CN113441134A - Preparation method and application of catalyst for organophosphorus pesticide production wastewater - Google Patents
Preparation method and application of catalyst for organophosphorus pesticide production wastewater Download PDFInfo
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- CN113441134A CN113441134A CN202110524579.1A CN202110524579A CN113441134A CN 113441134 A CN113441134 A CN 113441134A CN 202110524579 A CN202110524579 A CN 202110524579A CN 113441134 A CN113441134 A CN 113441134A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000002351 wastewater Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000003987 organophosphate pesticide Substances 0.000 title claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 22
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 4
- 239000005944 Chlorpyrifos Substances 0.000 claims description 3
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 150000003863 ammonium salts Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 abstract description 6
- 230000008020 evaporation Effects 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009279 wet oxidation reaction 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
Abstract
The invention relates to the technical field of wastewater treatment, in particular to a preparation method and application of a catalyst for organophosphorus pesticide production wastewater, which comprises the following steps: s1: preparation of the carrier: selecting diatomite which is not calcined at high temperature, stirring uniformly in deionized water at room temperature, performing suction filtration to obtain a solid, and drying the solid after suction filtration for later use; s2: preparing a precursor: selecting appropriate active metal inorganic salt, fully combining the active metal inorganic salt in a water-organic solvent solution, activating at high temperature, and naturally cooling to obtain a precursor for later use; s3: and (3) preparing a catalyst. The invention aims to provide a preparation method and application of a catalyst for organophosphorus pesticide production wastewater, so that the treatment temperature of COD (chemical oxygen demand) of high-COD wastewater can be effectively reduced in the evaporation concentration process, the requirement on equipment is reduced, and the operation cost in the high-COD wastewater treatment process is reduced.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a preparation method and application of a catalyst for organophosphorus pesticide production wastewater.
Background
The energy crisis and ecological problems are two major limiting factors of the current technological progress and human development. In the face of the current environmental protection policy of continuous high pressure, the investment of various fields and industries on environmental protection management is forced to be increased continuously. Active metals (noble metals or rare earth metals) are continuously researched and developed into high-activity catalysts in various forms, and a large number of reports are applied to the field of air pollution treatment, such as photocatalysts, high-temperature flameless combustion catalysts and the like. However, the active metal catalyst is applied to the wastewater/sewage treatment process, and related research reports are relatively few. In the organic phosphorus wastewater, high COD exists, and generally, the wastewater with high COD (COD is more than or equal to 5 multiplied by 105mg/L) can be effectively treated, and the treatment processes commonly adopted in the industry are wet oxidation technology, multi-effect evaporation and high-temperature combustion.
At present, in the process of treating high-COD wastewater, the treatment conditions relate to high temperature (300-1000 ℃) and high pressure (0.1-6 MPa), and due to the high temperature and high pressure, the operation risk coefficient is high, the potential safety hazard is large, the requirement on the material of equipment is high, the first-time investment cost is high, and the operation cost is increased in the operation process.
Disclosure of Invention
In view of the above, the present invention provides a preparation method and an application of a catalyst for wastewater from organophosphorus pesticide production, so that the treatment temperature of COD can be effectively reduced and the requirement on equipment can be reduced during the evaporation and concentration process of high COD wastewater, thereby reducing the operation cost during the treatment process of high COD wastewater.
The invention solves the technical problems by the following technical means:
a preparation method of a catalyst for organophosphorus pesticide production wastewater comprises the following steps:
s1: preparation of the carrier: selecting diatomite which is not calcined at high temperature, stirring uniformly in deionized water at room temperature, performing suction filtration to obtain a solid, and drying the solid after suction filtration for later use;
s2: preparing a precursor: selecting appropriate active metal inorganic salt, fully combining the active metal inorganic salt in a water-organic solvent solution, activating at high temperature, and naturally cooling to obtain a precursor for later use;
s3: preparation of the catalyst: and (3) carrying out ultrasonic treatment on the carrier prepared in the step S1 and the precursor prepared in the step S2 in a proper amount of deionized water, drying after the ultrasonic treatment is finished, finally putting the carrier and the precursor into a microwave reactor, heating by adopting a programmed heating mode, and keeping the temperature to obtain the supported multi-element active metal catalyst powder.
The diatomite has the structural characteristics of light weight, large specific surface area, porosity and the like, impurities in the diatomite are removed through water washing, and then the pore diameter of the diatomite is modified through drying and calcining, so that the load performance of the diatomite is enhanced; the catalytic degradation performance of the metal is enhanced by activating the inorganic salt of the active metal, and then the activated inorganic salt of the active metal is uniformly dispersed in the diatomite, so that the catalytic performance of the catalyst is synergistically enhanced. The catalyst prepared by the method has higher activity, can be stored for a long time and is convenient for long-term use.
Further, in the step S1, the stirring time of the diatomite is 1-4H, and the baking temperature of the diatomite solid is: the baking time is 50-70 ℃ as follows: 1-2H, and the mass of the deionized water is 2-3 times of that of the diatomite.
Through washing, stirring, suction filtration, get rid of the impurity in the diatomaceous earth, the rethread is toasted, makes the diatomaceous earth stereotype, the subsequent processing of being convenient for.
Further, in the step S2, the active metals are two or three of Cu/Mn/Ce inorganic salts.
Cu and Mn or Mn and Ce or Cu and Mn and Ce can synergistically enhance the degradation capability of the catalyst to wastewater in a Fenton catalytic system, and the degradation capability of the catalyst to wastewater is further improved by matching with diatomite.
Further, in the step S2, the mass ratio of the Cu/Mn/Ce inorganic salt is (1.2-2.5): (2-3): 1.
by controlling the mass ratio of the Cu/Mn/Ce inorganic salt, the Cu/Mn/Ce inorganic salt can achieve the maximum catalytic effect in the catalyst, thereby increasing the degradation capability of the catalyst.
Further, in the step S2, the organic solvent is one of polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polymaleic anhydride, and polyquaternary ammonium salt.
Further, in the step S2, the precursor is further pretreated before being activated at high temperature, and the pretreatment specifically includes the following steps: uniformly mixing inorganic salt of active metal in a water-polyethylene glycol mixed solution, adjusting the pH value of the mixed solution to 5-7, stirring at room temperature for 1-3H, performing ultrasonic treatment at room temperature for 3-7H after stirring is completed, recrystallizing the mixed solution at 70-100 ℃, performing centrifugal separation to obtain a recrystallized solid, and drying the solid at 50-70 ℃ to obtain a dried solid.
The three inorganic salts are fully mixed together by pretreating the inorganic salt of the active metal, and form a solid, so that the storage and the transportation are convenient.
Further, in the step S2, the conditions of high-temperature activation are as follows: calcining for 1-3h at 250-350 ℃.
The mixed solid of the active metal is calcined at a high temperature, so that the inorganic salt of the active metal is activated and the activity of the inorganic salt is enhanced.
Further, in the step S3, the mass ratio of the carrier to the precursor is: (3.5-5):1.
Further, in the step S3, the time of the ultrasonic treatment is: 2-5H, and the drying temperature is as follows: 50-60 ℃, and the temperature programmed is as follows: 150 ℃ and 300 ℃, and the heat preservation time is as follows: 1.5-5H.
The invention also discloses an application of the catalyst for the production wastewater of the organophosphorus pesticide, and the catalyst is applied to the production wastewater of chlorpyrifos in an organophosphorus pesticide chemical plant.
The preparation method and the application of the catalyst for the organophosphorus pesticide production wastewater have the following advantages:
1. the catalyst of the scheme of the application has the advantages of common and easily-obtained raw materials, simple preparation process, higher catalytic activity and contribution to industrial production;
2. the catalyst of the scheme of the application is applied to the evaporation concentration process of high COD wastewater, the treatment temperature can be effectively reduced to 150-250 ℃, and the catalyst can be used in a normal pressure environment, so that the treatment temperature and pressure of the wastewater are reduced, and the risk coefficient and the operation cost in the wastewater treatment process are reduced;
3. the catalyst of the scheme is applied to the evaporation and concentration process of high-COD wastewater, the treatment condition is relatively mild, the requirement on equipment material selection is not high, and the first investment cost is greatly reduced;
4. the catalyst of the scheme is wide in application range to high-COD wastewater, not only can be applied to organophosphorus pesticide production wastewater, but also can be applied to industrial wastewater, printing and dyeing wastewater, garbage penetrating fluid, domestic sewage and the like.
Detailed Description
Example 1 preparation of catalyst
S1: preparation of the carrier: selecting 100g of diatomite which is not calcined at high temperature, stirring the diatomite in deionized water with the mass of 2-3 times of that of the diatomite at room temperature for 1H, after stirring uniformly, carrying out suction filtration to obtain a solid, baking the solid after suction filtration for 1H at 70 ℃, and drying for later use;
s2: preparing a precursor: selecting inorganic salts of Cu and Mn, placing 10g of inorganic salts of Cu and 20g of inorganic salts of Mn in a water-polyethylene glycol solution, fully and uniformly stirring, adjusting the pH value of the mixed solution to 5-7 after uniform stirring, mechanically stirring for 1H again at room temperature, after stirring, ultrasonically treating for 3H at room temperature, after ultrasonic treatment, recrystallizing the mixed solution at 70-100 ℃ after recrystallization, then centrifugally separating to obtain recrystallized solid, drying the solid at 50-70 ℃, placing the solid in a calcining furnace, calcining for 3H at 250 ℃, after calcination, naturally cooling to obtain a precursor for later use;
s3: preparation of the catalyst: and (2) carrying out ultrasonic treatment on the carrier prepared in the step 35g S1 and the precursor prepared in the step 10g S2 in a proper amount of deionized water for 2-5h, drying at 50-60 ℃ after the ultrasonic treatment is finished, finally putting the carrier into a microwave reactor, and carrying out heat preservation at 150-300 ℃ for 1.5-5h by adopting a programmed heating mode to obtain the supported multi-element active metal catalyst powder.
Example 2 preparation of catalyst
S1: preparation of the carrier: selecting 120g of diatomite which is not calcined at high temperature, stirring for 2H at room temperature in deionized water with the mass of 2-3 times that of the diatomite, uniformly stirring, then carrying out suction filtration to obtain a solid, baking the solid subjected to suction filtration for 1.5H at the temperature of 60 ℃, and drying for later use;
s2: preparing a precursor: selecting inorganic salts of Mn and Ce, placing 13g of inorganic salts of Mn and 20g of inorganic salts of Ce in a water-polyethylene glycol solution for fully stirring, adjusting the pH value of the mixed solution to 5-7 after uniformly stirring, mechanically stirring for 2H again at room temperature, performing ultrasonic treatment for 5H at room temperature after stirring, recrystallizing the mixed solution at 70-100 ℃ after ultrasonic treatment, performing centrifugal separation after recrystallization to obtain recrystallized solid, drying the solid at 50-70 ℃, placing the solid in a calcining furnace, calcining for 2H at 300 ℃, and naturally cooling after calcination to obtain a precursor for later use;
s3: preparation of the catalyst: and (2) carrying out ultrasonic treatment on the carrier prepared in the step 40g S1 and the precursor prepared in the step 10g S2 in a proper amount of deionized water for 2-5h, drying at 50-60 ℃ after the ultrasonic treatment is finished, finally putting the carrier into a microwave reactor, and carrying out heat preservation at 150-300 ℃ for 1.5-5h in a programmed heating mode to obtain the supported multi-element active metal catalyst powder.
Example 3 preparation of catalyst III
S1: preparation of the carrier: selecting 150g of diatomite which is not calcined at high temperature, stirring for 3 hours at room temperature in deionized water with the mass of 2-3 times that of the diatomite, uniformly stirring, then carrying out suction filtration to obtain a solid, baking the solid subjected to suction filtration for 1 hour at 70 ℃, and drying for later use;
s2: preparing a precursor: selecting inorganic salts of Cu and Ce, placing 12g of inorganic salts of Cu and 25g of inorganic salts of Ce in a water-polyethylene glycol solution for fully stirring, adjusting the pH value of the mixed solution to 5-7 after uniformly stirring, mechanically stirring for 3H again at room temperature, performing ultrasonic treatment for 7H at room temperature after stirring, recrystallizing the mixed solution at 70-100 ℃ after ultrasonic treatment, performing centrifugal separation after recrystallization to obtain recrystallized solid, drying the solid at 50-70 ℃, placing the solid in a calcining furnace, calcining for 1H at 350 ℃, and naturally cooling after calcination to obtain a precursor for later use;
s3: preparation of the catalyst: and (2) carrying out ultrasonic treatment on the carrier prepared in the step 42g S1 and the precursor prepared in the step 10g S2 in a proper amount of deionized water for 2-5h, drying at 50-60 ℃ after the ultrasonic treatment is finished, finally putting the carrier into a microwave reactor, and carrying out heat preservation at 150-300 ℃ for 1.5-5h in a programmed heating mode to obtain the supported multi-element active metal catalyst powder.
Example 4 preparation of catalyst four
S1: preparation of the carrier: selecting 150g of diatomite which is not calcined at high temperature, stirring for 3 hours at room temperature in deionized water with the mass of 2-3 times that of the diatomite, uniformly stirring, then carrying out suction filtration to obtain a solid, baking the solid subjected to suction filtration for 1 hour at 70 ℃, and drying for later use;
s2: preparing a precursor: selecting inorganic salts of Cu, Mn and Ce, placing 15g of inorganic salt of Cu, 30g of inorganic salt of Ce and 10g of inorganic salt of Ce in a water-polyethylene glycol solution for fully stirring, adjusting the pH value of the mixed solution to 5-7 after uniformly stirring, mechanically stirring for 3H again at room temperature, after stirring, ultrasonically treating for 7H at room temperature, after ultrasonic treatment, recrystallizing the mixed solution at 70-100 ℃, then centrifugally separating to obtain recrystallized solid, drying the solid at 50-70 ℃, placing the solid in a calcining furnace, calcining for 1H at 350 ℃, and naturally cooling after calcining to obtain a precursor for later use;
s3: preparation of the catalyst: and (2) carrying out ultrasonic treatment on the carrier prepared in the step 50g S1 and the precursor prepared in the step 10g S2 in a proper amount of deionized water for 2-5h, drying at 50-60 ℃ after the ultrasonic treatment is finished, finally putting the carrier into a microwave reactor, and carrying out heat preservation at 150-300 ℃ for 1.5-5h in a programmed heating mode to obtain the supported multi-element active metal catalyst powder.
Taking the supported multi-element active metal catalyst prepared in the embodiment 1-4, selecting chlorpyrifos production wastewater of an organophosphorus pesticide chemical plant of Chongqing as a treatment object, detecting that CODcr of raw wastewater is 30000-50000mg/L, and respectively treating the wastewater by two ways, wherein the first way is to directly add the supported catalyst into quantitative wastewater, and then simulate MVR treatment conditions to carry out small-scale continuous treatment for 24 hours;
secondly, loading the supported catalyst powder on a filter screen, fixing the filter screen at a vapor phase outlet of water vapor, and then simulating MVR treatment conditions to carry out pilot plant continuous treatment for 24h (MVR process conditions are that the heat source temperature is 120-200 ℃, the reaction temperature is 85-103 ℃, and the negative pressure is-0.06-0.09 MPa), and detecting COD, wherein the detection result is as follows:
and (3) displaying a detection result: the wastewater is treated by the first mode, the COD of the obtained condensed wastewater is 40mg/L-100mg/L, and the COD of the residual liquid is less than or equal to 3.5 mg/L and less than or equal to 105 mg/L. The wastewater is treated by adopting the second mode, and the COD of the obtained condensed water is less than or equal to 38 mg/L.
From the above-mentioned result, when the high COD waste water treatment is applied to the supported multi-element active metal catalyst in the scheme, the high COD waste water can be evaporated and concentrated, the treatment temperature of COD can be effectively reduced, the requirement on equipment is reduced, the operation cost in the high COD waste water treatment process is reduced, the MVR evaporation treatment under the treatment condition is reduced, the COD in the obtained condensed waste water is less than or equal to 40mg/L, the primary discharge standard of Integrated wastewater discharge Standard (GB-8978/1996) is reached, if other indexes are qualified, the deep treatment is not needed, and the catalyst in the scheme can effectively reduce the COD content in the waste water.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (10)
1. A preparation method of a catalyst for organophosphorus pesticide production wastewater is characterized by comprising the following steps: the method comprises the following steps:
s1: preparation of the carrier: selecting diatomite which is not calcined at high temperature, stirring uniformly in deionized water at room temperature, performing suction filtration to obtain a solid, and drying the solid after suction filtration for later use;
s2: preparing a precursor: selecting appropriate active metal inorganic salt, fully combining the active metal inorganic salt in a water-organic solvent solution, activating at high temperature, and naturally cooling to obtain a precursor for later use;
s3: preparation of the catalyst: and (3) carrying out ultrasonic treatment on the carrier prepared in the step S1 and the precursor prepared in the step S2 in a proper amount of deionized water, drying after the ultrasonic treatment is finished, finally putting the carrier and the precursor into a microwave reactor, heating by adopting a programmed heating mode, and keeping the temperature to obtain the supported multi-element active metal catalyst powder.
2. The method for preparing the catalyst for organophosphorus pesticide production wastewater according to claim 1, wherein the method comprises the following steps: in the step S1, the stirring time of the diatomite is 1-4H, and the baking temperature of the diatomite solid is: the baking time is 50-70 ℃ as follows: 1-2H, and the mass of the deionized water is 2-3 times of that of the diatomite.
3. The method for preparing the catalyst for organophosphorus pesticide production wastewater according to claim 2, wherein the method comprises the following steps: in the step of S2, the active metals are two or three of Cu/Mn/Ce inorganic salts.
4. The method for preparing the catalyst for organophosphorus pesticide production wastewater according to claim 3, wherein the method comprises the following steps: in the step S2, the mass ratio of the Cu/Mn/Ce inorganic salt is (1.2-2.5): (2-3): 1.
5. the method for preparing the catalyst for organophosphorus pesticide production wastewater according to claim 4, wherein the method comprises the following steps: in the step S2, the organic solvent is one of polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polymaleic anhydride, and polyquaternary ammonium salt.
6. The method for preparing the catalyst for organophosphorus pesticide production wastewater according to claim 5, wherein the method comprises the following steps: in the step S2, the precursor is further pretreated before being activated at high temperature, and the pretreatment process is as follows: uniformly mixing inorganic salt of active metal in a water-polyethylene glycol mixed solution, adjusting the pH value of the mixed solution to 5-7, stirring at room temperature for 1-3H, performing ultrasonic treatment at room temperature for 3-7H after stirring is completed, recrystallizing the mixed solution at 70-100 ℃, performing centrifugal separation to obtain a recrystallized solid, and drying the solid at 50-70 ℃ to obtain a dried solid.
7. The method for preparing the catalyst for organophosphorus pesticide production wastewater according to claim 6, wherein the method comprises the following steps: in the step S2, the conditions of high-temperature activation are as follows: calcining for 1-3h at 250-350 ℃.
8. The method for preparing the catalyst for organophosphorus pesticide production wastewater according to claim 7, wherein the method comprises the following steps: in the step S3, the mass ratio of the carrier to the precursor is: (3.5-5): 1.
9. the method for preparing the catalyst for organophosphorus pesticide production wastewater according to claim 8, wherein the method comprises the following steps: in the step S3, the time of the ultrasonic treatment is: 2-5H, and the drying temperature is as follows: 50-60 ℃, and the temperature programmed is as follows: 150 ℃ and 300 ℃, and the heat preservation time is as follows: 1.5-5H.
10. The use of the catalyst for organophosphorus pesticide production wastewater as set forth in any one of claims 1 to 8, wherein: the catalyst is applied to the production wastewater of chlorpyrifos in an organophosphorus pesticide chemical plant.
Priority Applications (1)
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