Catalyst wastewater treatment agent and preparation method thereof

Abstract

A catalyst wastewater treatment agent, comprising the following raw materials in parts by mass: 20 to 35 parts of molecular sieve powder, 5 to 15 parts of modified bamboo charcoal powder, 5 to 12 parts of polyethylene amine, 0.5 to 3 parts of nucleating agent, 1 to 6 parts of polydimethylsiloxane, 1 to 3 parts of propylene glycol fatty acid ester, and 1 to 5 parts of stabilizer. The treatment agent can remove aluminum and heavy metal ion copper in catalyst wastewater well through reasonable compounding of various components, and its preparation process is simple, the operation process is easy to control, and it is convenient to expand production and then promote use.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater treatment generated in a catalyst preparation process, and in particular to a catalyst wastewater treatment agent and a preparation method thereof. Background Art

[0002] In the process of catalyst preparation, alumina carrier is the most widely used catalyst carrier, accounting for about 70% of industrial supported catalysts. Therefore, it is easy to produce a large amount of aluminum-containing wastewater in the catalyst production operation. Its unreasonable discharge will increase the aluminum ion content in drinking water. In recent years, medical research has shown that excessive intake of aluminum can cause many human diseases, such as renal failure and uremia. In addition, excessive aluminum in the body can promote blood and cardiovascular diseases and have a mutagenic effect on somatic cells or reproductive cells. Excessive aluminum dissolved in the soil will inhibit the growth of plant roots, affect their absorption of water and calcium and magnesium, reduce photosynthesis, and chelate with organic acids, adenosine triphosphate and deoxyribonucleic acid in cells, interfering with their normal metabolism, causing the death or reduction of crops; large amounts of aluminum will cause the death of many aquatic organisms such as fish.

[0003] Patent CN201210408597.4 discloses a method for treating vanadium-containing and aluminum-containing wastewater, which includes contacting the vanadium-containing and aluminum-containing wastewater with an alkaline substance and performing solid-liquid separation under the conditions of vanadium precipitation and aluminum precipitation to obtain a solid product and a filtrate, and subjecting the filtrate to biological treatment. The wastewater treated by the method of the present invention not only has a lower vanadium content and aluminum content, but also has a lower COD value, which can meet the standard for wastewater discharge. The process is simple to operate and the alkaline raw materials are widely available, but the method is generally suitable for the preliminary treatment of industrial wastewater. It is easy to generate mud residue that is troublesome to treat by only adding alkali treatment, and the amount of sludge generated is large, which is easy to cause secondary environmental pollution. At the same time, sometimes the large part of the precipitated flocs is relatively small, and it takes a long time to settle and settle, and the efficiency is low.

[0004] Patent CN201810314099.0 discloses a composite flocculant for treating aluminum-containing wastewater, and its preparation method is as follows: 1. Add soluble starch into water for gelatinization to obtain gelatinized starch; 2. Add sodium hydroxide to the gelatinized starch, mix evenly, and stir at 55°C-65°C for 1.5-2.5 hours to obtain an orange-red transparent solution; 3. Add sodium silicate to the orange-red transparent solution, mix evenly, and stir at 60°C-70°C for 1.5-2.5 hours. Obtain mixture A; 4. Cool mixture A, slowly add sulfuric acid solution to mixture A to adjust the pH value to 2.5-3.5, at which time the system is light blue, stir at 60°C-70°C for 1.5-2.5 hours to obtain mixture B; 5. Add anhydrous ferric sulfate to mixture B and mix evenly, at which time the system is yellow-brown, stir at 45°C-55°C for 3.5-4.5 hours, and cool to room temperature to obtain the composite flocculant for treating aluminum-containing wastewater. The flocculant is easy to use and low in cost, and can be directly used to remove various pollutants in aluminum-containing wastewater. However, this method is not easy to apply to actual production, because its preparation method is cumbersome and complicated, the terminal pH is not easy to control during the preparation process, and each operation step needs to judge the operation of the next step based on the color of the system, which is prone to misjudgment and affects the effect of the final prepared flocculant.

[0005] In addition, since the wastewater generated during the catalyst preparation process has complex composition, in addition to containing a high content of aluminum, it also contains a large amount of heavy metal ions, such as copper. Therefore, it is particularly important for current environmental governance to prepare a treatment agent that is effective in precipitating aluminum and various heavy metal copper ions in wastewater. Summary of the invention

[0006] In view of the fact that the treatment agent for precipitated aluminum in wastewater in the prior art is complicated to prepare and difficult to control, and various heavy metal copper ions cannot be well treated at the same time, the present invention provides a catalyst wastewater treatment agent and a preparation method thereof.

[0007] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0008] A catalyst wastewater treatment agent comprises the following raw materials in parts by mass: 20 to 35 parts of molecular sieve powder, 5 to 15 parts of modified bamboo charcoal powder, 5 to 12 parts of polyethylene amine, 0.5 to 3 parts of nucleating agent, 1 to 6 parts of polydimethylsiloxane, 1 to 3 parts of propylene glycol fatty acid ester, and 1 to 5 parts of stabilizer.

[0009] Furthermore, the preparation method of the modified bamboo charcoal powder is: sieve the bamboo charcoal powder through a 300-400 mesh sieve to obtain bamboo charcoal powder with uniform particle size, immerse the sieved bamboo charcoal powder in a carbon disulfide solution, and obtain the modified bamboo charcoal powder after filtering, washing and drying.

[0010] Furthermore, the concentration of the carbon disulfide solution is 0.1-0.5 g / L, the immersion time is 1-2.5 h, the washing process is washed with deionized water, and the drying condition is 3-5 h at a temperature of 50-65° C.

[0011] Furthermore, the nucleating agent is talc or mica.

[0012] Furthermore, the stabilizer is one of pyromellitic anhydride, pyromellitic acid, and epoxidized soybean oil.

[0013] Furthermore, the molecular sieve powder is zeolite molecular sieve powder is Y-type zeolite molecular sieve.

[0014] The preparation method of the catalyst wastewater treatment agent comprises the following steps:

[0015] S1: subjecting zeolite molecular sieve powder to high temperature activation treatment under nitrogen atmosphere to obtain activated zeolite molecular sieve;

[0016] S2: Place modified bamboo charcoal powder, polyethylene amine, polydimethylsiloxane and stabilizer in a reactor, stir evenly, and after a period of reaction, slowly add activated zeolite molecular sieve and propylene glycol fatty acid ester into the reactor, and at the same time drop an alkaline solution to adjust the pH to 7.5-9, and stir the materials in the reactor at a high speed for pre-emulsification;

[0017] S3: After the pre-emulsification is completed, a nucleating agent is added, and the reaction is carried out for a period of time under a nitrogen atmosphere and heat preservation treatment is performed. The sample in the reactor is taken out and cooled to room temperature to obtain a treating agent.

[0018] Furthermore, the activation conditions in step S1 are: high temperature activation treatment at 250-450° C. for 2-3.5 hours.

[0019] Furthermore, in step S2, the reaction time is 10-30 min, the alkali solution is one of ammonia water and sodium hydroxide, the high-speed stirring speed is 1500 rpm-2500 rpm, and the pre-emulsification time is 30-45 min.

[0020] Preferably, in step S2, an alkaline solution is added dropwise to adjust the pH to 8.0.

[0021] Furthermore, in step S3, the reaction time is 6-8 hours, and the heat preservation time is 1-1.5 hours.

[0022] The present invention has the following beneficial effects:

[0023] 1. The catalyst wastewater treatment agent provided by the present invention is added with modified bamboo charcoal powder and Y-type zeolite molecular sieve, and by adding polyvinyl amine, polydimethylsiloxane and stabilizer, the components of the treatment agent are reasonably compounded, and the removal rate of aluminum and copper in catalyst wastewater by the treatment agent is effectively improved.

[0024] 2. The catalyst wastewater treatment agent provided by the present invention can effectively accelerate the aggregation of precipitates by adding a nucleating agent during the preparation process. In addition, by adding a stabilizer during the preparation process, the problem of poor stability of precipitates during use of the treatment agent can be avoided.

[0025] 3. The catalyst wastewater treatment agent provided by the present invention can regulate the pH range in the pre-emulsification reaction, and thus the catalyst wastewater does not need to be alkalized in advance during the use of the prepared treatment agent, and can be directly added to the catalyst wastewater to remove aluminum and copper.

[0026] 4. The preparation method of the catalyst wastewater treatment agent provided by the present invention has a simple preparation process, and the reaction process is easy to control, which is convenient for expanding production. DETAILED DESCRIPTION

[0027] The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments.

[0028] The chemical reagents described in the following embodiments of the present invention, bamboo charcoal powder was purchased from Shandong Hengtai Biotechnology Co., Ltd., Y-type zeolite molecular sieve was purchased from Tianjin Nanhua Catalyst Co., Ltd., model NKF-7; others such as carbon disulfide, talc, mica, polyvinyl amine, polydimethylsiloxane, propylene glycol fatty acid ester, pyromellitic anhydride, pyromellitic acid, epoxy soybean oil, etc. can be purchased directly from the market.

[0029] Example 1

[0030] Preparation of modified bamboo charcoal powder

[0031] The bamboo charcoal powder was sieved through a 300-mesh sieve to obtain bamboo charcoal powder with uniform particle size. The sieved bamboo charcoal powder was immersed in a carbon disulfide solution with a concentration of 0.1 g / L for 1 hour. The immersion process was carried out in a closed environment. The powder was then filtered and washed with deionized water until the washing liquid did not contain carbon disulfide. The carbon disulfide in the washing liquid was recovered by heating to avoid carbon disulfide volatilization and pollution of the environment. The powder was dried at 65°C for 3 hours to obtain modified bamboo charcoal powder.

[0032] Preparation of treatment agent

[0033] S1: In a nitrogen atmosphere, Y-type zeolite molecular sieve (NKF-7) powder was subjected to high temperature activation treatment at 400°C for 2h to obtain an activated zeolite molecular sieve;

[0034] S2: 15 parts of modified bamboo charcoal powder, 10 parts of polyethylene amine, 3 parts of polydimethylsiloxane and 5 parts of pyromellitic anhydride are placed in a reactor according to weight parts, stirred evenly, reacted at 40°C for 30 minutes, and then 30 parts of activated Y-type zeolite molecular sieve and 1 part of propylene glycol fatty acid ester are slowly added to the reactor, and at the same time, 5% sodium hydroxide solution is added dropwise to adjust the pH to 8.0 while maintaining the temperature without limit, and the materials in the reactor are pre-emulsified at a high speed of 2500 rpm for 30 minutes;

[0035] S3: After the pre-emulsification, 1 part of talcum powder was added, and the mixture was reacted at 40°C for 6 hours under a nitrogen atmosphere. After the reaction, the mixture was kept warm at 30°C. The sample in the reactor was taken out and cooled to room temperature to obtain a treatment agent.

[0036] Example 2

[0037] Preparation of modified bamboo charcoal powder

[0038] The bamboo charcoal powder was sieved through a 300-mesh sieve to obtain bamboo charcoal powder with uniform particle size. The sieved bamboo charcoal powder was immersed in a carbon disulfide solution with a concentration of 0.1 g / L for 2 hours. The immersion process was carried out in a closed environment. The powder was then filtered and washed with deionized water until the washing liquid did not contain carbon disulfide. The carbon disulfide in the washing liquid was recovered by heating to avoid volatilization of carbon disulfide and pollution of the environment. The powder was dried at 65°C for 5 hours to obtain modified bamboo charcoal powder.

[0039] Preparation of treatment agent

[0040] S1: In a nitrogen atmosphere, Y-type zeolite molecular sieve (NKF-7) powder was subjected to high temperature activation treatment at 300°C for 3h to obtain an activated zeolite molecular sieve;

[0041] S2: 10 parts of modified bamboo charcoal powder, 10 parts of polyethylene amine, 1 part of polydimethylsiloxane and 3 parts of pyromellitic anhydride are placed in a reactor according to mass parts, stirred evenly, reacted for 20 minutes, and then 20 parts of activated Y-type zeolite molecular sieve and 3 parts of propylene glycol fatty acid ester are slowly added to the reactor, and while keeping the temperature unlimited, ammonia water is added dropwise to adjust the pH to 8.5, and the materials in the reactor are pre-emulsified at a high speed of 2000 rpm for 40 minutes;

[0042] S3: After the pre-emulsification, 1 part of talcum powder was added, and the mixture was reacted at 40°C for 6 hours under a nitrogen atmosphere. After the reaction, the mixture was kept warm at 30°C. The sample in the reactor was taken out and cooled to room temperature to obtain a treatment agent.

[0043] Example 3

[0044] Preparation of modified bamboo charcoal powder

[0045] The bamboo charcoal powder was sieved through a 400-mesh sieve to obtain bamboo charcoal powder with uniform particle size. The sieved bamboo charcoal powder was immersed in a carbon disulfide solution with a concentration of 0.5 g / L for 1 hour. The immersion process was carried out in a closed environment. The powder was then filtered and washed with deionized water until the washing liquid did not contain carbon disulfide. The carbon disulfide in the washing liquid was recovered by heating to avoid carbon disulfide volatilization and pollution of the environment. The powder was dried at 65°C for 3 hours to obtain modified bamboo charcoal powder.

[0046] Preparation of treatment agent

[0047] S1: In a nitrogen atmosphere, Y-type zeolite molecular sieve (NKF-7) powder was subjected to high temperature activation treatment at 400°C for 2h to obtain an activated zeolite molecular sieve;

[0048] S2: 5 parts of modified bamboo charcoal powder, 12 parts of polyethylene amine, 0.5 parts of polydimethylsiloxane and 5 parts of pyromellitic acid were placed in a reactor according to mass parts, stirred evenly, reacted for 10 minutes, and then 35 parts of activated Y-type zeolite molecular sieve and 3 parts of propylene glycol fatty acid ester were slowly added to the reactor. At the same time, 5% sodium hydroxide solution was added dropwise to adjust the pH to 8.0 while maintaining the temperature. The materials in the reactor were pre-emulsified at a high speed of 2500 rpm for 30 minutes:

[0049] S3: After the pre-emulsification is completed, 1 part by weight of mica is added, and the mixture is reacted at 40° C. for 6 hours under a nitrogen atmosphere. After the reaction, the mixture is heat-insulated at 30° C., and the sample in the reactor is taken out and cooled to room temperature to obtain a treatment agent.

[0050] Example 4

[0051] Preparation of modified bamboo charcoal powder

[0052] The bamboo charcoal powder was sieved through a 300-mesh sieve to obtain bamboo charcoal powder with uniform particle size. The sieved bamboo charcoal powder was immersed in a carbon disulfide solution with a concentration of 0.1 g / L for 2.5 hours. The immersion process was carried out in a closed environment. The powder was then filtered and washed with deionized water until the washing liquid did not contain carbon disulfide. The carbon disulfide in the washing liquid was recovered by heating to avoid the volatilization of carbon disulfide and polluting the environment. The powder was dried at 50°C for 5 hours to obtain the modified bamboo charcoal powder.

[0053] Preparation of treatment agent

[0054] S1: In a nitrogen atmosphere, Y-type zeolite molecular sieve (NKF-7) powder was subjected to high temperature activation treatment at 400°C for 2h to obtain an activated zeolite molecular sieve;

[0055] S2: 15 parts of modified bamboo charcoal powder, 10 parts of polyethylene amine, 3 parts of polydimethylsiloxane and 5 parts of epoxy soybean oil were placed in a reactor according to weight parts, stirred evenly, reacted for 30 minutes, and then 30 parts of activated Y-type zeolite molecular sieve and 1 part of propylene glycol fatty acid ester were slowly added to the reactor, and at the same time, 5% sodium hydroxide solution was added dropwise to adjust the pH to 9.0 while maintaining the temperature. The materials in the reactor were pre-emulsified at a high speed of 2500 rpm for 30 minutes;

[0056] S3: After the pre-emulsification, 1 part of talcum powder was added, and the mixture was reacted at 40°C for 6 hours under a nitrogen atmosphere. After the reaction, the mixture was kept warm at 30°C. The sample in the reactor was taken out and cooled to room temperature to obtain a treatment agent.

[0057] Comparative Example 1

[0058] In the preparation of modified bamboo charcoal powder, bamboo charcoal powder was replaced with activated carbon powder, and other operations were the same as those in Example 1.

[0059] Comparative Example 2

[0060] The bamboo charcoal powder is not subjected to modification treatment and is directly subjected to the operation of preparing the treating agent. The operation of preparing the treating agent is the same as that in Example 1.

[0061] Comparative Example 3

[0062] During the preparation of the treating agent, no Y-type zeolite molecular sieve was added, and other operations were the same as in Example 1.

[0063] Comparative Example 4

[0064] During the preparation of the treatment agent, the pH is not adjusted in step S2, and other operations are the same as in Example 1.

[0065] Comparative Example 5

[0066] During the preparation of the treating agent, no nucleating agent and stabilizer are added in step S2, and other operations are the same as in Example 1.

[0067] Performance testing of treatment agents

[0068] 100 mL of wastewater generated by Binzhou Zhongke Catalytic Technology Co., Ltd. in the process of preparing catalyst was taken. The pH of the catalyst wastewater was first detected to be 6.5, and the aluminum ion concentration in the catalyst wastewater was 86.7 mg / L, and the copper ion concentration was 46.9 mg / L.

[0069] Add the treatment agent prepared in the above examples and comparative examples, the amount of treatment agent added is 10% of the wastewater mass, and stir at room temperature for 2 hours. After filtering, take a sample and measure the aluminum and copper metal ion concentrations using an atomic absorption spectrophotometer. Calculate the heavy metal ion removal rate R (%) according to formula (1).

[0070] In formula (1), C0 and C1 are the concentrations of aluminum and copper metal ions in the wastewater before and after treatment, respectively, in mg / L.

[0071] As time changes, three samples are taken at each time point for testing, and the test results are averaged. The specific test results are shown in Table 1.

[0072] Table 1

[0073]

[0074] The treatment agent was added to the catalyst wastewater, and samples were taken at different time points to detect the removal effect of aluminum and heavy metal ion copper. According to the test results in Table 1 above, it can be clearly found that the treatment agent can achieve an aluminum removal rate of 99.8% within 60 minutes. In addition, the removal rate of copper ions can also reach 95.5%.

[0075] However, when the modified bamboo charcoal in the treatment agent is changed to activated carbon or unmodified bamboo charcoal, the removal rate of aluminum and copper in the treatment agent is significantly reduced; if no molecular sieve is added to the treatment agent, or the pH during pre-emulsification is not adjusted during the preparation of the treatment agent, the removal rate of aluminum and copper in the final prepared treatment agent will also be reduced.

[0076] For the treatment agent prepared in Comparative Example 5, the aluminum removal rate was only 40.2% at 20 min, 65.9% at 60 min, 87.4% at 120 min, and 95.2% at 180 min, and the generated sediment was unstable and easily dispersed.

[0077] Use of secondary treatment agents

[0078] In order to make the aluminum and copper contents in the effluent of catalyst wastewater treatment meet the discharge standards, the wastewater can be treated in a secondary manner. A treatment agent is added to the catalyst wastewater. The amount of the treatment agent added is 10% of the wastewater mass. Stir at room temperature for 2 hours. After the end, the precipitate is discharged, and then 5% by mass of the treatment agent is added to the catalyst wastewater. Repeat the above experiment, and take samples to measure the removal rates of aluminum and copper. This test only tested the removal rates of aluminum and copper at 60 minutes. The specific results are shown in Table 2 below.

[0079] Table 2

[0080]

[0081] By performing secondary treatment on the catalyst wastewater, it can be seen from Table 2 above that almost all of the aluminum in the catalyst wastewater can be removed. In addition, the removal of copper can also reach 99.9%.

[0082] The influence of temperature on the effect of treatment agent

[0083] The performance test method of the treatment agent prepared in Example 1 is the same as that of the above-mentioned treatment agent, except that the stirring temperature is changed to 25°C, 35°C, 50°C, and 80°C, respectively. The treatment samples are taken for 60 minutes, and the final test results are shown in Table 3 below.

[0084] Table 3

[0085]

[0086] By using the treatment agent prepared in Example 1 to treat the catalyst wastewater under different temperature conditions in Table 3 above, it can be clearly seen that when the temperature reaches 35-50°C, the removal rate of aluminum can be basically completely removed, and the removal rate of copper can also reach 99.8% at 50°C. However, when the temperature reaches 80°C, the removal effect of aluminum and copper deteriorates, possibly due to the excessively high temperature, which may cause some performance changes of the treatment agent.

Claims

1. A catalyst wastewater treatment agent, characterized in that: The treatment agent comprises the following raw materials in parts by weight: 20 to 35 parts of molecular sieve powder, 5 to 15 parts of modified bamboo charcoal powder, 5 to 12 parts of polyethylene amine, 0.5 to 3 parts of nucleating agent, 1 to 6 parts of polydimethylsiloxane, 1 to 3 parts of propylene glycol fatty acid ester, and 1 to 5 parts of stabilizer; the molecular sieve is a zeolite molecular sieve; The preparation method of the modified bamboo charcoal powder comprises: passing the bamboo charcoal powder through a 300-400 mesh sieve to obtain bamboo charcoal powder with uniform particle size, impregnating the sieved bamboo charcoal powder in a carbon disulfide solution, and filtering, washing and drying to obtain the modified bamboo charcoal powder after the impregnation is completed; The preparation method of the catalyst wastewater treatment agent comprises the following steps: S1: subjecting zeolite molecular sieve powder to high temperature activation treatment under nitrogen atmosphere to obtain activated zeolite molecular sieve; S2: Place modified bamboo charcoal powder, polyethylene amine, polydimethylsiloxane and stabilizer in a reactor, stir evenly, and after a period of reaction, slowly add activated zeolite molecular sieve and propylene glycol fatty acid ester into the reactor, and at the same time drop an alkaline solution to adjust the pH to 7.5-9, and stir the materials in the reactor at a high speed for pre-emulsification; S3: After the pre-emulsification is completed, a nucleating agent is added, and the reaction is carried out for a period of time under a nitrogen atmosphere and heat preservation treatment is performed. The sample in the reactor is taken out and cooled to room temperature to obtain a treating agent.

2. The catalyst wastewater treatment agent according to claim 1, characterized in that: The concentration of the carbon disulfide solution is 0.1-0.5 g / L, the immersion time is 1-2.5 h, the washing process is washed with deionized water, and the drying condition is 3-5 h at a temperature of 50-65° C.

3. The catalyst wastewater treatment agent according to claim 1, characterized in that: The nucleating agent is talc or mica.

4. The catalyst wastewater treatment agent according to claim 1, characterized in that: The stabilizer is one of pyromellitic anhydride, pyromellitic acid and epoxidized soybean oil.

5. The catalyst wastewater treatment agent according to claim 1, characterized in that: The zeolite molecular sieve powder is Y-type zeolite molecular sieve.

6. The catalyst wastewater treatment agent according to claim 1, characterized in that: The activation conditions in step S1 are: high temperature activation treatment at 250-450° C. for 2-3.5 hours.

7. The catalyst wastewater treatment agent according to claim 1, characterized in that: In step S2, the reaction time is 10-30 min, the alkali solution is one of ammonia water and sodium hydroxide, the high-speed stirring speed is 1500 rpm-2500 rpm, and the pre-emulsification time is 30-45 min.

8. The catalyst wastewater treatment agent according to claim 1, characterized in that: In step S2, an alkaline solution is added dropwise to adjust the pH to 8.

0.

9. The catalyst wastewater treatment agent according to claim 1, characterized in that: The reaction time in step S3 is 6-8 hours, and the temperature is kept for 1-1.5 hours.

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