CN112680235A - Secondary utilization method of inactivated non-noble metal chloroethylene catalyst carrier - Google Patents
Secondary utilization method of inactivated non-noble metal chloroethylene catalyst carrier Download PDFInfo
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Abstract
The invention provides a secondary utilization method of an inactivated non-noble metal chloroethylene catalyst carrier, which is characterized by comprising the following steps: pretreatment, mixing, loading, immobilization activation, drying, mixing and coating; the pretreatment comprises reduced pressure impurity removal, acid treatment, leaching, microwave treatment, modification, drying and grinding. The secondary utilization method of the inactivated non-noble metal chloroethylene catalyst carrier can restore the self-owned performance of the activated carbon carrier to a considerable degree; organic matters and heavy metals remained in the catalyst are effectively removed, and trace elements contained in the catalyst are effectively retained; the treated carrier activated carbon is transferred to a soil conditioner, so that the adsorbability of the deactivated catalyst carrier and trace elements contained in the deactivated catalyst are fully utilized, the waste deactivated catalyst is harmlessly treated, waste materials can be changed into valuable materials, and resources are recycled.
Description
Technical Field
The invention relates to the field of vinyl chloride catalysts, in particular to a secondary utilization method of an inactivated non-noble metal vinyl chloride catalyst carrier.
Background
Vinyl chloride, a monomer for the synthesis of polyvinyl chloride. The polyvinyl chloride resin is an important plastic raw material, is one of five general synthetic resins, has good physical and mechanical properties, and is widely applied to various fields in production and life. The production of vinyl chloride monomer is an important step in the polyvinyl chloride industry.
The synthesis process of vinyl chloride is divided into two major categories, namely an ethylene oxychlorination method and an acetylene hydrochlorination method, wherein the acetylene hydrochlorination method is taken as the main method. The catalyst for preparing polyvinyl chloride by adopting an acetylene hydrochlorination method mainly comprises a noble metal catalyst, a non-noble metal catalyst and a non-metal catalyst. Among them, the non-noble metal catalyst is most widely applied in the production process of preparing polyvinyl chloride by calcium carbide method due to the comprehensive influence of many factors such as catalytic efficiency, cost advantage and easy preparation degree. Compared with the other two catalysts, the non-noble metal catalyst has the advantages of low cost, small environmental hazard and high catalytic activity, and can reach the condition of industrial application.
At present, the adopted calcium carbide method for preparing non-noble metal catalyst of polyvinyl chloride usually adopts high-quality active carbon as a carrier, and loads catalytic active components and non-noble metals of tin, copper, barium, zinc, molybdenum, bismuth and the like. The applicant finds that the catalytic performance, the active component performance and the active carbon performance of the inactivated non-noble metal catalyst which can not continuously meet the industrial production requirements are reduced to a certain degree, and after the catalyst is reactivated and activated by adopting a specific treatment method, the comprehensive activity of the active carbon cannot meet the requirements of large-scale industrial production because the active carbon is influenced by vinyl chloride, and the catalyst is not suitable to be used as a catalyst for catalyzing the vinyl chloride. Meanwhile, although various performances of the inactivated non-noble metal catalyst are not ideal, the content of catalytic active organic substances (nitrogen-containing organic substances and the like) and heavy metals contained in the catalyst is still high, the catalyst has a certain poisoning effect on soil, water and organisms, and only the catalyst is treated as solid waste, so that the treatment energy consumption and the treatment cost are high, the recycling cannot be realized, and resources are wasted. Therefore, the applicant hopes to develop a new recycling way to recycle the non-noble metal catalyst, so as to change waste into valuable.
At present, soil acidification is aggravated due to a large amount of industrial activities in China and excessive application of farmland fertilizers, and the total content and the effective state content of heavy metals in soil are increased due to the emission of industrial wastes, so that the content of heavy metals in partial planted crops exceeds the standard, and attention is paid to soil restoration and treatment methods in recent years. The applicant finds that after the inactivated non-noble metal vinyl chloride catalyst is treated by a specific preparation method, the prepared active carbon carrier not only effectively removes harmful components, but also fully retains trace elements contained in the active carbon carrier; furthermore, through the treatment, the activated carbon can recover performance to a certain degree again, the activity is high, although the activated carbon is no longer suitable for the field of vinyl chloride catalysts, the activated carbon can be used for soil conditioning or remediation, a large amount of resources and cost consumed by preparation and activation of the activated carbon can be effectively saved, and the activated carbon has great significance for sustainable recycling of resources.
Meanwhile, the applicant also finds that the existing soil remediation agent is used in the soil conditioning process, the action time is short, the excellent performance of the soil cannot be maintained for a long time after the one-time remediation action is successful, and the later-stage reduction of the soil performance cannot be prevented.
Chinese patent CN110605106A discloses a regeneration method of harmlessly treated waste mercury catalyst activated carbon, which regenerates the harmlessly treated waste mercury catalyst activated carbon by acid treatment, calcium chloride separation, oxygen isolation of 650-. The patent has the disadvantages of high energy consumption and low energy efficiency ratio of the treatment process, and has low cost performance and low economic feasibility compared with the preparation and activation of new active carbon.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a secondary utilization method of an inactivated non-noble metal chloroethylene catalyst carrier, which aims to realize the following purposes:
(1) providing a secondary utilization method to realize secondary utilization of the inactivated non-noble metal chloroethylene catalyst carrier;
(2) the recovered inactivated non-noble metal chloroethylene catalyst carrier is used in a soil remediation agent for secondary utilization, and the soil remediation agent can overcome the problems that the action time is short, the excellent performance of soil cannot be maintained for a long time after the primary remediation action is successful, and the later decline of the soil performance cannot be prevented.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a secondary utilization method of a deactivated non-noble metal vinyl chloride catalyst carrier comprises the following steps: pretreatment, mixing, loading, immobilization activation, drying, mixing and coating;
the pretreatment comprises reduced pressure impurity removal, acid treatment, leaching, microwave treatment, modification, drying and grinding;
the step of removing impurities under reduced pressure, which is to place the inactivated non-noble metal chloroethylene catalyst under the vacuum degree of-0.09 to-0.07 MPa, heat up to 150 ℃ and 160 ℃, and preserve heat for 2 to 3 hours; in the heat preservation process, the inactivated non-noble metal chloroethylene catalyst is vibrated and mixed uniformly every 2 min;
and (3) decompressing and removing impurities, wherein the water content of the inactivated non-noble metal chloroethylene catalyst is lower than 2 percent.
Further, in the acid treatment, the deactivated non-noble metal chloroethylene catalyst subjected to the reduced pressure impurity removal is put into a phosphoric acid solution with the concentration of 2mol/L, the temperature is raised to 40-50 ℃, and the acid treatment is carried out;
the microwave treatment is to place the solid prepared in the leaching step in a vacuum environment and perform microwave treatment for 5-10min under the shaking condition of 700-800 RPM;
and (3) performing microwave treatment, wherein the microwave frequency is 22 MHz.
Further, the modification is to put the solids after the microwave treatment into a modification liquid with the volume 2-4 times, stir at 100-200RPM for 20-30min, then stand for 30min, filter out the solids, and complete the modification step;
the preparation method of the modified liquid comprises the following steps: cleaning and cutting pigskin, and putting into medical alcohol with concentration of 75% and volume of 2-3 times of pigskin for completely soaking for 15-20 min; filtering the pigskin, putting into 10-15 times volume of acetic acid solution, and extracting for 2-3 days at 0-5 ℃ with shaking; separating supernatant, and diluting with deionized water to 20-30 times; adding potassium permanganate, and adjusting the concentration of the potassium permanganate in the solution to be 0.05-0.08mol/L to prepare the modified solution.
Further, mixing, namely mixing and granulating the activated carbon with the particle size D50 of 100-200 meshes, which is prepared by grinding, bentonite, shell powder and modified adhesive in predetermined parts to prepare mixed particles with the particle size of 0.7-1.0 mm;
the activated carbon is as follows: bentonite: shell powder: the weight ratio of the modified glue is 10-15:3-5:5-8: 0.2-0.5.
Further, in the loading, 0.5-0.8 time volume of functional loading liquid is uniformly sprayed on the surface of the mixed particles, and the mixed particles are kept stand for 2-3 hours at the temperature of 80-85 ℃;
standing, wherein the ventilation wind speed is 0.1-0.15m/s in the standing process;
the functional loading liquid comprises potassium fulvate, potassium ferrate and coconut oil alcohol.
Further, the load is prepared by putting predetermined parts of potassium fulvate, potassium ferrate and coconut oil alcohol into 2-3 times volume of absolute ethyl alcohol, heating to 30-40 ℃, performing ultrasonic dispersion treatment for 3 times, and performing single ultrasonic dispersion for 20-30 min;
the ratio of the parts by weight of the potassium fulvate, the potassium ferrate and the coconut oil alcohol is 2-5:1-3: 1-3.
Further, the immobilization activation is to place the functional particles prepared in the loading step into N2Irradiating by using an ultraviolet high-pressure mercury lamp under the shaking condition of 500-600RPM in the atmosphere for solid-borne activation treatment for 5-15 min.
Further, the coating comprises: primary spraying;
the first spraying is to uniformly spray a coating agent at the temperature of 70-80 ℃ on the surface of the functional particles, then uniformly spray a predetermined part of auxiliary materials on the surface of the functional particles sprayed with the coating agent, and dry the functional particles for 30-50min at the temperature of 70-80 ℃;
the coating agent comprises: functional particles: the weight ratio of the auxiliary materials is 3-5:5-6: 0.3-0.5;
the coating agent is a water-soluble alkyd resin polymer coating agent prepared by a fatty acid method.
Further, the coating also comprises: secondary spraying;
the secondary spraying is carried out, wherein a coating agent with the temperature of 70-80 ℃ is sprayed on the surface of the functional particles after the primary spraying, finally, a predetermined part of superfine bentonite is uniformly sprayed on the surface of the functional particles sprayed with the coating agent, and the coating agent is dried for 30-50min at the temperature of 70-80 ℃ to prepare the soil remediation agent;
the coating agent comprises: functional particles: the weight ratio of the superfine bentonite is 2-3:5-6: 0.05-0.1;
the coating agent is a water-soluble alkyd resin polymer coating agent prepared by a fatty acid method.
Further, mixing the materials, namely mixing the aluminum oxide, the calcium oxide, the magnesium oxide, the manganese carbonate, the sodium bicarbonate and the betaine in predetermined parts, and grinding the mixture until the particle size is 5-10 microns to obtain an auxiliary material;
the weight ratio of the aluminum oxide to the calcium oxide to the magnesium oxide to the manganese carbonate to the sodium bicarbonate to the betaine is 5:5:1:2:1: 0.2.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the secondary utilization method of the inactivated non-noble metal chloroethylene catalyst carrier, the activated carbon carrier can restore the self-owned performance to a considerable degree through a specific method; a large amount of resources and cost consumed by the preparation and activation operation of the activated carbon are effectively saved, and sustainable resource recycling is realized.
(2) According to the secondary utilization method of the inactivated non-noble metal chloroethylene catalyst carrier, residual organic matters and heavy metals in the catalyst are effectively removed through a specific method, and trace elements contained in the catalyst are effectively retained.
(3) According to the method for recycling the inactivated non-noble metal chloroethylene catalyst carrier, the treated carrier active carbon is transferred to the soil conditioner, the adsorbability of the inactivated catalyst carrier and trace elements contained in the inactivated catalyst are fully utilized, so that the waste inactivated catalyst is subjected to harmless treatment, the storage and treatment pressure of industrial waste is greatly relieved, waste can be changed into valuable, and the cyclic recycling of resources is realized.
(4) According to the method for recycling the inactivated non-noble metal chloroethylene catalyst carrier, the prepared soil remediation agent can maintain the soil performance for a long time, and the pH of the soil is 6.5-7.2 after the soil remediation agent is applied for 18 months.
(5) According to the secondary utilization method of the inactivated non-noble metal chloroethylene catalyst carrier, the soil remediation agent prepared by the method is applied for 18 months, and the soil volume weight is 1.13-1.20g/cm3The porosity of the soil is 56-61%, and the content of water-stable aggregates larger than 0.25mm in the soil is improved by 81-83%.
(6) The soil remediation agent prepared by the secondary utilization method of the inactivated non-noble metal chloroethylene catalyst carrier can passivate heavy metal elements, effectively eliminate soil continuous cropping obstacles, effectively inhibit the occurrence of soil-borne diseases, simultaneously maintain the excellent performance of soil and prevent the reduction of the performance of the soil.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A secondary utilization method of a deactivated non-noble metal vinyl chloride catalyst carrier comprises the following steps: pretreatment, mixing, loading, solid-supported activation, drying, mixing and coating.
The pretreatment comprises reduced pressure impurity removal, acid treatment, leaching, microwave treatment, modification, drying and grinding.
The reduced pressure impurity removal is carried out, the inactivated non-noble metal chloroethylene catalyst is placed under the vacuum degree of-0.07 MPa, the temperature is raised to 150 ℃, and the heat preservation time is 2 hours; in the heat preservation process, the inactivated non-noble metal chloroethylene catalyst is vibrated and mixed uniformly every 2 min; and after the decompression impurity removal is finished, the water content of the inactivated non-noble metal chloroethylene catalyst is lower than 2%.
In the acid treatment, the deactivated non-noble metal chloroethylene catalyst subjected to the reduced pressure impurity removal is put into an acid treatment solution with the volume 2 times that of the deactivated non-noble metal chloroethylene catalyst, the temperature is raised to 40 ℃, and the acid treatment is carried out for 20 min; stirring at a speed of 50RPM during the acid treatment process to ensure that the catalyst is fully mixed with the acid treatment solution, and filtering out solids after the acid treatment is completed.
The acid treatment solution is a phosphoric acid solution with the concentration of 2 mol/L.
In the leaching, the solid prepared in the acid washing step is leached by NaOH solution with the volume 2 times that of the solid, and after leaching is finished, leachate is kept stand for 20 min; and then uniformly spraying sufficient deionized water on the solid until the pH of the solid is 7-8, and draining water.
The concentration of the NaOH solution is 20%.
And in the microwave treatment, the solid prepared in the leaching step is placed in a vacuum environment, and is subjected to microwave treatment for 5min under the shaking condition of 700 RPM.
And (3) performing microwave treatment, wherein the microwave frequency is 22 MHz.
And in the modification step, the solids after the microwave treatment are put into 2-volume modification liquid, stirred at 100-200RPM for 20min, then kept stand for 30min, and the solids are filtered out, so that the modification step is completed.
The preparation method of the modified liquid comprises the following steps: cleaning pigskin, cutting into small pieces with length and width of 0.4cm, soaking in 2 times volume of 75% medical alcohol for 15min, filtering, adding into 10 times volume of acetic acid solution, and extracting at 5 deg.C under shaking for 2 days; separating out supernatant liquor, and diluting to 20 times by using deionized water; and adding potassium permanganate, and adjusting the concentration of the potassium permanganate in the solution to be 0.05mol/L to prepare the modified solution.
And (3) drying, namely placing the modified solid at 80 ℃, drying at low temperature for 3h, wherein the ventilation air speed is 0.2m/s in the drying process, and finishing the drying step to obtain the activated carbon.
And grinding, namely grinding the dried active carbon until the particle size D50 is 100 meshes for later use.
And mixing, namely mixing and granulating the activated carbon prepared by grinding with bentonite, shell powder and modified glue in a predetermined part to prepare mixed particles with the particle size of 0.7 mm.
The activated carbon is as follows: bentonite: shell powder: the weight ratio of the modified glue is 10:5:5: 0.2.
The bentonite has the particle size of 300 meshes, the whiteness of 95 and the apparent viscosity of 28mPa & S.
The shell powder has the particle size of 200 meshes, the calcium content of 43 percent, the arsenic content of 0.24mg/kg, the lead content of 1.7mg/kg and the mercury content of 0.02 mg/kg.
The modified glue is prepared by putting pectin into 30 times volume of deionized water, uniformly dispersing, heating to 50 ℃, preserving heat, putting sodium alginate in equal parts by weight to the pectin, and uniformly mixing by ultrasonic.
And in the loading step, 0.5 time of volume of functional loading liquid is uniformly sprayed on the surface of the mixed particles, and the mixed particles are kept stand for 2 hours at the temperature of 80 ℃ to complete the loading step, so that the functional particles are prepared.
And standing, wherein the ventilation wind speed is 0.1m/s in the standing process.
The functional loading solution is prepared by putting predetermined parts of potassium fulvate, potassium ferrate and coconut oil alcohol into 2 times volume of absolute ethyl alcohol, heating to 30 ℃, and performing ultrasonic dispersion treatment for 3 times, wherein the single ultrasonic dispersion time is 20 min.
And carrying out ultrasonic treatment, wherein the ultrasonic frequency is 22 KHz.
The ratio of the parts by weight of the potassium fulvate, the potassium ferrate and the coconut oil alcohol is 2:1: 1.
The immobilization activation is to place the functional particles prepared in the loading step in N2Irradiating with ultraviolet high-pressure mercury lamp under shaking condition of 500RPM for 5 min.
The ultraviolet high-pressure mercury lamp irradiates, and the distance between a light source and the mixed particles is 20 cm.
The ultraviolet high-pressure mercury lamp has the luminous flux of 21Klm, the color rendering index of 45 and the mercury vapor pressure of 120 kPa.
And (3) drying, namely placing the functional particles prepared in the immobilization activation step at 78 ℃ under the condition of micro negative pressure, and performing shaking drying at 500RPM for 1h to finish the drying step for later use.
The auxiliary materials are prepared by mixing aluminum oxide, calcium oxide, magnesium oxide, manganese carbonate, sodium bicarbonate and betaine in predetermined parts, and grinding until the particle size is 5 micrometers.
The weight ratio of the aluminum oxide to the calcium oxide to the magnesium oxide to the manganese carbonate to the sodium bicarbonate to the betaine is 5:5:1:2:1: 0.2.
And the coating comprises primary spraying and secondary spraying.
And the first spraying is to uniformly spray a coating agent at the temperature of 70 ℃ on the surface of the functional particles, then uniformly spray a predetermined part of auxiliary materials on the surface of the functional particles sprayed with the coating agent, and drying for 30min at the temperature of 70 ℃.
The coating agent comprises: functional particles: the weight ratio of the auxiliary materials is 3:5: 0.5.
And (3) performing secondary spraying, namely spraying a coating agent with the temperature of 70 ℃ on the surfaces of the functional particles again, finally uniformly spraying a predetermined part of superfine bentonite on the surfaces of the functional particles sprayed with the coating agent, and drying for 30min at the temperature of 70 ℃ to obtain the soil repairing agent.
The coating agent comprises: functional particles: the weight ratio of the superfine bentonite is 2:5: 0.1.
The coating agent is a water-soluble alkyd resin polymer coating agent prepared by a fatty acid method.
The acid value of the water-soluble alkyd resin is 50 mgKOH/g.
The particle size of the superfine bentonite is 500 meshes.
The following specifications of soil were used as test soil samples: the soil has a pH of 5.8 and a soil volume weight of 1.65g/cm3The soil porosity was 41%. The soil conditioner prepared by the method for recycling the inactivated non-noble metal chloroethylene catalyst carrier is used for conditioning and repairing the test soil sample, and the pH of the soil is 6.5 after the soil conditioner is detected and applied for 18 months; the volume weight of the soil is 1.13g/cm3The soil porosity is 58%, and the content of water-stable aggregates larger than 0.25mm in the soil is improved by 81%; meanwhile, heavy metal elements can be passivated, soil continuous cropping obstacles can be effectively eliminated, and occurrence of soil-borne diseases can be effectively inhibited.
Example 2
A secondary utilization method of a deactivated non-noble metal vinyl chloride catalyst carrier comprises the following steps: pretreatment, mixing, loading, solid-supported activation, drying, mixing and coating.
The pretreatment comprises reduced pressure impurity removal, acid treatment, leaching, microwave treatment, modification, drying and grinding.
The reduced pressure impurity removal is carried out, the inactivated non-noble metal chloroethylene catalyst is placed under the vacuum degree of-0.09 MPa, the temperature is raised to 156 ℃, and the heat preservation time is 2.5 h; in the heat preservation process, the inactivated non-noble metal chloroethylene catalyst is vibrated and mixed uniformly every 2 min; and after the decompression impurity removal is finished, the water content of the inactivated non-noble metal chloroethylene catalyst is lower than 2%.
In the acid treatment, the deactivated non-noble metal chloroethylene catalyst subjected to the reduced pressure impurity removal is put into an acid treatment solution with the volume being 3 times that of the deactivated non-noble metal chloroethylene catalyst, the temperature is raised to 45 ℃, and the acid treatment is carried out for 35 min; stirring at a speed of 60RPM during the acid treatment process to ensure that the catalyst is fully mixed with the acid treatment solution, and filtering out solids after the acid treatment is completed.
The acid treatment solution is a phosphoric acid solution with the concentration of 2 mol/L.
In the leaching, the solid prepared in the acid washing step is leached by NaOH solution with the volume 2 times that of the solid, and after leaching is finished, leachate is kept stand for 30 min; and then uniformly spraying sufficient deionized water on the solid until the pH of the solid is 7-8, and draining water.
The concentration of the NaOH solution is 20-30%.
And in the microwave treatment, the solid prepared in the leaching step is placed in a vacuum environment, and is subjected to microwave treatment for 7min under the shaking condition of 00 RPM.
And (3) performing microwave treatment, wherein the microwave frequency is 22 MHz.
And (3) modifying, namely putting the solids subjected to microwave treatment into a modification solution with the volume being 3 times that of the solids, stirring at 150RPM for 30min, standing for 30min, and filtering out the solids to finish the modifying step.
The preparation method of the modified liquid comprises the following steps: cleaning pigskin, cutting into pieces with length and width of 0.2cm, soaking in 2.5 times volume of 75% medical alcohol for 20min, filtering, adding into 12 times volume of acetic acid solution, and extracting at 2 deg.C under shaking for 3 days; separating out supernatant liquor, and diluting to 22 times by using deionized water; and adding potassium permanganate, and adjusting the concentration of the potassium permanganate in the solution to be 0.06mol/L to prepare the modification solution.
And (3) drying, namely drying the modified solid at a low temperature of 85 ℃ for 4h, wherein the ventilation air speed is 0.2m/s in the drying process, and finishing the drying step to obtain the activated carbon.
And grinding, namely grinding the dried active carbon until the particle size D50 is 200 meshes for later use.
And mixing, namely mixing and granulating the activated carbon prepared by grinding with bentonite, shell powder and modified glue in a predetermined part to prepare mixed particles with the particle size of 0.7 mm.
The activated carbon is as follows: bentonite: shell powder: the weight ratio of the modified glue is 15:4:6: 0.4.
The bentonite has the particle size of 350 meshes, the whiteness of 96 and the apparent viscosity of 30mPa & S.
The shell powder has the particle size of 400 meshes, the calcium content of 43 percent, the arsenic content of 0.24mg/kg, the lead content of 1.7mg/kg and the mercury content of 0.02 mg/kg.
The modified glue is prepared by putting pectin into 30 times volume of deionized water, uniformly dispersing, heating to 60 ℃, preserving heat, putting sodium alginate in equal parts by weight to the pectin, and uniformly mixing with ultrasonic waves.
And in the loading step, 0.7 time of volume of functional loading liquid is uniformly sprayed on the surface of the mixed particles, and the mixed particles are kept stand for 3 hours at the temperature of 80 ℃ to complete the loading step, so that the functional particles are prepared.
And standing, wherein the ventilation wind speed is 0.12m/s in the standing process.
The functional loading solution is prepared by putting predetermined parts of potassium fulvate, potassium ferrate and coconut oil alcohol into 3 times volume of absolute ethyl alcohol, heating to 40 ℃, and performing ultrasonic dispersion treatment for 3 times, wherein the single ultrasonic dispersion time is 30 min.
And carrying out ultrasonic treatment, wherein the ultrasonic frequency is 24 KHz.
The ratio of the parts by weight of the potassium fulvate, the potassium ferrate and the coconut oil alcohol is 4:1: 3.
The immobilization activation is to place the functional particles prepared in the loading step in N2Irradiating with ultraviolet high-pressure mercury lamp under shaking condition of 600RPM for 10 min.
And irradiating by the ultraviolet high-pressure mercury lamp, wherein the distance between a light source and the mixed particles is 25 cm.
The ultraviolet high-pressure mercury lamp has the luminous flux of 23Klm, the color rendering index of 50 and the mercury vapor pressure of 200 kPa.
And (3) drying, namely placing the functional particles prepared in the immobilization activation step at 80 ℃ under the condition of micro negative pressure, and performing oscillation drying at 600RPM for 2h to finish the drying step for later use.
The auxiliary materials are prepared by mixing aluminum oxide, calcium oxide, magnesium oxide, manganese carbonate, sodium bicarbonate and betaine in predetermined parts, and grinding until the particle size is 5 micrometers.
The weight ratio of the aluminum oxide to the calcium oxide to the magnesium oxide to the manganese carbonate to the sodium bicarbonate to the betaine is 5:5:1:2:1: 0.2.
And the coating comprises primary spraying and secondary spraying.
And the first spraying is to uniformly spray a coating agent at the temperature of 70 ℃ on the surface of the functional particles, then uniformly spray a predetermined part of auxiliary materials on the surface of the functional particles sprayed with the coating agent, and drying for 50min at the temperature of 80 ℃.
The coating agent comprises: functional particles: the weight ratio of the auxiliary materials is 5:5: 0.4.
And (3) performing secondary spraying, namely spraying a coating agent with the temperature of 80 ℃ on the surface of the functional particle again, finally uniformly spraying a predetermined part of superfine bentonite on the surface of the functional particle sprayed with the coating agent, and drying for 50min at the temperature of 80 ℃ to obtain the soil repairing agent.
The coating agent comprises: functional particles: the weight ratio of the superfine bentonite is 3:5: 0.1.
The coating agent is a water-soluble alkyd resin polymer coating agent prepared by a fatty acid method.
The acid value of the water-soluble alkyd resin is 70 mgKOH/g.
The particle size of the superfine bentonite is 600 meshes.
The following specifications of soil were used as test soil samples: the soil has a pH of 5.8 and a soil volume weight of 1.65g/cm3The porosity of the soil is41 percent. The soil conditioner prepared by the method for recycling the inactivated non-noble metal chloroethylene catalyst carrier is used for conditioning and repairing the test soil sample, and the pH of the soil is 6.8 after the soil conditioner is detected and applied for 18 months; the total number of microorganisms in each gram of soil is 440 multiplied by 104(ii) a The volume weight of the soil is 1.20g/cm3The porosity of the soil is 61%, and the content of water-stable aggregates larger than 0.25mm in the soil is improved by 83%; meanwhile, heavy metal elements can be passivated, soil continuous cropping obstacles can be effectively eliminated, and occurrence of soil-borne diseases can be effectively inhibited.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A secondary utilization method of a deactivated non-noble metal vinyl chloride catalyst carrier is characterized by comprising the following steps: pretreatment, mixing, loading, immobilization activation, drying, mixing and coating;
the pretreatment comprises reduced pressure impurity removal, acid treatment, leaching, microwave treatment, modification, drying and grinding;
the step of removing impurities under reduced pressure, which is to place the inactivated non-noble metal chloroethylene catalyst under the vacuum degree of-0.09 to-0.07 MPa, heat up to 150 ℃ and 160 ℃, and preserve heat for 2 to 3 hours; in the heat preservation process, the inactivated non-noble metal chloroethylene catalyst is vibrated and mixed uniformly every 2 min;
and (3) decompressing and removing impurities, wherein the water content of the inactivated non-noble metal chloroethylene catalyst is lower than 2 percent.
2. The method for recycling the deactivated non-noble metal vinyl chloride catalyst carrier as recited in claim 1, wherein the acid treatment comprises putting the deactivated non-noble metal vinyl chloride catalyst subjected to the reduced pressure impurity removal into a phosphoric acid solution with a concentration of 2mol/L, raising the temperature to 40-50 ℃ and performing the acid treatment;
the microwave treatment is to place the solid prepared in the leaching step in a vacuum environment and perform microwave treatment for 5-10min under the shaking condition of 700-800 RPM;
and (3) performing microwave treatment, wherein the microwave frequency is 22 MHz.
3. The method for recycling the inactivated non-noble metal vinyl chloride catalyst carrier as claimed in claim 1, wherein the modification comprises the steps of putting the solids subjected to microwave treatment into a modification solution with the volume 2-4 times that of the modification solution, stirring at 100-200RPM for 20-30min, standing for 30min, filtering out the solids, and completing the modification step;
the preparation method of the modified liquid comprises the following steps: cleaning and cutting pigskin, and putting into medical alcohol with concentration of 75% and volume of 2-3 times of pigskin for completely soaking for 15-20 min; filtering the pigskin, putting into 10-15 times volume of acetic acid solution, and extracting for 2-3 days at 0-5 ℃ with shaking; separating supernatant, and diluting with deionized water to 20-30 times; adding potassium permanganate, and adjusting the concentration of the potassium permanganate in the solution to be 0.05-0.08mol/L to prepare the modified solution.
4. The method as claimed in claim 1, wherein the mixing step comprises mixing and granulating the activated carbon with particle size D50 of 100-200 meshes with bentonite, shell powder and modified rubber in predetermined parts to obtain mixed particles with particle size of 0.7-1.0 mm;
the activated carbon is as follows: bentonite: shell powder: the weight ratio of the modified glue is 10-15:3-5:5-8: 0.2-0.5.
5. The method for recycling the deactivated non-noble metal vinyl chloride catalyst carrier as recited in claim 1, wherein the loading step comprises uniformly spraying 0.5-0.8 times of volume of functional loading liquid on the surface of the mixed particles, and standing for 2-3h at 80-85 ℃;
standing, wherein the ventilation wind speed is 0.1-0.15m/s in the standing process;
the functional loading liquid comprises potassium fulvate, potassium ferrate and coconut oil alcohol.
6. The method for recycling the inactivated non-noble metal vinyl chloride catalyst carrier according to claim 1, wherein the loading is carried out by putting predetermined parts of potassium fulvate, potassium ferrate and coconut oil alcohol into 2-3 times of absolute ethyl alcohol, heating to 30-40 ℃, carrying out ultrasonic dispersion treatment for 3 times, and carrying out single ultrasonic dispersion for 20-30 min;
the ratio of the parts by weight of the potassium fulvate, the potassium ferrate and the coconut oil alcohol is 2-5:1-3: 1-3.
7. The method of claim 1, wherein the immobilization activation comprises placing the functional particles obtained from the loading step in N2Irradiating by using an ultraviolet high-pressure mercury lamp under the shaking condition of 500-600RPM in the atmosphere for solid-borne activation treatment for 5-15 min.
8. The method of claim 1, wherein the coating comprises: primary spraying;
the first spraying is to uniformly spray a coating agent at the temperature of 70-80 ℃ on the surface of the functional particles, then uniformly spray a predetermined part of auxiliary materials on the surface of the functional particles sprayed with the coating agent, and dry the functional particles for 30-50min at the temperature of 70-80 ℃;
the coating agent comprises: functional particles: the weight ratio of the auxiliary materials is 3-5:5-6: 0.3-0.5;
the coating agent is a water-soluble alkyd resin polymer coating agent prepared by a fatty acid method.
9. The method of claim 1, wherein the coating further comprises: secondary spraying;
the secondary spraying is carried out, wherein a coating agent with the temperature of 70-80 ℃ is sprayed on the surface of the functional particles after the primary spraying, finally, a predetermined part of superfine bentonite is uniformly sprayed on the surface of the functional particles sprayed with the coating agent, and the coating agent is dried for 30-50min at the temperature of 70-80 ℃ to prepare the soil remediation agent;
the coating agent comprises: functional particles: the weight ratio of the superfine bentonite is 2-3:5-6: 0.05-0.1;
the coating agent is a water-soluble alkyd resin polymer coating agent prepared by a fatty acid method.
10. The method for recycling the inactivated non-noble metal vinyl chloride catalyst carrier as claimed in claim 1, wherein the mixing material is prepared by mixing predetermined parts of alumina, calcium oxide, magnesium oxide, manganese carbonate, sodium bicarbonate and betaine, and grinding the mixture to a particle size of 5-10 microns to obtain an auxiliary material;
the weight ratio of the aluminum oxide to the calcium oxide to the magnesium oxide to the manganese carbonate to the sodium bicarbonate to the betaine is 5:5:1:2:1: 0.2.
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