36 mg/L.
Firstly, adding 3.125g/L of aluminum sulfate into the wastewater, dissolving and stirring, then adopting a dilute sulfuric acid solution with the mass concentration of 10% to adjust the initial pH value to 7, and introducing the waste liquid into an electric flocculation device. Connecting the anode and cathode of a power supply with the anode and cathode of the electric flocculation device, turning on the power supply and the aeration system, and controlling the current density to be 30mA/cm2The aeration flow rate is 20L/h, and the reaction time is 30 min. And carrying out vacuum filtration on the wastewater, and recovering filter residues. Adjusting the pH value of the filtrate to 8 by adopting sodium hydroxide with the mass concentration of 15%, and introducing into a multidimensional electrocatalytic oxidation device. Adding a NaCl solution with the mass concentration of 20% and a hydrogen peroxide solution into a multidimensional electrocatalytic oxidation device, controlling the NaCl concentration in the filtrate to be 10g/L and the hydrogen peroxide concentration to be 0.08wt%, switching on a power supply, and controlling the current density to be 200mA/cm2And reacting for 3 hours. Detecting the silicon concentration (by SiO) of the wastewater2Meter), COD concentration, pH, and the results are shown in the following table.
| Water sample | pH value | Silicon concentration (in SiO)2Meter) mg/L | COD concentration (mg/L) |
| EU stock solution | 11.78 | 13047.52 | 2076.36 |
| Electroflocculation of the filtrate | 6.34 | 226.84 | 1496.35 |
| Electrocatalysis water outlet | 7.08 | 167.37 | 34.82 |
Example 2
The ZHP molecular sieve washing waste liquid is used as a treatment object, the waste water contains a hexamethylene diamine template agent, the initial pH value of the waste water is 7.64, and the concentration of silicon (SiO is used as2) 747.58mg/L, and the COD concentration of the wastewater is 476.27 mg/L.
According to the water quality, 0.5g/L aluminum sulfate is added into the waste water, stirred and dissolved, then the pH value is adjusted to 6 by adopting sodium hydroxide with the mass concentration of 15%, and the waste liquid is led into an electric flocculation device. Connecting the anode and cathode of a power supply with the anode and cathode of the electric flocculation device, turning on the power supply and the aeration system, and controlling the current density to be 30mA/cm2The aeration flow rate is 20L/h, and the reaction time is 20 min. And carrying out vacuum filtration on the wastewater, and recovering filter residues. Adjusting the pH value of the filtrate to 7 by adopting sodium hydroxide with the mass concentration of 15%, and introducing into a multidimensional electrocatalytic oxidation device. Adding NaCl solution with mass concentration of 20% and hydrogen peroxide into the multidimensional electro-catalytic device, controlling the concentration of NaCl in the filtrate to be 5/L and the concentration of hydrogen peroxide to be 0.05wt%, turning on the power supply, and controlling the current density to be 100mA/cm2And reacting for 1.5 h. Detecting the silicon concentration (by SiO) of the wastewater2Meter), COD concentration, pH, and the results are shown in the following table.
| Water sample | pH value | Silicon concentration (in SiO)2Meter) mg/L | COD concentration (mg/L) |
| ZHP washing stock solution | 7.64 | 747.58 | 476.27 |
| Electroflocculation of the filtrate | 5.72 | 6.84 | 359.61 |
| Electrocatalysis water outlet | 6.38 | 5.47 | 16.85 |
According to the embodiment 1 and the embodiment 2, after the silicon-aluminum molecular sieve wastewater is treated by the method, the silicon concentration and the COD concentration in the wastewater can be obviously reduced. The wastewater with lower silicon content or lower COD concentration can reach the national discharge standard after being treated by the method.
Claims (10)
1. A method for treating waste liquid of a silicon-aluminum molecular sieve is characterized by comprising the following steps:
(1) adding aluminum salt in a certain proportion into the waste liquid of the silicon-aluminum molecular sieve according to the silicon content, and adjusting the pH value to 6-8;
(2) introducing the waste liquid treated in the step (1) into an electric flocculation device for flocculation and precipitation treatment;
(3) carrying out solid-liquid separation on the waste liquid after the electric flocculation treatment to obtain filter residues, and recycling the filter residues as raw materials to obtain filtrate;
(4) adjusting the pH value of the filtrate obtained in the step (3) to 7-9, introducing the filtrate into a multidimensional electrocatalytic oxidation device, adding a NaCl solution and hydrogen peroxide into the electrocatalytic oxidation device, controlling the concentration of NaCl in the filtrate to be 5-10 g/L and the concentration of hydrogen peroxide to be 0.05-0.5 wt%, starting the multidimensional electrocatalytic oxidation device for deep treatment, and reacting for 1-4 h to meet the requirements of discharging or next-stage treatment on water inlet.
2. The method for treating the waste liquid of the silicon-aluminum molecular sieve of claim 1, wherein in the step (1), the waste liquid of the silicon-aluminum molecular sieve is a waste liquid containing aluminosilicate and amine organic template; the amine organic template agent in the silicon-aluminum molecular sieve waste liquid is tetrapropylammonium hydroxide or hexamethylenediamine, n-butylamine and dibromohexamethylenediamine.
3. The method for treating the waste liquid of the silicoaluminophosphate molecular sieve of claim 1 or 2, wherein the concentration of silicate in the waste liquid of the silicoaluminophosphate molecular sieve is 0.3 to 20g/L, the pH value is 5 to 14, and the COD concentration is 500 to 20000 mg/L.
4. The method for treating the waste liquid of the silicon-aluminum molecular sieve of claim 1 or 2, wherein in the step (1), the mass ratio of the addition amount of the aluminum salt to the silicon content in the waste liquid is 1: 10-3, and the aluminum salt is aluminum sulfate, aluminum oxide or aluminum chloride.
5. The method for treating the waste liquid of the silicoaluminophosphate molecular sieve according to claim 1 or 2, wherein in the step (2), the electrocoagulation device comprises a direct current power supply, a cathode plate and an anode plate, a reaction tank and an aeration system, wherein inert polar plates are used as the cathode plate and the anode plate, the cathode plate and the anode plate are arranged at intervals to form a parallel loop, and the anode and the cathode of the electrocoagulation device are connected with the anode and the cathode of the direct current power supply to perform electrocoagulation treatment.
6. The method of claim 1 or 2The method for treating the waste liquid of the silicon-aluminum molecular sieve is characterized in that in the step (2), the reaction current density of the electric flocculation device is 20-60 mA/cm2The aeration rate is 20-80L/h, and the reaction time is 20-60 min.
7. The method for treating the waste liquid of the silicoaluminophosphate molecular sieve of claim 1 or 2, wherein in the step (4), the multidimensional electrocatalytic oxidation device comprises an anode, a cathode, a particle electrode, a direct current power supply, a circulating system and an electrocatalytic oxidation reaction tank.
8. The method for treating the waste liquid of the silicon-aluminum molecular sieve of claim 1 or 2, wherein in the step (4), the specific steps are as follows:
(a) adjusting the pH value of the filtrate to 7-9, and introducing into a multidimensional electrocatalytic oxidation device;
(b) adding NaCl solution and hydrogen peroxide into the multidimensional electrocatalytic oxidation device, and controlling the concentration of NaCl in the filtrate to be 5-10 g/L and the concentration of hydrogen peroxide to be 0.05-0.5 wt%;
(c) starting the multidimensional electrocatalytic oxidation device, and controlling the reaction current density to be 100-300 mA/cm2And controlling the reaction time to be 2-4 h according to the COD concentration of the inlet water.
9. The method for treating the waste liquid of the silicoaluminophosphate molecular sieve of claim 1 or 2, wherein in the step (1) and the step (4), the method for adjusting the pH value comprises using an aqueous solution of an acid with a mass concentration of 10% -15% or an aqueous solution of a base with a mass concentration of 10% -20%, wherein the acid is sulfuric acid or hydrochloric acid, and the base is sodium hydroxide or aluminum hydroxide.
10. The method for treating the waste liquid of the silicon-aluminum molecular sieve according to claim 1 or 2, wherein in the step (4), the added NaCl is a NaCl solution with the mass concentration of 15-20%; the added hydrogen peroxide is H2O2The mass concentration of the hydrogen peroxide solution is 37 percent.
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| CN112694099A (en) * | 2019-10-21 | 2021-04-23 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and synthetic method thereof |
| CN111960813B (en) * | 2020-08-21 | 2023-06-09 | 浙江天地环保科技股份有限公司 | High-value utilization post-treatment system and method for molecular sieve synthesis waste liquid |
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Effective date of registration: 20230327 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: SINOPEC CATALYST Co.,Ltd. Address before: 410000 No. 288, Shiyanhu Road, Jinping Community, Tiaoma Town, Yuhua District, Changsha City, Hunan Province Patentee before: HUNAN LYUWANG ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |