CN113526771A - Treatment method of wastewater in allylamine production process and application of wastewater in allylamine production process - Google Patents
Treatment method of wastewater in allylamine production process and application of wastewater in allylamine production process Download PDFInfo
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- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000002351 wastewater Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 29
- 230000007062 hydrolysis Effects 0.000 claims abstract description 28
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 27
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 23
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 23
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Inorganic materials [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000000413 hydrolysate Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 6
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 31
- 229910001431 copper ion Inorganic materials 0.000 abstract description 30
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000003672 processing method Methods 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 description 34
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 239000011780 sodium chloride Substances 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 13
- 230000006837 decompression Effects 0.000 description 12
- 230000003301 hydrolyzing effect Effects 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 238000007605 air drying Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000005189 flocculation Methods 0.000 description 7
- 230000016615 flocculation Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 6
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical class [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- -1 iodine ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The application provides a method for treating wastewater in an allylamine production process and application thereof in the allylamine production process; the processing method comprises the following steps: carrying out first hydrolysis on the wastewater, and then carrying out first solid-liquid separation; and (3) carrying out oxidation treatment on the liquid obtained by the first solid-liquid separation by using an oxidant, and then carrying out second solid-liquid separation. This application is through adopting the simple technology of hydrolysis and oxidation treatment, can effectively get rid of high COD, high ammonia nitrogen and complex copper ion in the waste water in the allylamine production technology simultaneously for waste water after handling reaches the primary standard in GB18918-2002, and surplus COD volume is less than 100ppm, and surplus ammonia nitrogen volume is less than 10ppm, and surplus copper volume can reach and not check out.
Description
Technical Field
The application relates to the field of wastewater treatment, in particular to a method for treating wastewater in an allylamine production process and application of the wastewater in the allylamine production process.
Background
The MAA (allylamine) production process generates a large amount of wastewater (containing sodium ions) with high COD, high ammonia nitrogen and complex copper ions in the production process. In the prior art, the wastewater is oxidized by adopting oxidants such as hydrogen peroxide, ozone, nitrite and peroxide, but only ammonia nitrogen (inorganic ammonia nitrogen compounds, organic ammonia nitrogen compounds and the like) in the wastewater can be treated, and no obvious treatment effect is generated on complex copper ions; the other method is to adopt heavy metal chelating agent, flocculating agent, adsorbent and sodium sulfide precipitation (in this way, H is generated)2S gas, high risk), ion exchange and the like, on one hand, most heavy metal chelating agents, flocculating agents and adsorbents are expensive, and special large-scale equipment is required for treatment, so that the treatment equipment has high input cost, and on the other hand, the method has no obvious effect on treating ammonia nitrogen and COD.
Disclosure of Invention
The application aims to provide a treatment method capable of effectively removing COD (chemical oxygen demand), ammonia nitrogen and complex copper ions in wastewater in an allylamine production process and application of the treatment method in the allylamine production process.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a method for treating wastewater in an allylamine production process, comprising:
carrying out first hydrolysis on the wastewater, and then carrying out first solid-liquid separation;
and (3) carrying out oxidation treatment on the liquid obtained by the first solid-liquid separation by using an oxidant, and then carrying out second solid-liquid separation.
In some embodiments, the temperature of the first hydrolysis is 100-.
In some embodiments, the first solid-liquid separation and the second solid-liquid separation are both by filtration;
preferably, the filtration is performed by using filter paper and a filter membrane; more preferably, the pore size of the PP filter membrane is 15-20 mu m.
In some embodiments, the oxidizing agent comprises at least one of sodium hypochlorite and potassium hypochlorite;
preferably, the oxidant is a sodium hypochlorite aqueous solution with the mass fraction of 6-14%.
In some embodiments, the temperature of the oxidation treatment is 65 to 75 ℃.
In some embodiments, the processing method further comprises: carrying out second hydrolysis on the liquid obtained by the second solid-liquid separation;
preferably, the temperature of the second hydrolysis is 98-102 ℃;
preferably, the liquid obtained by the second solid-liquid separation is subjected to second hydrolysis until the hydrolysate is detected to be free from color change by adopting starch-potassium iodide test paper.
In some embodiments, the second hydrolysis further comprises, after the first hydrolysis: adjusting the pH value of the hydrolysate by using an alkaline substance, and then concentrating;
preferably, the concentration is performed by vacuum concentration.
In some embodiments, the concentration treatment further comprises cooling crystallization;
preferably, the method further comprises a third solid-liquid separation after the temperature reduction and crystallization;
preferably, the method further comprises drying the solid obtained by the third solid-liquid separation after the third solid-liquid separation.
In some embodiments, the pH of the hydrolysate is adjusted to 6.0-7.0 using an alkaline substance;
the alkaline substance comprises at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water;
preferably, the alkaline substance is sodium hydroxide.
The application also provides an application of the method for treating the wastewater in the allylamine production process.
The beneficial effect of this application:
(1) this application is through adopting the simple technology of hydrolysis and oxidation treatment, can effectively get rid of high COD, high ammonia nitrogen and complex copper ion in the waste water in the allylamine production technology simultaneously for waste water after handling reaches the primary standard in GB18918-2002, and surplus COD volume is less than 100ppm, and surplus ammonia nitrogen volume is less than 10ppm, and surplus copper volume can reach and not check out.
(2) Furthermore, after the oxidant is selected to be at least one of sodium hypochlorite and potassium hypochlorite for oxidation treatment, excessive oxidant can be decomposed through hydrolysis, and then alkaline substances are further adopted to adjust the pH value of hydrolysate and then concentration treatment is carried out, so that the treated condensed water reaches the direct formula standard, or the condensed water can be directly used in the allyl amine production process, and the purposes of energy conservation and emission reduction are achieved; and simultaneously recovering industrial sodium chloride and/or potassium chloride which meet the high-grade products.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a process flow diagram of a method of treating wastewater in accordance with an embodiment of the present application.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Referring to fig. 1, the present application provides a method for treating wastewater from allylamine production process, comprising:
s100, carrying out first hydrolysis on the wastewater, and then carrying out first solid-liquid separation.
The temperature of the first hydrolysis is 100-105 ℃; the complex copper ions are unstable at high temperature and are easy to decompose; hydrolysis temperature is controlled to be between 100 and 105 ℃, a complex copper ion structure can be better destroyed, precipitates (containing copper oxide, copper aeruginosa and copper hydroxide) are further fully formed under the condition that oxygen, carbon dioxide and water exist, and inorganic ammonia nitrogen enters a tail gas absorption treatment system in the form of ammonia gas to be treated and then is discharged; the specific reaction equation of the hydrolysis is as follows:
it should be noted that when the first hydrolysis temperature is lower than 100 ℃, only a small amount of copper oxide precipitate is generated, and the copper oxide precipitate cannot be hydrolyzed sufficiently, and the hydrolyzed solution is blue; whereas temperatures above 105 c are difficult to achieve.
The first solid-liquid separation can adopt a filtration mode; preferably, filter paper and a PP filter membrane are adopted for filtration; the pore size of the pp filters is 15-20 μm. It should be noted that the precipitate could not be filtered out completely with only filter paper or with a common filter membrane.
S200, oxidizing the liquid obtained by the first solid-liquid separation by using an oxidizing agent, and then performing second solid-liquid separation.
In some embodiments, the temperature of the oxidation treatment is 65-75 ℃, which can effectively oxidize the complex copper ions and the like which are not completely decomposed to generate nitrogen, carbon dioxide, precipitates and the like, and oxidize ammonia nitrogen to generate nitrogen, carbon dioxide and the like, and the generated gases are sent to a tail gas absorption treatment system to be treated and then discharged.
The oxidant includes at least one of sodium hypochlorite and potassium hypochlorite. The use of an oxidizing agent containing potassium hypochlorite water produces potassium chloride, which is finally recovered to obtain a mixture of sodium chloride and potassium chloride, which needs to be separated again, thus increasing the complexity and cost of the treatment; preferably, the oxidant is sodium hypochlorite aqueous solution with the mass fraction of 6-14%; the sodium hypochlorite aqueous solution belongs to a strong oxidant, and excessive hypochlorite can be decomposed by heating after the oxidation reaction is finished, so that the quality of the product cannot be influenced; and sodium chloride with high purity can be continuously recovered.
Specifically, the chemical equation of the oxidation reaction of this step is as follows:
performing solid-liquid separation on the oxidation treatment liquid obtained by the oxidation treatment, wherein the solid-liquid separation preferably adopts a filter paper + PP filter membrane (15-20 mu m) filtration mode, and if the obtained filtrate is colorless transparent filtrate, the complex copper ions are fully oxidized; if the obtained filtrate is light cyan, which indicates that a small amount of complex copper ions exist, a small amount of oxidant needs to be added continuously to continue oxidizing flocculation, and then filtering is carried out until colorless transparent filtrate is obtained.
In some embodiments, the treatment method further comprises S300, subjecting the liquid obtained by the second solid-liquid separation to a second hydrolysis; preferably, the temperature of the second hydrolysis is 98-102 ℃, so that the excessive sodium hypochlorite and/or potassium hypochlorite water solution is fully decomposed; when the temperature of the second hydrolysis is lower than 98 ℃, the hydrolysis speed becomes slow, which is not beneficial to the practical production operation; temperatures above 102 ℃ are difficult to achieve; the specific reaction equation of this step is as follows:
the second hydrolysis reaction is carried out until the hydrolysate is detected to be not discolored by adopting starch-potassium iodide test paper, which indicates that excessive hypochlorite is completely decomposed after the oxidation reaction; this is because iodine turns blue when encountering starch, and if hypochlorite exists, it will undergo an oxidation reaction with iodine ions to produce iodine, which can be detected by a color change of the starch-potassium iodide test paper.
In some embodiments, the treatment method further comprises S400, adjusting the pH of the hydrolyzed solution after the second hydrolysis with an alkaline substance, and then performing a concentration treatment.
In some embodiments, the pH of the hydrolysate is adjusted to 6.0-7.0 using an alkaline substance.
The alkaline substance comprises at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water; preferably, the alkaline substance is sodium hydroxide; the cost of the sodium hydroxide is lower than that of other alkaline substances, the wastewater in the production process of the allylamine contains sodium ions, and the sodium hydroxide is preferably adopted, so that the subsequent separation difficulty caused by introducing other salts and the like by using other alkaline substances of potassium hydroxide and lithium hydroxide is avoided, the phenomenon that carbon dioxide is generated by adjusting the pH value by using sodium carbonate and sodium bicarbonate so as to cause flushing loss is avoided, and the subsequent separation difficulty and a small amount of ammonia gas caused by ammonium chloride, namely ammonium salt, generated by adjusting the pH value by using ammonia water are avoided.
Preferably, the concentration adopts a reduced pressure concentration mode; specifically, the temperature is controlled to be 55-65 ℃, the vacuum degree is less than or equal to-0.070 MPa, at least a solvent residue is concentrated under reduced pressure, and water vapor generated in the process of concentration under reduced pressure is cooled to form condensed water.
Cooling and crystallizing after the concentration treatment, preferably cooling to 0-5 ℃ for crystallizing for 1 h; and (3) cooling and crystallizing, then carrying out third solid-liquid separation (preferably in a filtering mode), finally drying the solid obtained by the third solid-liquid separation, preferably carrying out forced air drying in a forced air drying box at 60-70 ℃, and recovering to obtain sodium chloride and/or potassium chloride which meet the high-grade standard of industrial sodium chloride.
The application also provides an application of the method for treating the wastewater in the allylamine production process.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Carrying out sample detection before treatment on wastewater containing complex copper ions and the like generated in the allyl amine production process; adding 600g of waste water containing complex copper ions and the like generated in the production process of allylamine into a 1L reaction bottle; starting an oil bath, heating to the temperature of 103 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and verdigris are generated); the hydrolyzed mixture was cooled to room temperature and then filtered through a filter paper + pp filter (pore size 15 μm) to remove solids.
(2) Heating the filtrate filtered in the step (1) to 70 ℃ in an oil bath, and slowly dropwise adding a sodium hypochlorite solution with the mass fraction of 10% to perform oxidation reaction until a large amount of precipitates and flocculates; then the mixture after the oxidation reaction is cooled to room temperature and filtered by a filter paper + pp filter membrane (the aperture is 15 mu m) to remove solid precipitate flocculates, so as to obtain colorless transparent filtrate (if the filtrate is light cyan, and trace complex copper ions exist, a small amount of sodium hypochlorite solution needs to be added continuously to continue flocculation, and then the filtration is carried out until colorless transparent filtrate is obtained).
(3) Heating the colorless transparent filtrate obtained in the step (2) to 100 ℃ in an oil bath, stirring and hydrolyzing until no color change is detected by using starch-potassium iodide test paper.
(4) Adjusting the pH to 6.5 by using a sodium hydroxide solution; then carrying out reduced pressure concentration at the temperature of 60 ℃ and the vacuum degree of-0.070 MPa until a small amount of solvent is remained; and (3) sampling and detecting condensed water formed by cooling water vapor generated in the decompression concentration process.
(5) Cooling the product after decompression concentration to 5 ℃, stirring and crystallizing for 1 h; and then filtering the crystallized material, collecting the solid, drying the solid in a 65 ℃ forced air drying box, and recovering the dried solid, namely sodium chloride.
Example 2
(1) Carrying out sample detection before treatment on wastewater containing complex copper ions and the like generated in the allyl amine production process; adding 600g of waste water containing complex copper ions and the like generated in the production process of allylamine into a 1L reaction bottle; starting an oil bath for heating, controlling the internal temperature to be 100 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and verdigris are generated); the hydrolyzed mixture was cooled to room temperature and then filtered through a filter paper + pp filter (pore size 20 μm) to remove the solids.
(2) Heating the filtrate filtered in the step (1) to 65 ℃ in an oil bath, and slowly dropwise adding a sodium hypochlorite solution with the mass fraction of 6% for oxidation reaction until a large amount of precipitates and flocculates; then the mixture after the oxidation reaction is cooled to room temperature and filtered by a filter paper + pp filter membrane (with the aperture of 20 mu m) to remove solid precipitate flocculates, so as to obtain colorless transparent filtrate (if the filtrate is light cyan, and trace complex copper ions exist, a small amount of sodium hypochlorite solution needs to be added continuously to continue flocculation, and then the filtration is carried out until colorless transparent filtrate is obtained).
(3) Heating the colorless transparent filtrate obtained in the step (2) to 98 ℃ in an oil bath, stirring and hydrolyzing until no color change is detected by using starch-potassium iodide test paper.
(4) Adjusting the pH to 6 by using a sodium hydroxide solution; then carrying out reduced pressure concentration at the temperature of 60 ℃ and the vacuum degree of-0.050 MPa until a small amount of solvent remains; and (3) sampling and detecting condensed water formed by cooling water vapor generated in the decompression concentration process.
(5) Cooling the product after decompression concentration to 0 ℃, stirring and crystallizing for 0.5 h; then filtering the crystallized material, collecting the solid, placing the solid in a 60 ℃ forced air drying oven for drying, and recovering the dried solid, namely sodium chloride.
Example 3
(1) Carrying out sample detection before treatment on wastewater containing complex copper ions and the like generated in the allyl amine production process; adding 600g of waste water containing complex copper ions and the like generated in the production process of allylamine into a 1L reaction bottle; starting an oil bath for heating, controlling the internal temperature to be 105 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and verdigris are generated); the hydrolyzed mixture was cooled to room temperature and then filtered through a filter paper + pp filter (pore size 20 μm) to remove the solids.
(2) Heating the filtrate filtered in the step (1) to 75 ℃ in an oil bath, and slowly dropwise adding a sodium hypochlorite solution with the mass fraction of 14% to perform oxidation reaction until a large amount of precipitates and flocculates; then the mixture after the oxidation reaction is cooled to room temperature and filtered by a filter paper + pp filter membrane (with the aperture of 20 mu m) to remove solid precipitate flocculates, so as to obtain colorless transparent filtrate (if the filtrate is light cyan, and trace complex copper ions exist, a small amount of sodium hypochlorite solution needs to be added continuously to continue flocculation, and then the filtration is carried out until colorless transparent filtrate is obtained).
(3) Heating the colorless transparent filtrate obtained in the step (2) to 102 ℃ in an oil bath, stirring and hydrolyzing until no color change is detected by using starch-potassium iodide test paper.
(4) Adjusting the pH to 7 by using a sodium hydroxide solution; then, carrying out reduced pressure concentration at the temperature of 60 ℃ and the vacuum degree of-0.060 MPa until a small amount of solvent is remained; and (3) sampling and detecting condensed water formed by cooling water vapor generated in the decompression concentration process.
(5) Cooling the product after decompression concentration to 3 ℃, stirring and crystallizing for 1 h; then filtering the crystallized material, collecting the solid, placing the solid in a forced air drying oven at 70 ℃ for drying, and recovering the dried solid, namely sodium chloride.
Example 4
(1) Carrying out sample detection before treatment on wastewater containing complex copper ions and the like generated in the allyl amine production process; adding 10kg of waste water containing complex copper ions and the like generated in the allyl amine production process into a 20L reaction kettle; starting the high-low temperature all-in-one machine, heating to the temperature of 103 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and verdigris are generated); and (3) refrigerating the hydrolyzed mixture to room temperature through a high-low temperature all-in-one machine, and filtering by using filter paper and a pp filter membrane (with the aperture of 15 mu m) to remove solids.
(2) Heating the filtrate filtered in the step (1) to 70 ℃ by a high-low temperature all-in-one machine, and slowly dropwise adding a sodium hypochlorite solution with the mass fraction of 10% for oxidation reaction until a large amount of precipitates and flocculates; and then cooling the mixture after the oxidation reaction to room temperature through a high-low temperature all-in-one machine, filtering by using filter paper + pp filter membranes (with the aperture of 15 mu m), removing solid precipitate flocculates, and obtaining colorless transparent filtrate (if the filtrate is light cyan, indicating that trace complex copper ions exist, continuously adding a small amount of sodium hypochlorite solution for continuous flocculation, and filtering until colorless transparent filtrate is obtained).
(3) And (3) heating the colorless transparent filtrate obtained in the step (2) to 100 ℃ by a high-low temperature all-in-one machine, stirring and hydrolyzing until no color change is detected by using starch-potassium iodide test paper.
(4) Adjusting the pH to 6.5 by using a sodium hydroxide solution; then carrying out reduced pressure concentration at the temperature of 60 ℃ and the vacuum degree of-0.080 MPa until a small amount of solvent remains; and (3) sampling and detecting condensed water formed by cooling water vapor generated in the decompression concentration process.
(5) Cooling the product after decompression concentration to 5 ℃, stirring and crystallizing for 1 h; and then filtering the crystallized material, collecting the solid, drying the solid in a 65 ℃ forced air drying box, and recovering the dried solid, namely sodium chloride.
Example 5
(1) Carrying out sample detection before treatment on wastewater containing complex copper ions and the like generated in the allyl amine production process; adding 200g of wastewater containing complex copper ions and the like generated in the allylamine production process into a 500mL reaction kettle; starting the high-low temperature all-in-one machine, heating to the temperature of 103 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and verdigris are generated); and (3) refrigerating the hydrolyzed mixture to room temperature through a high-low temperature all-in-one machine, and filtering by using filter paper and a pp filter membrane (with the aperture of 15 mu m) to remove solids.
(2) Heating the filtered filtrate obtained in the step (1) to 80 ℃, and slowly dropwise adding a sodium hypochlorite solution with the mass fraction of 10% for oxidation reaction until a large amount of precipitates and flocculates; and then cooling the mixture after the oxidation reaction to room temperature through a high-low temperature all-in-one machine, filtering by using filter paper + pp filter membranes (with the aperture of 15 mu m), removing solid precipitate flocculates, and obtaining colorless transparent filtrate (if the filtrate is light cyan, indicating that trace complex copper ions exist, continuously adding a small amount of sodium hypochlorite solution for continuous flocculation, and filtering until colorless transparent filtrate is obtained).
(3) And (3) heating the colorless transparent filtrate obtained in the step (2) to 100 ℃ by a high-low temperature all-in-one machine, stirring and hydrolyzing until no color change is detected by using starch-potassium iodide test paper.
(4) Adjusting the pH to 6.0 by using a sodium hydroxide solution; then carrying out reduced pressure concentration at the temperature of 60 ℃ and the vacuum degree of-0.080 MPa until a small amount of solvent remains; and (3) sampling and detecting condensed water formed by cooling water vapor generated in the decompression concentration process.
(5) Cooling the product after decompression concentration to 5 ℃, stirring and crystallizing for 1 h; and then filtering the crystallized material, collecting the solid, drying the solid in a 65 ℃ forced air drying box, and recovering the dried solid, namely sodium chloride.
Example 6
(1) Carrying out sample detection before treatment on wastewater containing complex copper ions and the like generated in the allyl amine production process; adding 200g of wastewater containing complex copper ions and the like generated in the allylamine production process into a 500mL reaction kettle; starting the high-low temperature all-in-one machine, heating to the temperature of 103 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and verdigris are generated); and (3) refrigerating the hydrolyzed mixture to room temperature through a high-low temperature all-in-one machine, and filtering by using filter paper and a pp filter membrane (with the aperture of 15 mu m) to remove solids.
(2) Heating the filtered filtrate obtained in the step (1) to 60 ℃ by a high-low temperature all-in-one machine, and slowly dropwise adding a sodium hypochlorite solution with the mass fraction of 10% to perform oxidation reaction until a large amount of precipitates and flocculates; and then cooling the mixture after the oxidation reaction to room temperature through a high-low temperature all-in-one machine, filtering by using filter paper + pp filter membranes (with the aperture of 15 mu m), removing solid precipitate flocculates, and obtaining colorless transparent filtrate (if the filtrate is light cyan, indicating that trace complex copper ions exist, continuously adding a small amount of sodium hypochlorite solution for continuous flocculation, and filtering until colorless transparent filtrate is obtained).
(3) And (3) heating the colorless transparent filtrate obtained in the step (2) to 101 ℃ by a high-low temperature all-in-one machine, stirring and hydrolyzing until no color change is detected by using starch-potassium iodide test paper.
(4) Adjusting the pH to 7.0 by using a sodium hydroxide solution; then carrying out reduced pressure concentration at the temperature of 60 ℃ and the vacuum degree of-0.080 MPa until a small amount of solvent remains; and (3) sampling and detecting condensed water formed by cooling water vapor generated in the decompression concentration process.
(5) Cooling the product after decompression concentration to 5 ℃, stirring and crystallizing for 1 h; and then filtering the crystallized material, collecting the solid, drying the solid in a 65 ℃ forced air drying box, and recovering the dried solid, namely sodium chloride.
The wastewater containing the complex copper ions and the like generated in the allylamine production process used in examples 1 to 5 was a wastewater of a different lot, and the same lot as that used in examples 6 and 5. The results of comparing the measured data before and after the wastewater treatment in examples 1 to 6 are shown in Table 1 below; the purity analysis results of the finally recovered sodium chloride are shown in table 2 below.
TABLE 1
Table 2:
remarking: the detection method of the content of the copper ions is carried out according to a conventional titration method or an ion chromatography method.
And (4) conclusion: by adopting the wastewater treatment process, high COD, high ammonia nitrogen and complex copper ions in the wastewater in the allylamine production process can be effectively removed at the same time, so that the treated wastewater reaches the primary standard in GB18918-2002, the residual COD content is lower than 100ppm, the residual ammonia nitrogen content is lower than 10ppm, and the residual copper content can reach the level of undetected;
in example 5, the oxidation reaction temperature in the step (2) is increased to 80 ℃, and the amount of the sodium hypochlorite aqueous solution added is increased (sodium hypochlorite decomposition is accelerated) when the oxidation reaction temperature is too high, so that the content of the recovered sodium chloride is lower; in example 6, the oxidation reaction temperature in step (2) is reduced to 60 ℃, the hydrolysis time is prolonged (the reaction activity is reduced) when the oxidation reaction temperature is too low, the COD and ammonia nitrogen contents of the finally obtained condensed water are slightly higher, and the content of the obtained recovered sodium chloride is slightly lower.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A method for treating wastewater in an allylamine production process is characterized by comprising the following steps:
carrying out first hydrolysis on the wastewater, and then carrying out first solid-liquid separation;
and (3) carrying out oxidation treatment on the liquid obtained by the first solid-liquid separation by using an oxidant, and then carrying out second solid-liquid separation.
2. The method as claimed in claim 1, wherein the temperature of the first hydrolysis is 100-105 ℃.
3. The method of claim 1, wherein the first solid-liquid separation and the second solid-liquid separation are filtration;
preferably, the filtration is performed by using filter paper and a PP filter membrane; more preferably, the pore size of the filter membrane is 15-20 μm.
4. The method of claim 1 wherein said oxidizing agent comprises at least one of sodium hypochlorite and potassium hypochlorite;
preferably, the oxidant is a sodium hypochlorite aqueous solution with the mass fraction of 6-14%.
5. The method of claim 1 wherein the temperature of said oxidizing treatment is 65-75 ℃.
6. The method of treating wastewater from the allylamine production process of claim 4, further comprising: carrying out second hydrolysis on the liquid obtained by the second solid-liquid separation;
preferably, the temperature of the second hydrolysis is 98-102 ℃;
preferably, the liquid obtained by the second solid-liquid separation is subjected to second hydrolysis until the hydrolysate is detected to be free from color change by adopting starch-potassium iodide test paper.
7. The method of claim 6, further comprising, after said second hydrolysis: adjusting the pH value of the hydrolysate by using an alkaline substance, and then concentrating;
preferably, the concentration is performed by vacuum concentration.
8. The method of claim 7, further comprising cooling and crystallizing the wastewater from the allylamine production process after the concentration;
preferably, the method further comprises a third solid-liquid separation after the temperature reduction and crystallization;
preferably, the method further comprises drying the solid obtained by the third solid-liquid separation after the third solid-liquid separation.
9. The method for treating wastewater from allylamine production according to claim 7, wherein a basic substance is used to adjust the pH of the hydrolyzed solution to 6.0 to 7.0;
the alkaline substance comprises at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water;
preferably, the alkaline substance is sodium hydroxide.
10. An application of the waste water treating method in the production of allyl amine.
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