CN102153163A - Method for treating wastewater containing cycloheximide and hexamethylene diamine - Google Patents
Method for treating wastewater containing cycloheximide and hexamethylene diamine Download PDFInfo
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- CN102153163A CN102153163A CN2011101399392A CN201110139939A CN102153163A CN 102153163 A CN102153163 A CN 102153163A CN 2011101399392 A CN2011101399392 A CN 2011101399392A CN 201110139939 A CN201110139939 A CN 201110139939A CN 102153163 A CN102153163 A CN 102153163A
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- fiber
- waste water
- hexanediamine
- hexamethylene diamine
- cycloheximide
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Abstract
The invention discloses a method for treating wastewater containing cycloheximide and hexamethylene diamine and belongs to the technical field of wastewater treatment. The method comprises the following steps that the wastewater containing cycloheximide and hexamethylene diamine is mixed and contacted with a fibrous adsorbent in a container or is contacted with the fibrous adsorbent in an absorption column in a flowing mode, so that cycloheximide and hexamethylene diamine in the wastewater are adsorbed by carboxyl on fibers; and after the fibers adsorb cycloheximide and hexamethylene diamine to be saturated, the obtained product is subjected to elution regeneration by diluted acid and the product can be used continuously repeatedly. The method has high adsorbing speed, high sensitivity and high adsorption capacity for amine. High-concentration amine hydrochloride in eluent can be recycled as required.
Description
Technical field
The present invention relates to a kind of method of handling trade effluent, relate in particular to a kind of fiber adsorbing substance that utilizes and handle the method that contains U-4527 and hexanediamine waste water, belong to technical field of waste water processing.
Background technology
Hexamethyleneimine is called hexamethylene imine, azepan etc. again, English name hexamethyleneimine, abbreviation HMI, molecular formula C
6H
13N, molecular weight 99.17.U-4527 is a kind of important organic chemical industry's intermediate, is again a kind of organic pollutant with toxicity and difficult for biological degradation.Hexanediamine, promptly 1, the 6-hexanediamine claims 1 again, English name hexamethylenediamine, abbreviation HMD, molecular formula C
6H
16N
2, molecular weight 116.20.Hexanediamine is important Organic Chemicals, especially for the production of nylon.Hexanediamine also has certain environmental toxicity, and has the characteristics of difficult for biological degradation.U-4527 usually occurs as the byproduct in the hexanediamine production, therefore in the nylon production process, can produce the waste water that contains U-4527 and hexanediamine inevitably, though these two kinds of aminated compoundss content in waste water is not high, but biological degradation had stronger toxicity, in case be drained in the composite waste, can have influence on the effect of entire sewage treatment project.Therefore, it is very necessary studying the treatment technology that contains U-4527 and hexanediamine waste water pointedly.
At present for the waste water that contains U-4527, hexanediamine and other aminated compoundss, the existing bibliographical information that adopts methods such as extraction, distillation, absorption, reverse osmosis, biological treatment to handle, wherein have: document " reclaims U-4527 " from hexanediamine is produced waste liquid (chemical industry environmental protection with the present invention is comparatively closely-related, 1989, the 9th the 2nd phase of volume) from waste water, repeatedly extracts U-4527 with toluene, the extraction liquid anhydrous magnesium sulfate drying, filter the back and feed exsiccant HCl gas, generate white flocks with the U-4527 reaction and separated.Document " reverse osmosis method reclaims the research of U-4527 from waste water " (membrane science and technology, 1994, the 14th the 3rd phase of volume) adopt Cellulose diacetate reverse osmosis membrane or polyimide reverse osmosis membrane, more than 95%, cycles of concentration can reach 6-8 doubly to the rejection of U-4527.Chinese patent CN201010514379.X " a kind of processing method of industrial waste water that contains hexanediamine " carries out anaerobic biological treatment, anaerobic treatment, oxygen consumption processing to waste water successively, and the trade effluent that contains hexanediamine can be discharged by stably reaching standard.Document " exploitation of hexanediamine waste water and application " (Hebei chemical industry, 2008, the 31st the 7th phase of volume) adopts the settlement separate operational path that removes alkali, reduces pressure stepwise distillation, catalytic reduction, dewaters and extract, to the organic waste water that contains amine such as the hexanediamine separation of purifying, make it to have to recycle and be worth.Document " design and operation that the hexanediamine waste water treatment engineering is transformed " (Chinese water supply and drainage,, the 24th the 8th phase of volume in 2008) adopts acidication+A/O art breading hexanediamine waste water, and COD, ammonia nitrogen all reach design requirements.Waste water and storng-acid cation exchange resin after Chinese patent CN200810021929.7 " a kind of method of processing dimethylamine waste water by ion-exchange method " will filter carry out ion-exchange, dimethylamine is removed rate 〉=96% in the waste water, and the dimethylamine after the desorb forms the recyclable utilization of dimethylamine salt of high density.Chinese patent CN200610038529.8 " adopts difunctional plastic resin treatment to contain the method for Tolylamine waste water " will contain toluene waste water by being filled with the treatment unit of difunctional resin, the saturated back of resin absorption diluted acid desorption and regeneration, the high density Tolylamine solution that desorption gets off reclaims the Tolylamine product through operations such as toning alkali, rectifying.Chinese patent CN200510043556.X " extracts the method for O-Phenylene Diamine " with waste water by the adsorption column of wide aperture resin is housed from the O-Phenylene Diamine factory effluent, make organism resin absorption such as O-Phenylene Diamine, carrying out desorb with ethanolic soln then reclaims, distillation back raffinate carries out the temperature control cooling, and the O-Phenylene Diamine crystallization is separated out.
The method of above-mentioned bibliographical information respectively has its advantage, yet exists some deficiency maybe to need to develop perfect aspect simultaneously, and for example: the extraction efficiency of solvent extration is not high, still residual more U-4527 in the waste water behind multi-stage solvent extraction; Reverse osmosis method needs bigger operating pressure, and is high not enough to the cycles of concentration of waste water; Distillation method heating power consumption is more, is unsuitable for handling the waste water of lower concentration; Biological treatment needs bigger place and long processing cycle usually; Absorption method does not relate to the processing to U-4527 and hexanediamine waste water as yet, and the sorbent material that is adopted is traditional resin form sorbent material, does not relate to the sorbent material of fibre shape as yet.
Summary of the invention
The object of the present invention is to provide a kind of fiber adsorbing substance that utilizes to handle the novel method that contains U-4527 and hexanediamine waste water by chemisorption.
Technical scheme of the present invention is: will contain U-4527 and hexanediamine waste water and mix with fiber adsorbing substance in the container and contact, or contact with fiber adsorbing substance in the adsorption column with flow pattern, make U-4527 and hexanediamine in the waste water adsorbed by the carboxyl of fiber surface; After fiber absorption is saturated, utilize diluted acid to carry out wash-out regeneration, can continue to reuse.
Concrete grammar provided by the invention is: (mass percentage concentration of contained U-4527 is 0.01 ~ 1.0% in the waste water will to contain U-4527 and hexanediamine waste water, the mass percentage concentration of hexanediamine is 0.01-1.0%) mix and to contact with fiber adsorbing substance in the container, or contact with fiber adsorbing substance in the adsorption column with flow pattern, make U-4527 and hexanediamine in the waste water adsorbed by the carboxyl of fiber surface; After fiber absorption is saturated, utilize diluted acid (sulfuric acid of 0.5-2M or the hydrochloric acid of 1-4M) to carry out wash-out regeneration, continue to be used for to carry out wastewater treatment.Absorption and regenerated reaction principle (is example with the U-4527) as shown below:
The fiber adsorbing substance that is adopted is that (length is 2-10cm by acrylic fiber, fiber number is 1-5dtex, contain the acrylonitrile unit more than 90% in the structure) obtain through the chemical modification processing, it is carboxyl that its surface has adsorbing chemical group, content is 3.0-8.0 mmol/g fiber.Its synthetic method is referring to " preparation of Subacidity cation exchange fiber and the research of application " (ion-exchange and absorption, 1993, the 9th rolled up for the 6th phase) and " preparation of Carboxylic Ion Exchange Fibers and performance " (synthetic fiber industry, calendar year 2001, the 24th the 6th phase of volume).
Beneficial effect of the present invention is: the fiber adsorbing substance that (1) is adopted has higher carboxyl-content, and these carboxyls mainly are distributed in fiber surface, can obtain utilizing more fully in absorption, and help adsorbing fast and wash-out; (2) fiber is a kind of chemisorption to the absorption of U-4527 in the waste water and hexanediamine, not only adsorptive capacity is big, rate of adsorption is fast, and adsorb highly sensitive, clearance is high (by the fiber adsorption column total nitrogen content of waste water is reduced to below the 10ppm, clearance reaches more than 98.5%); (3) chemisorption is a kind of selectively quantitative absorption, can accurately calculate the ratio of waste water and sorbent material according to the concentration of amine in fiber carboxyl-content and the waste water; (4) carboxyl of fiber absorption saturated after, the regeneration of available diluted acid (sulfuric acid or hydrochloric acid) wash-out realizes repeatedly recycling.
Embodiment
For the present invention is described in detail better, as follows for embodiment:
Embodiment 1:
Measuring 100mL waste water (mass percentage concentration of U-4527 and hexanediamine is respectively 0.3% and 0.1%) joins in the 250mL ground Erlenmeyer flask, drop into the above-mentioned fiber adsorbing substance of 0.5g (carboxyl-content of fiber is 6.5mmol/g), at room temperature airtight mixing vibration, the total nitrogen in different time water sampling total nitrogen/total organic carbon analyzer mensuration water (
TN).Raw wastewater
TNBe 701ppm, behind the vibration 2min
TNPromptly reduce to 214ppm, behind the 5min
TNReduce to 186ppm, behind the 3h that continues to vibrate
TNNo considerable change.Explanation is under the excessive situation of amine, and fiber is promptly near saturated behind the absorption 5min.Fiber is right during 5min
TNAdsorptive capacity be 7.4mmol/g, be higher than theoretical adsorptive capacity 6.5mmol/g(carboxyl and adsorb by 1:1 with amino) this is because 1 hexanediamine of absorption promptly is equivalent to adsorb 2 amino.The present embodiment explanation, under the situation of mixing contact, present method not only processing speed is fast, and can make full use of the adsorptive power of fiber.
Embodiment 2:
Measure 10mL waste water (mass percentage concentration of U-4527 and hexanediamine is respectively 0.3% and 0.1%) and be diluted to 100mL with deionized water, join in the 250mL ground Erlenmeyer flask, drop into the above-mentioned fiber adsorbing substance of 0.5g (carboxyl-content of fiber is 6.5mmol/g), at room temperature airtight mixing vibration is measured in the water with total nitrogen/total organic carbon analyzer at the different time water sampling
TNRaw wastewater
TNBe 70.1ppm, behind the vibration 1min
TNPromptly reduce to 8.1ppm, behind the 5min
TNReduce to 6.7ppm, behind the 3h that continues to vibrate
TNNo considerable change.Explanation is under the excessive situation of fiber adsorbing substance, and promptly near maximum material removal rate, this moment is right behind the absorption 5min
TNClearance be 90.5%.The present embodiment explanation, under the situation that mixing contacts, waste strength is lower and fiber is excessive, present method not only processing speed is fast, and can reach higher removal.
Embodiment 3:
The above-mentioned fiber adsorbing substance of 2g (carboxyl-content of fiber is 6.5mmol/g) is filled in the adsorption column of long 5cm, diameter 1cm, at room temperature by peristaltic pump with waste water (mass percentage concentration of U-4527 and hexanediamine is respectively 0.3% and 0.1%,
TNBe 701ppm) with the flow velocity of 2mL/min from the bottom up by the fiber adsorption column, get at different time and to flow out water sample and measure in the water with total nitrogen/total organic carbon analyzer
TNWhen the outflow volume of water is 0-225mL, record in the water
TNStable content is right at 8.0-10ppm(
TNClearance be more than 98.5%), when flowing out 250mL
TNRise to 54ppm rapidly, when flowing out 275mL
TNRisen to 274mL.When explanation was the 250mL left and right sides in the processing water yield, near penetrating, this moment, fiber was right for fibre columns
TNAdsorptive capacity be about 6.2mmol/g, a little less than the adsorptive capacity 7.4mmol/g among the embodiment 1, this is because guaranteeing that the fiber of adsorption column end can not adsorb saturated fully under the situation of adsorption effect.Adopt ways such as reducing flow velocity and improvement adsorption column size that the fiber utilization rate is increased.The present embodiment explanation, under the situation that adopts fibre columns absorption, present method can reach very high clearance, and the adsorptive power of fiber can obtain utilizing more fully.
Embodiment 4:
Regenerate to having adsorbed saturated fibre columns among the embodiment 3 with dilute hydrochloric acid, its method is: at room temperature pass through fibre columns with 15mL 1.5M hydrochloric acid from the bottom up with the flow velocity of 1mL/min, carboxyl is recovered to make the amine that adsorbs on the fiber be eluted simultaneously, and elutriant is collected separately; Use the 100mL deionized water to pass through fibre columns again, unnecessary hydrochloric acid is rinsed well with the flow velocity of 5mL/min; Continue then to carry out wastewater treatment test according to the method for embodiment 3.According to
TNMeasurement result, in the elutriant amine concentration be raw wastewater 15-20 doubly.After 50 absorption and regeneration, this fibre columns still can be handled the waste water about 200mL, and treatment effect is suitable with embodiment 3.Present embodiment explanation, but fiber adsorbing substance repeated multiple times of the present invention use, and treatment effect does not have obvious reduction; Contain the U-4527 and the hexamethylene-diamine hydrochloride of high density in the hydrochloric acid elutriant, can reclaim valuable raw material by methods such as evaporation concentration, extractions as required.
Claims (3)
1. a processing contains the method for U-4527 and hexanediamine waste water, it is characterized in that: will contain U-4527 and hexanediamine waste water and mix with fiber adsorbing substance in the container and contact, or contact with fiber adsorbing substance in the adsorption column with flow pattern, make U-4527 and hexanediamine in the waste water adsorbed by the carboxyl on the fiber; This fiber adsorbing substance is to be 2-10cm by length, and fiber number is 1-5dtex, and the acrylic fiber that contains the acrylonitrile unit more than 90% in the structure is handled through chemical modification and obtained, and its carboxyl-content is a 3.0-8.0 mmol/g fiber.
2. processing as claimed in claim 1 contains the method for U-4527 and hexanediamine waste water, it is characterized in that: the mass percentage concentration of contained U-4527 is 0.01 ~ 1.0% in the waste water, and the mass percentage concentration of hexanediamine is 0.01-1.0%.
3. processing as claimed in claim 1 contains the method for U-4527 and hexanediamine waste water, it is characterized in that: after fiber absorption is saturated, utilize diluted acid to carry out wash-out regeneration, can continue to reuse.
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| CN 201110139939 CN102153163B (en) | 2011-05-27 | 2011-05-27 | Method for treating wastewater containing cycloheximide and hexamethylene diamine |
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| CN 201110139939 CN102153163B (en) | 2011-05-27 | 2011-05-27 | Method for treating wastewater containing cycloheximide and hexamethylene diamine |
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| CN102153163B CN102153163B (en) | 2013-03-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853243A (en) * | 2022-05-19 | 2022-08-05 | 山东潍坊润丰化工股份有限公司 | Recycling treatment method for 1,2,3, 6-tetrahydrophthalimide production wastewater |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110171879A (en) * | 2019-06-17 | 2019-08-27 | 南京大学 | A kind of fermentation waste water treatment process containing acrylonitrile |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5830387A (en) * | 1981-08-18 | 1983-02-22 | Asahi Chem Ind Co Ltd | Treatment of waste water containing amines |
| CN101337707A (en) * | 2008-08-08 | 2009-01-07 | 合肥工业大学 | Method for processing dimethylamine waste water by ion-exchange method |
| CN101993178A (en) * | 2010-10-21 | 2011-03-30 | 神马实业股份有限公司 | Method for treating industrial wastewater containing hexamethylenediamine |
-
2011
- 2011-05-27 CN CN 201110139939 patent/CN102153163B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5830387A (en) * | 1981-08-18 | 1983-02-22 | Asahi Chem Ind Co Ltd | Treatment of waste water containing amines |
| CN101337707A (en) * | 2008-08-08 | 2009-01-07 | 合肥工业大学 | Method for processing dimethylamine waste water by ion-exchange method |
| CN101993178A (en) * | 2010-10-21 | 2011-03-30 | 神马实业股份有限公司 | Method for treating industrial wastewater containing hexamethylenediamine |
Non-Patent Citations (3)
| Title |
|---|
| 《河南化工》 20071220 刘艾杉等 弱酸性离子交换纤维吸附水中的氨和有机胺的研究 第21页右栏第4行-第23页右栏第12行 1-3 第24卷, 第12期 * |
| 刘艾杉等: "弱酸性离子交换纤维吸附水中的氨和有机胺的研究", 《河南化工》 * |
| 沙保峰等: "改性聚丙烯腈纤维处理电镀废水的试验研究", 《中国给水排水》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853243A (en) * | 2022-05-19 | 2022-08-05 | 山东潍坊润丰化工股份有限公司 | Recycling treatment method for 1,2,3, 6-tetrahydrophthalimide production wastewater |
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