CN108046291B - Recycling and reusing of byproduct ammonium chloride in kresoxim-methyl production process - Google Patents
Recycling and reusing of byproduct ammonium chloride in kresoxim-methyl production process Download PDFInfo
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 114
- 239000006227 byproduct Substances 0.000 title claims abstract description 35
- 239000005800 Kresoxim-methyl Substances 0.000 title claims abstract description 28
- ZOTBXTZVPHCKPN-HTXNQAPBSA-N kresoxim-methyl Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1COC1=CC=CC=C1C ZOTBXTZVPHCKPN-HTXNQAPBSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 45
- 238000000855 fermentation Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002361 compost Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001953 recrystallisation Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 16
- 230000004151 fermentation Effects 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 241000894006 Bacteria Species 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- 239000012452 mother liquor Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000002068 microbial inoculum Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000009264 composting Methods 0.000 abstract description 2
- 238000012271 agricultural production Methods 0.000 abstract 1
- 230000029219 regulation of pH Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000011282 treatment Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 229920000742 Cotton Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 241000219146 Gossypium Species 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- -1 amide aldehyde Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000009776 industrial production Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 150000001263 acyl chlorides Chemical class 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 241000482268 Zea mays subsp. mays Species 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 240000002024 Gossypium herbaceum Species 0.000 description 1
- 235000004341 Gossypium herbaceum Nutrition 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 235000013348 organic food Nutrition 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses a technology for recycling and reusing a byproduct ammonium chloride in the kresoxim-methyl production process, which comprises the following steps: feeding, adsorption filtering, pH regulation, adsorption filtering, primary recrystallization, secondary recrystallization, drying, composting and fermenting to obtain the finished product. The technology has the advantages that the operation process of the ammonium chloride recovery process is simple, the equipment is simple, the recycling of water in the recovery process can be realized, the recovered ammonium chloride can be subjected to compost fermentation to prepare a finished product, the finished product is used for agricultural production, and the purpose of resource recovery and reutilization is achieved.
Description
The technical field is as follows:
the invention relates to the technical field of resource recycling, in particular to a recycling and reusing technology of a byproduct ammonium chloride in a kresoxim-methyl production process.
Background art:
ammonium chloride wastewater is very common in industrial production and usually contains some organic impurities which cannot be directly utilized. In the industrial production process of the agricultural bactericide kresoxim-methyl, a large amount of by-product ammonium chloride solid is generated, wherein the by-product ammonium chloride solid contains organic impurities such as toluene, methanol, acyl chloride, amide aldehyde acid ester and the like. If the ammonium chloride containing organic impurities is directly used as hazardous waste for treatment, the environment is polluted, the cost is increased, and resources are wasted.
At present, physical, chemical and biological means are generally adopted to treat high-concentration ammonium chloride wastewater, and a membrane treatment technology and an electrodialysis method are mainly adopted, but the defects of the method are that the process is complex and the cost is high. Patent CN 103408038A provides a treatment method for recovering ammonium chloride, which is based on the principle of the homogeneous ion effect of hough's chloride, and is to add a certain amount of sodium chloride into ammonium chloride wastewater, and to "force" out ammonium chloride by repeatedly using sodium chloride, but the method has the disadvantages that sodium ion impurities in sodium chloride are introduced, which affects the purity of recovered ammonium chloride, and is not beneficial to the removal of organic impurities. Aiming at the defects, the method for recovering the ammonium chloride provided by the invention has the advantages of simple process and low price, no other impurities are introduced in the recovery process, and the recovered ammonium chloride has high purity.
With the proposal of sustainable agriculture, organic compost applied in organic agriculture meets the requirements of green food in China and organic food in China internationally. The organic compost is prepared by preparing organic wastes into finished compost through four stages of a medium temperature stage, a high temperature stage, a cooling stage and a decomposing stage under the action of aerobic microorganisms. The process needs to provide certain nutrition and proper carbon-nitrogen ratio. According to the GB/T2946-2008 regulation, the nitrogen content of first-class agricultural ammonium chloride is 25.0%, and the purity of the ammonium chloride is calculated to be more than 99.0%. If a technology is found to recover the by-product ammonium chloride to ensure that the purity of the by-product ammonium chloride is more than 99.0 percent, the by-product ammonium chloride can be used as a nitrogen source for agricultural compost fermentation. And the recovered qualified ammonium chloride is used for agricultural compost fermentation, so that the adverse effects on crops and soil caused by the overproof chloride ions caused by directly applying an ammonium chloride fertilizer can be effectively avoided, and the requirement on a nitrogen source in the compost fermentation process can be met. Has good economic benefit and environmental benefit.
The invention content is as follows:
the invention aims to provide a technology for recycling and reusing a byproduct ammonium chloride in the kresoxim-methyl production process.
The invention is implemented by the following technical scheme: aiming at the defects of the recovery process of the byproduct ammonium chloride generated in the current kresoxim-methyl production process, the technology for recovering and recycling the byproduct ammonium chloride in the kresoxim-methyl production process is provided, the byproduct ammonium chloride is thoroughly treated through the steps of feeding → adsorption filtration → pH adjustment → adsorption filtration → primary recrystallization → secondary recrystallization → drying, and the recovered ammonium chloride is used for agricultural compost fermentation, and the specific steps are as follows:
a method for recovering a byproduct ammonium chloride in the kresoxim-methyl production process comprises the following specific steps:
(1) dissolving a byproduct ammonium chloride containing organic impurities generated in the kresoxim-methyl production process into water at 10-40 ℃, and uniformly stirring to obtain an ammonium chloride solution containing the organic impurities;
(2) adding activated carbon powder into the ammonium chloride solution containing organic impurities obtained in the step (1), stirring, adsorbing and filtering;
(3) adjusting the pH value of the filtrate obtained in the step (2) to 7.5-9.0;
(4) adding activated carbon powder into the solution obtained in the step (3), stirring, adsorbing and filtering;
(5) distilling the filtrate obtained in the step (4) in a vacuum state until a certain volume is distilled out, cooling, crystallizing, and filtering to leave filter residues;
(6) in a vacuum state, repeatedly carrying out secondary recrystallization on the mother liquor filtered out by the primary recrystallization in the step (5), and filtering to leave filter residues;
(7) and (4) drying the filter residue obtained by twice filtering in the steps (5) and (6), namely the ammonium chloride crystal, and storing for later use.
The by-product ammonium chloride containing organic impurities in the step (1) accounts for 25-40% of the mass of the water.
And (3) adding the activated carbon powder in the step (2) according to 0.5-1.5 per mill (W/W) of the total mass, and stirring and adsorbing for 1-2 hours.
The reagent used for adjusting the pH value in the step (3) is ammonia water.
And (3) adding the activated carbon powder in the step (4) according to 0.5-1.0 per mill, and stirring and adsorbing for 1-2 hours.
And (3) evaporating the clear filtrate obtained in the step (5) at 70-80 ℃ in vacuum, cooling to 35-45 ℃ when the clear filtrate is evaporated and concentrated to 10% -20% of the original volume, separating out ammonium chloride crystals, and filtering.
And (4) evaporating the filtered mother liquor obtained in the step (6) at 70-80 ℃ in vacuum, cooling to 35-45 ℃ when the filtered mother liquor is evaporated and concentrated to 20% -30% of the original volume, separating out ammonium chloride crystals, and filtering.
And (4) drying the recrystallized ammonium chloride obtained by filtering in the step (5) and the step (6) at the temperature of between 30 and 50 ℃.
A method for recycling and reusing a byproduct ammonium chloride in the kresoxim-methyl production process comprises the following specific steps:
and (3) recovering the obtained ammonium chloride as a nitrogen source for composting fermentation, uniformly mixing water, a microbial inoculum activating component and decomposed bacteria obtained by high-temperature decomposition to obtain a mixed material, performing high-temperature decomposition, turning over the material for fermentation, transferring the mixed material to a post-fermentation workshop for post-fermentation after the temperature is reduced, and drying and packaging the material to obtain a finished product.
The addition amount of the ammonium chloride is 1.0-1.5% of the content of chloride ions, the addition amount of the thoroughly decomposed bacteria is 0.05-0.2% (W/W) of the dry weight of the mixed material, the addition amount of the activating component is 2-20 times of the mass of the thoroughly decomposed bacteria, when the mixed material is subjected to high-temperature decomposition, pile turning is started when the temperature is higher than 50 ℃, pile turning is normally performed once a day, pile turning is required when the temperature is higher than 60 ℃, pile turning is maintained for 10-15 days, the moisture content of the material is controlled to be below 15% when the mixed material is dried, and the finished product is prepared by packaging.
When the mixture was dissolved, it showed a dark brown-yellow color due to the high content of the amide aldehydic acid ester, in which the acid chloride was partially hydrolyzed in water and an offensive odor was emitted. Activated carbon is a non-polar molecule that readily adsorbs non-polar or very low polar adsorbates, and the pH of the solution is between 3 and 5 when the mixture is dissolved, indicating that acid chlorides are hydrolyzed, while amides are generally more difficult to hydrolyze. The unshared electron pair on the amino nitrogen in the amide molecule forms a conjugated system with pi electrons of the carbonyl group, so that the electron cloud density on the nitrogen is reduced, the polarity of an N-H bond is increased, and weak acidity is expressed. Therefore, after primary adsorption, the amide aldehyde acid ester with high polarity still remains to make the solution appear yellow green, and when the pH is adjusted to be alkaline after the ammonia water is added, the polarity of the N-H bond is reduced, so that the purer ammonium chloride is obtained.
Compared with the prior art, the invention has the following advantages:
1. the technology for recovering and recycling the byproduct ammonium chloride in the kresoxim-methyl production process has the advantages of simple operation process, simple equipment and lower cost.
2. The invention avoids the introduction of other impurities, the purity of the ammonium chloride obtained by detection and recovery can reach more than 99.0 percent, the removal rate of organic matters is 100 percent, and the ammonium chloride meets the standard of agricultural ammonium chloride.
3. The invention adopts the active carbon to adsorb the organic impurities twice, can effectively improve the utilization rate of the active carbon and reduce the cost.
4. The invention adopts twice recrystallization technology, can improve the precipitation efficiency of ammonium chloride crystals and reduce the amount of residual distillation mother liquor.
5. The distilled effluent generated in the crystallization process can be reused for feeding, and can be recycled, so that the industrial water is saved.
6. The ammonium chloride obtained by the invention is used for compost fermentation, so that the adverse effect on crops and soil caused by the overproof chloride ions when the ammonium chloride fertilizer is directly applied can be effectively avoided, and the requirement on a nitrogen source in the compost fermentation can be met.
Drawings
FIG. 1 is a liquid phase detection diagram of organic impurities contained in ammonium chloride before recovery according to the present invention;
FIG. 2 is a liquid phase detection diagram of organic impurities contained in the recovered ammonium chloride of the present invention;
as can be seen from the figure, the impurity peak is contained before the recovery, and the impurity peak is not existed after the recovery, which shows that the impurity in the ammonium chloride is removed by the process, and the high-purity ammonium chloride is obtained.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A technology for recycling and reusing a byproduct ammonium chloride in the kresoxim-methyl production process comprises the following specific steps:
(1) feeding material
Adding ammonium chloride which is a byproduct generated in the kresoxim-methyl production process and contains organic impurities according to 25-40% of the mass of water, and uniformly stirring and dissolving to obtain an ammonium chloride solution containing the organic impurities;
(2) adsorption filtration
Adding 0.5-1.5 ‰ (W/W) ammonium chloride solution containing organic impurities into activated carbon powder, stirring for adsorbing for 1-2 hr, and filtering;
(3) adjusting pH
The reagent used for adjusting the pH is one or more of acid-base adjusting agents such as ammonia water and the like. Adjusting the pH value to 7.5-9.0 by taking the condition that other impurity ions are not introduced as a standard;
(4) adsorption filtration
Adding 0.5-1.0 ‰ (W/W) of ammonium chloride solution with adjusted pH into activated carbon powder, stirring for adsorbing for 1-2 hr, and filtering;
(5) primary recrystallization
Evaporating the obtained clear filtrate at 70-80 deg.C under vacuum, concentrating to 10-20% of original volume, cooling to 35-45 deg.C, precipitating ammonium chloride crystal, and filtering.
(6) Secondary recrystallization
And (3) in a vacuum state, evaporating the filtered mother liquor obtained after primary recrystallization at 70-80 ℃ in vacuum, cooling to 35-45 ℃ when the filtered mother liquor is evaporated and concentrated to 20-30% of the original volume, separating out ammonium chloride crystals, and filtering.
(7) Drying
And (4) drying the recrystallized ammonium chloride obtained by filtering in the step (5) and the step (6) at the temperature of between 30 and 50 ℃.
(8) Compost fermentation
A. Using the recovered ammonium chloride as a nitrogen source for compost fermentation, wherein the addition amount of the ammonium chloride is 1.0-1.5% (W/W) of the content of chloride ions;
B. decomposing bacteria and an activating component with the mass 2-20 times of that of the decomposing bacteria, wherein the dry weight of the mixed material obtained by high-temperature decomposition is 0.05-0.2% (W/W);
C. decomposing the mixed materials at high temperature, turning the piles once a day under normal conditions when the temperature is higher than 50 ℃, turning the piles when the temperature is higher than 60 ℃, maintaining for 10-15 days, and starting after-fermentation after the temperature is reduced;
D. and (4) post-fermentation, namely transferring the mixed material after high-temperature decomposition to a post-fermentation workshop, drying to control the moisture of the material to be below 15%, and packaging the finished product.
In order to make the purpose, technical scheme and beneficial effects of the invention more clear, the invention adopts the following specific examples to explain the technical scheme of the invention in detail.
TABLE 1 solubility of ammonium chloride in water
Example 1
Recovery of ammonium chloride (recovery of ammonium chloride in kresoxim-methyl production process)
A great amount of ammonium chloride salt solid as by-product is generated in the industrial production process of kresoxim-methyl as agricultural insecticide, which contains toluene, methanol, acyl chloride, amide aldehyde acid ester and other organic impurities. The color is yellowish brown, has pungent odor, and is dissolved in water at pH 3-5;
taking 90kg (according to 30 percent of adding amount) of a byproduct ammonium chloride sample, dissolving in water and fixing the volume to 300L;
adding 300g (added according to 1.0 per mill) of activated carbon powder, stirring and adsorbing for 2h, and filtering;
adjusting the pH value to 7.5 by ammonia water;
adding 150g (added according to 0.5 per mill) of activated carbon powder, stirring and adsorbing for 2h, and filtering;
distilling at 70 deg.C for recrystallization, concentrating to 10% of original volume, and filtering;
performing secondary distillation and recrystallization at 70 ℃, and filtering when the solution is concentrated to 30 percent of the original volume;
drying the ammonium chloride crystals obtained by filtering twice at 50 ℃;
the color of the recovered ammonium chloride finished product is pure white, the purity of the ammonium chloride is detected to be 97.82% without pungent smell, and organic matters are not detected;
adding the ammonium chloride obtained in the step according to 1.0% (W/W) of chloride ions, adding 0.1% of decomposed bacteria on the dry weight of the mixed material, activating components 10 times of the mass of the decomposed bacteria and water 100 times of the mass of the decomposed bacteria, and uniformly mixing;
performing high-temperature decomposition, turning the piles when the temperature is higher than 50 ℃, turning the piles once a day and turning the piles when the temperature is higher than 60 ℃, and maintaining for 15 days; after the temperature is reduced, transferring the mixture to a post-fermentation workshop, drying the mixture to control the moisture of the materials to be below 15%, and packaging the finished product.
Example 2
Recovery of ammonium chloride (recovery of ammonium chloride in kresoxim-methyl production process)
A great amount of ammonium chloride salt solid as by-product is generated in the industrial production process of kresoxim-methyl as agricultural insecticide, which contains toluene, methanol, acyl chloride, amide aldehyde acid ester and other organic impurities. The color is yellowish brown, has pungent odor, and is dissolved in water at pH 3-5;
dissolving 105kg (according to 35% of adding amount) of by-product ammonium chloride in water to reach a constant volume of 300L;
adding 450g (added according to 1.5 per mill) of activated carbon powder, stirring and adsorbing for 1.5h, filtering,
adjusting the pH value to 8.0 by ammonia water;
adding 150g (added according to 0.5 per mill) of activated carbon powder, stirring and adsorbing for 1.5h, and filtering;
distilling at 80 deg.C for recrystallization, concentrating to 20% of original volume, and filtering;
performing secondary distillation and recrystallization at 80 ℃, and filtering when the solution is concentrated to 20 percent of the original volume;
drying the ammonium chloride crystals obtained by filtering twice at 40 ℃;
the recovered ammonium chloride finished product is pure white and has no pungent smell, the purity of the ammonium chloride is 98.65 percent through detection, and organic matters are not detected.
Adding ammonium chloride obtained in the step according to 1.2% (W/W) of chloride ions, adding 0.1% of decomposed bacteria on the dry weight of the mixed material, activating components 15 times of the mass of the decomposed bacteria and water 100 times of the mass of the decomposed bacteria, and uniformly mixing;
performing high-temperature decomposition, starting turning when the temperature is higher than 50 ℃, turning once the next day, turning at the temperature higher than 60 ℃, and maintaining for 15 days;
after the temperature is reduced, transferring the mixture to a post-fermentation workshop, drying the mixture to control the moisture of the materials to be below 15%, and packaging the finished product.
Example 3
Recovery of ammonium chloride (recovery of ammonium chloride in kresoxim-methyl production process)
A great amount of ammonium chloride salt solid as by-product is generated in the industrial production process of kresoxim-methyl as agricultural insecticide, which contains toluene, methanol, acyl chloride, amide aldehyde acid ester and other organic impurities. The color is yellowish brown, has pungent odor, and is dissolved in water at pH 3-5;
dissolving 120kg (40% of the added amount) of the by-product ammonium chloride in water to reach a constant volume of 300L;
adding 450g (added according to 1.5 per mill) of activated carbon powder, stirring and adsorbing for 2h, filtering,
adjusting the pH value to 8.5 by ammonia water;
adding 240g (added according to 0.8 per mill) of activated carbon powder, stirring and adsorbing for 1.5h, and filtering;
distilling at 80 deg.C for recrystallization, concentrating to 15% of original volume, and filtering;
performing secondary distillation and recrystallization at 80 ℃, and filtering when the solution is concentrated to 30 percent of the original volume;
drying the ammonium chloride crystals obtained by filtering twice at 40 ℃;
the recovered ammonium chloride finished product is pure white and has no pungent smell, the purity of the ammonium chloride is detected to be 98.57%, and organic matters are not detected.
Adding ammonium chloride obtained in the step according to 1.3% (W/W) of chloride ions, adding 0.15% of decomposed bacteria on the dry weight of the mixed material, an activating component 20 times the mass of the decomposed bacteria and water 100 times the mass of the decomposed bacteria, and uniformly mixing;
performing high-temperature decomposition, starting turning when the temperature is higher than 50 ℃, turning once the next day, turning at the temperature higher than 60 ℃, and maintaining for 12 days;
after the temperature is reduced, transferring the mixture to a post-fermentation workshop, drying the mixture to control the moisture of the materials to be below 15%, and packaging the finished product.
Example 4
Recovery of ammonium chloride (recovery of ammonium chloride in kresoxim-methyl production process)
A great amount of ammonium chloride salt solid as by-product is generated in the industrial production process of kresoxim-methyl as agricultural insecticide, which contains toluene, methanol, acyl chloride, amide aldehyde acid ester and other organic impurities. The color is yellowish brown, has pungent odor, and is dissolved in water at pH 3-5;
taking 90kg (according to 30 percent of adding amount) of by-product ammonium chloride, dissolving in water and fixing the volume to 300L;
adding 360g (added according to 1.2 ‰) of activated carbon powder, stirring for adsorbing for 1.5 hr, filtering,
adjusting the pH value to 9.0 by ammonia water;
adding 300g (added according to 1.0 per mill) of activated carbon powder, stirring and adsorbing for 2h, and filtering;
distilling at 80 deg.C for recrystallization, concentrating to 15% of original volume, and filtering;
performing secondary distillation and recrystallization at 80 ℃, and filtering when the solution is concentrated to 25 percent of the original volume;
drying the ammonium chloride crystals obtained by filtering twice at 45 ℃;
the recovered ammonium chloride finished product is pure white and has no pungent smell, the purity of the ammonium chloride is 98.75 percent through detection, and organic matters are not detected.
Adding ammonium chloride obtained in the step according to 1.3% (W/W) of chloride ions, adding 0.15% of decomposed bacteria on the dry weight of the mixed material, an activating component 20 times the mass of the decomposed bacteria and water 100 times the mass of the decomposed bacteria, and uniformly mixing;
performing high-temperature decomposition, starting turning when the temperature is higher than 50 ℃, turning once the next day, turning at the temperature higher than 60 ℃, and maintaining for 12 days;
after the temperature is reduced, transferring the mixture to a post-fermentation workshop, drying the mixture to control the moisture of the materials to be below 15%, and packaging the finished product.
Examples of the experiments
EXAMPLE 1 application of recovered ammonium chloride to corn field
The four organic composts obtained in example 1, example 2 and example 3 and example 4 were applied to field corn plants as treatment 1, treatment 2 and treatment 4, respectively, and the control group was organic composts without ammonium chloride. The other growth conditions are consistent, and the compost is applied to five groups according to the normal proportion until the corn is mature and harvested. Five groups of data are recorded in statistics, the following table shows the influence of different treatments on the growth shape of the corn, and the phenomena of increased ear length, reduced tip projection and increased yield per mu of the corn after the ammonium chloride is added are generally seen.
TABLE 2 Effect of Simultaneous treatment on corn growth shape
Note: the data in the table are the average values of each group; the lower case letters in the same column indicate that there was a significant difference at the 0.05 level between the two groups.
EXAMPLE 2 application of recovered ammonium chloride to field Cotton
The four organic composts obtained in example 1, example 2 and example 3 and example 4 were applied to field corn plants as treatment 1, treatment 2 and treatment 4, respectively, and the control group was organic composts without ammonium chloride. The other growth conditions are consistent, and the compost is applied to five groups according to the normal proportion until the cotton is mature and harvested. Two groups of data are recorded in statistics, and table 3 shows that the influence of different treatments on the economic properties of cotton, under the condition of consistent planting density, compost added with ammonium chloride is applied to increase the number and weight of cotton bolls of single cotton plants, the clothes content is obviously improved, the yield of seed cotton is improved, and table 4 shows that organic fertilizer added with ammonium chloride also has a certain improvement effect on the fiber quality of cotton.
TABLE 3 influence of different treatments on economic traits of cotton
Note: the data in the table are the average values of each group; the lower case letters in the same column indicate that there was a significant difference at the 0.05 level between the two groups.
TABLE 4 Effect of different treatments on Cotton fiber quality
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A method for recovering a byproduct ammonium chloride in the kresoxim-methyl production process is characterized by comprising the following specific steps:
(1) dissolving a byproduct ammonium chloride containing organic impurities generated in the kresoxim-methyl production process into water at 10-40 ℃, and uniformly stirring to obtain an ammonium chloride solution containing the organic impurities;
(2) adding activated carbon powder into the ammonium chloride solution containing organic impurities obtained in the step (1), stirring, adsorbing and filtering;
(3) adjusting the pH value of the filtrate obtained in the step (2) to 7.5-9.0;
(4) adding activated carbon powder into the solution obtained in the step (3), stirring, adsorbing and filtering;
(5) distilling the filtrate obtained in the step (4) in a vacuum state until a certain volume is distilled out, cooling, crystallizing, and filtering to leave filter residues;
(6) in a vacuum state, repeatedly carrying out secondary recrystallization on the mother liquor filtered out by the primary recrystallization in the step (5), and filtering to leave filter residues; (7) drying the filter residue obtained by twice filtering in the steps (5) and (6), namely ammonium chloride crystals, and storing for later use;
the by-product ammonium chloride containing organic impurities in the step (1) accounts for 25-40% of the mass of water;
adding the activated carbon powder in the step (2) according to 0.5-1.5 per mill (W/W) of the total mass, and stirring and adsorbing for 1-2 hours;
the reagent used for adjusting the pH value in the step (3) is ammonia water;
and (3) adding the activated carbon powder in the step (4) according to 0.5-1.0 per mill (W/W) of the total mass, and stirring and adsorbing for 1-2 hours.
2. The method for recovering the byproduct ammonium chloride in the kresoxim-methyl production process according to claim 1, wherein the clarified filtrate obtained in the step (5) is evaporated in vacuum at 70-80 ℃, and when the clarified filtrate is evaporated and concentrated to 10-20% of the original volume, the clarified filtrate is cooled to 35-45 ℃, and ammonium chloride crystals are separated out and filtered.
3. The method for recovering the byproduct ammonium chloride in the kresoxim-methyl production process according to claim 1, wherein the filtered mother liquor obtained in the step (6) is vacuum evaporated at 70-80 ℃, and when the filtered mother liquor is evaporated and concentrated to 20% -30% of the original volume, the filtered mother liquor is cooled to 35-45 ℃, ammonium chloride crystals are separated out, and then the filtered mother liquor is filtered.
4. The method for recovering the ammonium chloride as the byproduct in the kresoxim-methyl production process according to claim 1, wherein the recrystallized ammonium chloride obtained by filtering in the steps (5) and (6) is dried at 30-50 ℃.
5. A method for recycling and reusing a byproduct ammonium chloride in the kresoxim-methyl production process is characterized by comprising the following specific steps:
the ammonium chloride recovered by the recovery method according to claim 1 is used as a nitrogen source for compost fermentation, water, a microbial inoculum activating component and decomposed bacteria obtained by high-temperature decomposition are uniformly mixed to be used as a mixed material for high-temperature decomposition, the mixed material is turned to be fermented, after the temperature is reduced, the mixed material is transferred to a post-fermentation workshop for post-fermentation, and a finished product is prepared by drying and packaging;
the addition amount of the ammonium chloride is 1.0-1.5% (W/W) of the content of chloride ions, the addition amount of the thoroughly decomposed bacteria is 0.05-0.2% (W/W) of the dry weight of the mixed material, the addition amount of the activating component is 2-20 times of the mass of the thoroughly decomposed bacteria, when the mixed material is thoroughly decomposed at high temperature, the stack turning is started when the temperature is higher than 50 ℃, the stack turning is carried out once a day under normal conditions, the stack turning is required when the temperature exceeds 60 ℃, the stack turning is maintained for 10-15 days, and the moisture of the material is controlled to be below 15% during drying, and the finished product is prepared by packaging.
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| CN104591465A (en) * | 2015-01-30 | 2015-05-06 | 深圳市危险废物处理站有限公司 | Method for recycling and processing ammonia-nitrogen-containing wastewater in circuit board etching waste liquor recycling industry |
| CN104726510A (en) * | 2013-12-24 | 2015-06-24 | 中粮生物化学（安徽）股份有限公司 | Method for preparing lysine through fermenting |
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| CN104726510A (en) * | 2013-12-24 | 2015-06-24 | 中粮生物化学（安徽）股份有限公司 | Method for preparing lysine through fermenting |
| CN104591465A (en) * | 2015-01-30 | 2015-05-06 | 深圳市危险废物处理站有限公司 | Method for recycling and processing ammonia-nitrogen-containing wastewater in circuit board etching waste liquor recycling industry |
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