CN113526771B - 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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- CN113526771B CN113526771B CN202110996972.0A CN202110996972A CN113526771B CN 113526771 B CN113526771 B CN 113526771B CN 202110996972 A CN202110996972 A CN 202110996972A CN 113526771 B CN113526771 B CN 113526771B
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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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 31
- 230000007062 hydrolysis Effects 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 28
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 23
- 238000001914 filtration Methods 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
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 9
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 6
- 239000000413 hydrolysate Substances 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 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
- 230000008569 process Effects 0.000 abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 10
- 238000003672 processing method Methods 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 18
- 229910001868 water Inorganic materials 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000011780 sodium chloride Substances 0.000 description 14
- 238000005189 flocculation Methods 0.000 description 13
- 230000016615 flocculation Effects 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
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 230000008859 change Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000004065 wastewater treatment Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 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
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group 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
- 239000002738 chelating agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 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
- 239000013049 sediment Substances 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
- 108010009736 Protein Hydrolysates Proteins 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
- 230000009286 beneficial effect Effects 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
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method 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
- 238000005259 measurement 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction 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
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (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 of the wastewater 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 oxidizing the liquid obtained by the first solid-liquid separation by adopting an oxidant, and then performing second solid-liquid separation. The application can simultaneously and effectively remove high COD, high ammonia nitrogen and complex copper ions in the wastewater in the allylamine production process by adopting simple processes of hydrolysis and oxidation treatment, so that the treated wastewater reaches the first-level standard in GB18918-2002, the residual COD amount is lower than 100ppm, the residual ammonia nitrogen amount is lower than 10ppm, and the residual copper amount can reach the condition that the wastewater is not checked.
Description
Technical Field
The application relates to the field of wastewater treatment, in particular to a wastewater treatment method in an allylamine production process and application of the wastewater treatment method in the allylamine production process.
Background
The MAA (allylamine) production process can generate 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 waste water is oxidized by adopting oxidizing agents such as hydrogen peroxide, ozone, nitrite, peroxide and the like, but ammonia nitrogen (inorganic ammonia nitrogen compounds, organic ammonia nitrogen compounds and the like) in the waste water can be treated only, and no obvious treatment effect is achieved on complex copper ions; the other is to treat the wastewater by adopting a heavy metal chelating agent, a flocculating agent, an adsorbent, sodium sulfide precipitation (H 2 S gas is generated in the mode, the danger is high), 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 to be equipped for treatment, so that the investment cost of the treatment equipment is high, and on the other hand, the mode has no obvious effect on ammonia nitrogen and COD treatment.
Disclosure of Invention
The application aims to provide a treatment method capable of effectively removing COD, 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 above purpose, the application adopts the following technical scheme:
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 oxidizing the liquid obtained by the first solid-liquid separation by adopting an oxidant, and then performing second solid-liquid separation.
In some embodiments, the temperature of the first hydrolysis is 100-105 ℃.
In some embodiments, the first solid-liquid separation and the second solid-liquid separation are both filtration;
preferably, the filtration adopts filter paper and filter membrane filtration; more preferably, the pore size of the PP filter membrane is 15-20 μm.
In some embodiments, the oxidizing agent comprises at least one of sodium hypochlorite and potassium hypochlorite;
preferably, the oxidant is sodium hypochlorite aqueous solution with the mass fraction of 6-14%.
In some embodiments, the temperature of the oxidation treatment is 65-75 ℃.
In some embodiments, the treatment 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 the second hydrolysis until the hydrolysis liquid is detected to be not discolored by adopting starch-potassium iodide test paper.
In some embodiments, the second post-hydrolysis further comprises: alkaline substances are adopted to adjust the pH value of the hydrolysate, and then concentration treatment is carried out;
preferably, the concentration is performed by vacuum concentration.
In some embodiments, the concentration treatment further comprises cooling crystallization;
preferably, the cooling crystallization further comprises a third solid-liquid separation;
Preferably, the third solid-liquid separation further comprises drying the solid obtained by the third solid-liquid separation.
In some embodiments, the pH of the hydrolysate is adjusted to 6.0-7.0 with 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 wastewater treatment method in the allylamine production process.
The application has the beneficial effects that:
(1) The application can simultaneously and effectively remove high COD, high ammonia nitrogen and complex copper ions in the wastewater in the allylamine production process by adopting simple processes of hydrolysis and oxidation treatment, so that the treated wastewater reaches the first-level standard in GB18918-2002, the residual COD amount is lower than 100ppm, the residual ammonia nitrogen amount is lower than 10ppm, and the residual copper amount can reach the condition that the wastewater is not checked.
(2) Further, after the oxidant is subjected to oxidation treatment by at least one of sodium hypochlorite and potassium hypochlorite, the excessive oxidant can be decomposed through hydrolysis, and then the pH of the hydrolysate is further regulated by an alkaline substance and then concentrated, so that the treated condensate water reaches the direct formula standard, or can be directly used in the allylamine production process, and the purposes of energy conservation and emission reduction are achieved; and simultaneously recovering the industrial sodium chloride and/or potassium chloride which meet the quality products.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being 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 wastewater treatment method according to an embodiment of the present application.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, 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, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list 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 ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"Parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g, 2.689g, or the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. or the mass of the A component is aK, the mass of the B component is bK (K is any number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"And/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
Referring to fig. 1, the present application provides a method for treating wastewater in an 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 ℃; complex copper ions are unstable at high temperature and are easy to decompose; the hydrolysis temperature is controlled between 100 ℃ and 105 ℃, the complex copper ion structure can be better destroyed, and under the condition of the existence of oxygen, carbon dioxide and water, sediment (containing copper oxide, copper green and copper hydroxide) is further fully formed, and inorganic ammonia nitrogen enters an exhaust gas absorption treatment system in an ammonia form for treatment and then is discharged; the hydrolysis specific reaction equation is as follows:
When the first hydrolysis temperature is lower than 100 ℃, only a small amount of copper oxide precipitate is formed, the copper oxide precipitate cannot be fully hydrolyzed, and the hydrolyzed solution is blue; and temperatures above 105 ℃ are difficult to achieve.
The first solid-liquid separation can adopt a filtering mode; preferably, filter paper and PP filter membrane are adopted for filtration; the pore size of the pp filter membrane is 15-20 μm. It should be noted that the precipitate could not be completely filtered off by using only filter paper or by using a common filter membrane.
And S200, oxidizing the liquid obtained by the first solid-liquid separation by adopting an oxidant, and then performing second solid-liquid separation.
In some embodiments, the temperature of the oxidation treatment is 65-75 ℃, and the oxidation treatment can effectively oxidize the complex copper ions which are not decomposed before to generate nitrogen, carbon dioxide, sediment and the like, oxidize ammonia nitrogen to generate nitrogen, carbon dioxide and the like, and send the generated gases into a tail gas absorption treatment system for treatment and then discharge.
The oxidizing agent includes at least one of sodium hypochlorite and potassium hypochlorite. It should be noted that, when the oxidant containing potassium hypochlorite water is used, potassium chloride is generated, and finally, a mixture of sodium chloride and potassium chloride is recovered, and re-separation is needed, so that the processing complexity and cost are increased; preferably, the oxidant adopts 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 a product is not affected; and can continuously recycle to obtain sodium chloride with high purity.
Specifically, the chemical equation of the oxidation reaction at this step is as follows:
The oxidation treatment liquid obtained by the oxidation treatment is subjected to solid-liquid separation, 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 fact that the complex copper ions are fully oxidized is indicated; if the obtained filtrate is light cyan, which indicates that a small amount of complex copper ions exist, a small amount of oxidant is needed to be added continuously for continuous oxidation flocculation, and then the filtrate is filtered until colorless and 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 excess sodium hypochlorite and/or potassium hypochlorite aqueous solution is sufficiently decomposed; when the temperature of the second hydrolysis is lower than 98 ℃, the hydrolysis speed is reduced, which is unfavorable for the actual production operation; and temperatures above 102 ℃ are difficult to achieve; the specific reaction equation for this step is as follows:
The second hydrolysis reaction is carried out until starch-potassium iodide test paper is adopted to detect that the hydrolysis liquid does not change color, so that the excessive hypochlorite is completely decomposed after the oxidation reaction; this is because iodine turns blue when it meets starch, and if hypochlorite is also present, it will react with iodine ions to produce iodine, which can be detected by the color change of starch-potassium iodide paper.
In some embodiments, the treatment method further comprises S400 of adjusting the pH of the hydrolyzed solution after the second hydrolysis with an alkaline substance, followed by concentration treatment.
In some embodiments, alkaline materials are used to adjust the pH of the hydrolysate to 6.0-7.0.
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; the cost of sodium hydroxide is lower than that of other alkaline substances, and the waste water per se contains sodium ions in the allylamine production process, preferably sodium hydroxide is adopted, so that the subsequent separation difficulty caused by the introduction of other alkaline substances such as potassium hydroxide and lithium hydroxide into other salts is avoided, the carbon dioxide generated by the adjustment of the pH value by using sodium carbonate and sodium bicarbonate is avoided, the flushing loss is caused, and the subsequent separation difficulty and a small amount of ammonia gas caused by the generation of ammonium chloride, namely ammonium salt, by using ammonia water to adjust the pH value 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 minus 0.070MPa, at least a certain amount of solvent remains are concentrated under reduced pressure, and the condensed water is formed after water vapor generated in the reduced pressure concentration process is cooled.
Cooling and crystallizing, preferably cooling to 0-5 ℃ and crystallizing for 1h after concentration treatment; and after cooling crystallization, the solid-liquid separation is further carried out (preferably in a filtering mode), and finally, the solid obtained by the third solid-liquid separation is dried, preferably, the solid is dried in a blast drying box at 60-70 ℃ in a blast manner, and sodium chloride and/or potassium chloride reaching the industrial sodium chloride superior level standard are recovered.
The application also provides an application of the wastewater treatment method in the allylamine production process.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
(1) Detecting a sample before treatment of wastewater containing complex copper ions and the like generated in the allylamine production process; 600g of wastewater containing complex copper ions and the like generated in the allylamine production process is added into a 1L reaction bottle; starting an oil bath to heat until the temperature reaches 103 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and copper green are generated); after the hydrolyzed mixture was cooled to room temperature, the solid was removed by filtration through a filter paper+pp filter (pore size: 15 μm).
(2) Heating the filtrate obtained in the step (1) to 70 ℃ in an oil bath, slowly dropwise adding sodium hypochlorite solution with the mass fraction of 10% for oxidation reaction until a large amount of precipitation flocculation; then the mixture after the oxidation reaction is cooled to room temperature and filtered by adopting filter paper and a pp filter membrane (the aperture is 15 mu m), and solid precipitation floccules are removed to obtain colorless transparent filtrate (if the filtrate is light cyan, a small amount of sodium hypochlorite solution is required to be added for continuous flocculation if a trace amount of complex copper ions exist, and then the filtrate is filtered until colorless transparent filtrate is obtained).
(3) And (3) heating the colorless transparent filtrate obtained in the step (2) to 100 ℃ in an oil bath, and 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 sodium hydroxide solution; then concentrating under reduced pressure at 60 ℃ and vacuum degree of-0.070 MPa until a small amount of solvent remains; and sampling and detecting condensed water formed by water vapor generated in the decompression concentration process when the condensed water is cooled.
(5) Cooling the product after the decompression concentration to 5 ℃, stirring and crystallizing for 1h; and then filtering the crystallization material, collecting the solid, drying in a blast drying oven at 65 ℃, and recovering the dried solid, namely sodium chloride.
Example 2
(1) Detecting a sample before treatment of wastewater containing complex copper ions and the like generated in the allylamine production process; 600g of wastewater containing complex copper ions and the like generated in the allylamine production process is added 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 copper green are generated); after the hydrolyzed mixture was cooled to room temperature, the solid was removed by filtration through a filter paper+pp filter (pore size 20 μm).
(2) Heating the filtrate obtained in the step (1) to 65 ℃ in an oil bath, slowly dropwise adding sodium hypochlorite solution with the mass fraction of 6% to perform oxidation reaction until a large amount of precipitation flocculation; then the mixture after the oxidation reaction is cooled to room temperature and filtered by adopting filter paper and a pp filter membrane (the pore diameter is 20 mu m), and solid precipitated flocculate is removed to obtain colorless transparent filtrate (if the filtrate is light cyan, a small amount of sodium hypochlorite solution is required to be added continuously for flocculation if a trace amount of complex copper ions exist, and then the filtrate is filtered until colorless transparent filtrate is obtained).
(3) And (3) heating the colorless transparent filtrate obtained in the step (2) to 98 ℃ in an oil bath, and stirring and hydrolyzing until no color change is detected by using starch-potassium iodide test paper.
(4) Adjusting the pH to 6 by using sodium hydroxide solution; then concentrating under reduced pressure at 60 ℃ and vacuum degree of-0.050 MPa until a small amount of solvent remains; and sampling and detecting condensed water formed by water vapor generated in the decompression concentration process when the condensed water is cooled.
(5) Cooling the product after the decompression concentration to 0 ℃, stirring and crystallizing for 0.5h; and then filtering the crystallization material, collecting the solid, drying in a blast drying oven at 60 ℃, and recovering the dried solid, namely sodium chloride.
Example 3
(1) Detecting a sample before treatment of wastewater containing complex copper ions and the like generated in the allylamine production process; 600g of wastewater containing complex copper ions and the like generated in the allylamine production process is added 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 copper green are generated); after the hydrolyzed mixture was cooled to room temperature, the solid was removed by filtration through a filter paper+pp filter (pore size 20 μm).
(2) Heating the filtrate obtained in the step (1) to 75 ℃ in an oil bath, slowly dropwise adding sodium hypochlorite solution with the mass fraction of 14% to perform oxidation reaction until a large amount of precipitation flocculation; then the mixture after the oxidation reaction is cooled to room temperature and filtered by adopting filter paper and a pp filter membrane (the pore diameter is 20 mu m), and solid precipitated flocculate is removed to obtain colorless transparent filtrate (if the filtrate is light cyan, a small amount of sodium hypochlorite solution is required to be added continuously for flocculation if a trace amount of complex copper ions exist, and then the filtrate is filtered until colorless transparent filtrate is obtained).
(3) And (3) heating the colorless transparent filtrate obtained in the step (2) to 102 ℃ in an oil bath, and stirring and hydrolyzing until no color change is detected by using starch-potassium iodide test paper.
(4) Adjusting the pH to 7 by using sodium hydroxide solution; then concentrating under reduced pressure at 60 ℃ and vacuum degree of-0.060 MPa until a small amount of solvent remains; and sampling and detecting condensed water formed by water vapor generated in the decompression concentration process when the condensed water is cooled.
(5) Cooling the product after the decompression concentration to 3 ℃, stirring and crystallizing for 1h; and then filtering the crystallization material, collecting the solid, drying in a blast drying oven at 70 ℃, and recovering the dried solid, namely sodium chloride.
Example 4
(1) Detecting a sample before treatment of wastewater containing complex copper ions and the like generated in the allylamine production process; adding 10kg of wastewater containing complex copper ions and the like generated in the allylamine production process into a 20L reaction kettle; starting a high-low temperature integrated machine to heat to 103 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and copper green are generated); the hydrolyzed mixture was cooled to room temperature by a high-low temperature integrated machine, and then filtered through a filter paper+pp filter membrane (pore size: 15 μm) to remove solids.
(2) Heating the filtrate obtained in the step (1) to 70 ℃ by a high-low temperature integrated machine, and slowly dripping sodium hypochlorite solution with the mass fraction of 10% for oxidation reaction until a large amount of precipitation flocculation; and then cooling the mixture after the oxidation reaction to room temperature by a high-low temperature integrated machine, filtering by adopting filter paper+pp filter membrane (aperture 15 mu m), removing solid precipitate flocculate, and obtaining colorless transparent filtrate (if the filtrate is light cyan, which indicates that trace complex copper ions exist, a small amount of sodium hypochlorite solution needs to be continuously added for continuous flocculation, and filtering until colorless transparent filtrate is obtained).
(3) Heating the colorless transparent filtrate obtained in the step (2) to 100 ℃ by a high-low temperature integrated machine, and 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 sodium hydroxide solution; then concentrating under reduced pressure at 60 ℃ and vacuum degree of-0.080 MPa until a small amount of solvent remains; and sampling and detecting condensed water formed by water vapor generated in the decompression concentration process when the condensed water is cooled.
(5) Cooling the product after the decompression concentration to 5 ℃, stirring and crystallizing for 1h; and then filtering the crystallization material, collecting the solid, drying in a blast drying oven at 65 ℃, and recovering the dried solid, namely sodium chloride.
Example 5
(1) Detecting a sample before treatment of wastewater containing complex copper ions and the like generated in the allylamine production process; 200g of wastewater containing complex copper ions and the like generated in the allylamine production process is added into a 500mL reaction kettle; starting a high-low temperature integrated machine to heat to 103 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and copper green are generated); the hydrolyzed mixture was cooled to room temperature by a high-low temperature integrated machine, and then filtered through a filter paper+pp filter membrane (pore size: 15 μm) to remove solids.
(2) Heating the filtered filtrate obtained in the step (1) to 80 ℃ by a high-low temperature integrated machine, and slowly dripping sodium hypochlorite solution with the mass fraction of 10% for oxidation reaction until a large amount of precipitation flocculation; and then cooling the mixture after the oxidation reaction to room temperature by a high-low temperature integrated machine, filtering by adopting filter paper+pp filter membrane (aperture 15 mu m), removing solid precipitate flocculate, and obtaining colorless transparent filtrate (if the filtrate is light cyan, which indicates that trace complex copper ions exist, a small amount of sodium hypochlorite solution needs to be continuously added for continuous flocculation, and filtering until colorless transparent filtrate is obtained).
(3) Heating the colorless transparent filtrate obtained in the step (2) to 100 ℃ by a high-low temperature integrated machine, and 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 sodium hydroxide solution; then concentrating under reduced pressure at 60 ℃ and vacuum degree of-0.080 MPa until a small amount of solvent remains; and sampling and detecting condensed water formed by water vapor generated in the decompression concentration process when the condensed water is cooled.
(5) Cooling the product after the decompression concentration to 5 ℃, stirring and crystallizing for 1h; and then filtering the crystallization material, collecting the solid, drying in a blast drying oven at 65 ℃, and recovering the dried solid, namely sodium chloride.
Example 6
(1) Detecting a sample before treatment of wastewater containing complex copper ions and the like generated in the allylamine production process; 200g of wastewater containing complex copper ions and the like generated in the allylamine production process is added into a 500mL reaction kettle; starting a high-low temperature integrated machine to heat to 103 ℃, stirring and hydrolyzing until the solution is dark green (black copper oxide and copper green are generated); the hydrolyzed mixture was cooled to room temperature by a high-low temperature integrated machine, and then filtered through a filter paper+pp filter membrane (pore size: 15 μm) to remove solids.
(2) Heating the filtered filtrate obtained in the step (1) to 60 ℃ by a high-low temperature integrated machine, slowly dripping sodium hypochlorite solution with the mass fraction of 10% for oxidation reaction until a large amount of precipitation flocculation; and then cooling the mixture after the oxidation reaction to room temperature by a high-low temperature integrated machine, filtering by adopting filter paper+pp filter membrane (aperture 15 mu m), removing solid precipitate flocculate, and obtaining colorless transparent filtrate (if the filtrate is light cyan, which indicates that trace complex copper ions exist, a small amount of sodium hypochlorite solution needs to be continuously added for continuous flocculation, and filtering until colorless transparent filtrate is obtained).
(3) Heating the colorless transparent filtrate obtained in the step (2) to 101 ℃ by a high-low temperature integrated machine, and 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 sodium hydroxide solution; then concentrating under reduced pressure at 60 ℃ and vacuum degree of-0.080 MPa until a small amount of solvent remains; and sampling and detecting condensed water formed by water vapor generated in the decompression concentration process when the condensed water is cooled.
(5) Cooling the product after the decompression concentration to 5 ℃, stirring and crystallizing for 1h; and then filtering the crystallization material, collecting the solid, drying in a blast drying oven at 65 ℃, and recovering the dried solid, namely sodium chloride.
The wastewater containing complex copper ions and the like produced in the allylamine production process used in examples 1 to 5 was wastewater of different batches, and wastewater of the same batch used in examples 6 and 5. The comparative results of the data of the above examples 1 to 6 before and after wastewater treatment 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:
Remarks: the copper ion content detection method is carried out according to a conventional titration method or ion chromatography method.
Conclusion: by adopting the wastewater treatment process provided by the embodiment of the application, 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 first-level standard in GB18918-2002, the residual COD amount is lower than 100ppm, the residual ammonia nitrogen amount is lower than 10ppm, and the residual copper amount can reach the condition that the wastewater is not checked;
In example 5, the oxidation reaction temperature in the step (2) is increased to 80 ℃, and the amount of sodium hypochlorite aqueous solution added is increased (sodium hypochlorite decomposition is accelerated) under the condition that 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) was reduced to 60 ℃, and the hydrolysis time was prolonged (the reactivity was reduced) when the oxidation reaction temperature was too low, and the COD and ammonia nitrogen content of the finally obtained condensate water were slightly higher, and the content of the recovered sodium chloride was slightly lower.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, 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 below, 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 (4)
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;
Oxidizing the liquid obtained by the first solid-liquid separation by adopting an oxidant, and then performing second solid-liquid separation;
the temperature of the first hydrolysis is 100-105 ℃;
The oxidant comprises at least one of sodium hypochlorite and potassium hypochlorite;
the temperature of the oxidation treatment is 65-75 ℃;
carrying out second hydrolysis on the liquid obtained by the second solid-liquid separation;
the temperature of the second hydrolysis is 98-102 ℃;
The second hydrolysis further comprises: regulating pH of the hydrolysate to 6.0-7.0 with alkaline matter, and concentrating; the first solid-liquid separation and the second solid-liquid separation adopt a filtering mode;
The filtration adopts filter paper and PP filter membrane filtration;
the pore diameter of the filter membrane is 15-20 mu m;
The alkaline substance is sodium hydroxide;
performing second hydrolysis on the liquid obtained by the second solid-liquid separation until the hydrolysis liquid is detected to be not discolored by adopting starch-potassium iodide test paper;
The concentration treatment further comprises cooling crystallization;
the cooling crystallization step further comprises a third solid-liquid separation step;
And drying the solid obtained by the third solid-liquid separation after the third solid-liquid separation.
2. The method for treating wastewater in an allylamine production process according to claim 1, wherein the oxidizing agent is an aqueous sodium hypochlorite solution with a mass fraction of 6-14%.
3. The method for treating wastewater in an allylamine production process according to claim 1, wherein the concentration is performed by vacuum concentration.
4. Use of a method for treating wastewater from an allylamine production process according to any one of claims 1 to 3 in an allylamine production process.
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| SU1481209A1 (en) * | 1987-06-03 | 1989-05-23 | Уфимский Нефтяной Институт | Method of treating waste water containing copper-ammonia complexes |
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