CN104557596A - Method for treating N,N-dimethyl-1,3-propane diamine waste liquor - Google Patents

Method for treating N,N-dimethyl-1,3-propane diamine waste liquor Download PDF

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Publication number
CN104557596A
CN104557596A CN201410796500.0A CN201410796500A CN104557596A CN 104557596 A CN104557596 A CN 104557596A CN 201410796500 A CN201410796500 A CN 201410796500A CN 104557596 A CN104557596 A CN 104557596A
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China
Prior art keywords
dmapa
waste liquid
dimethyl
waste
liquid
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CN201410796500.0A
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Inventor
余照权
张涌
刘振华
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GUANGZHOU FLOWER'S SONG FINE CHEMICAL CO Ltd
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GUANGZHOU FLOWER'S SONG FINE CHEMICAL CO Ltd
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Priority to CN201410796500.0A priority Critical patent/CN104557596A/en
Publication of CN104557596A publication Critical patent/CN104557596A/en
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Abstract

The invention discloses a method for treating N,N-dimethyl-1,3-propane diamine waste liquor. The method comprises the following steps: adding fatty acids with the mass of m1 into a reaction kettle, slowly stirring, heating to the temperature of 100-110 DEG C, slowly dripping DMAPA waste liquor with the mass of m2 and the concentration of wt%, raising the temperature in the reaction kettle to the temperature of 115-125 DEG C after the dripping operation is finished, collecting the secondary waste liquor after the reaction is finished, and detecting the content of residual DMAPA in the secondary waste liquor. The treatment method is easy to operate, any equipment does not need to be increased, distillation and purification or secondary rectification and other operations are not needed, the content of DMAPA in the treated secondary wastewater is less than or equal to 0.5 percent, the emission standard is met, and the overall efficiency is obvious.

Description

A kind of method of process N, N-dimethyl-1,3-propylene diamine waste liquid
Technical field
The present invention relates to raw material disposal recovery and reuse technology field in the production of novel material tensio-active agent, being specifically related to the N to producing in cocoamidopropyl dimethylamine amine reaction process, the treatment process of N-dimethyl-1,3-propylene diamine devil liquor recovery recycling.
Background technology
At surfactant industry, cocoamidopropyl dimethylamine amine (being called for short PKO) is the intermediate synthesizing numerous tensio-active agent, apply widely, and the synthesis of PKO is mainly by lipid acid and N, N-dimethyl-1,3-propylene diamine amidate action obtains.Wherein, N, N-dimethyl-1,3-propylene diamine (be called for short DMAPA) be a kind of volatile, be not easy to decompose, inflammable, toxicity large, stimulate strong to skin and cornea, and can cause the material of burning, environmental pollution is serious.Therefore, the discharge of less DMAPA or even zero release are very necessary, meet the outstanding advantages of novel surfactant mainly in safety and environmental protection.In the production of PKO, due to the high boiling characteristic of lipid acid, for ensureing that lipid acid fully reacts mainly by increasing the molar mass of DMAPA, guarantee that residual fat acid content≤1.5% meets rower, the mol ratio of lipid acid and DMAPA is usually at 1:1.25-1.3.Because DMAPA is volatile, by last underpressure distillation removing little over the DMAPA of amount, finally the remaining DMAPA content in PKO can be down to less than 0.3%.But amidate action is dehydration reaction, the DMAPA distilled out will mix with water, form general mass concentration at the DMAPA waste liquid of about 40%, directly discharge not only according to the waste becoming raw material, more because its volatility, toxicity and corrodibility cause severe contamination to environment.
At present, common DMAPA method for treating waste liquid has following three kinds: 1, if application number is for as described in the patent of invention of 201210550452.8, water-removal agent (as calcium oxide, magnesium hydroxide, sodium methylate etc.) is added in DMAPA waste liquid, the aqueous solution of water-removal agent and DMAPA layering, again the DMAPA solution on upper strata is input to still kettle and carries out underpressure distillation, reach the object of DMAPA recycling eventually through collection distillate.2, application number be 02822683.6 invention utilize two platen presses of the binary mixture of rectifying homogeneous phase azeotropic, from the aqueous solution, be separated the method for this amine by the aqueous solution of continuous still battery amine.3, if application number is the method for a kind of dynamical distillation processing separation of amine aqueous solution as described in the invention of 200510075475.8.
In aforesaid method, method 1 needs outsourcing device to comprise interface liquid level gauge, still kettle, storage tank etc., and need to add water-removal agent, the aqueous solution of water-removal agent also needs process, because this aqueous solution must have the peculiar smell of certain DMAPA, the production of other products can not be directly used in; All need to adopt secondary and above rectifier unit to the recovery of amine in method 2,3, the amine of ability separating high-purity.The construction investment of these two kinds of methods is excessive, and energy consumption is high, sees in cost angle, and cost recovery is higher than the value of Recycling of waste liquid.Above-mentioned 3 kinds of methods all need to invest corresponding equipment, although the 1st kind of facility investment is little, follow-up also need solves the water-removal agent solution-treated problem containing peculiar smell.Therefore, seek the Method and process that processing cost is low, the DMAPA devil liquor recovery process of energy-saving and emission-reduction recycles and seem particularly urgent.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of process N, N-dimethyl-1, the method of 3-propylene diamine waste liquid, this treatment process is simple to operate, does not need to increase any equipment, more do not need to carry out the operation such as distilation or secondary rectifying, in secondary wastewater after treatment, content≤0.5% of DMAPA, reaches emission standard, and overall efficiency is remarkable.
For solving the problem, the technical solution adopted in the present invention is as follows:
A kind of method of process N, N-dimethyl-1,3-propylene diamine waste liquid, it comprises the following steps: be m by quality 1lipid acid drop in reactor, slowly stir, and be warming up to 100 ~ 110 DEG C, slowly dripping quality is m 2, concentration is the DMAPA waste liquid of wt%, by the temperature to 115 in reactor ~ 125 DEG C after dripping, reacted rear collection water of condensation (secondary liquid waste), detected the content of remaining DMAPA in water of condensation (secondary liquid waste); Wherein, wt%≤80% and m 2× wt%≤m 1× 10%.
As preferably of the present invention, the time for adding of described DMAPA waste liquid is 2 ~ 6h.
As preferably of the present invention, after reactor is warming up to 115 ~ 125 DEG C, the reaction times of described DMAPA waste liquid and lipid acid is 2 ~ 5h.
Particularly, the content of remaining DMAPA measures in accordance with the following steps: weighing m 3g secondary liquid waste, adds deionized water 30ml, adds tetrabromo-mcresolsulfonphthalein-methyl red mixture indicator 2 that volume ratio is 3:1, with the hydrochloric acid standard solution titration of 0.1M, solution is terminal by green to redness, and it is v ml that note consumes volume, calculates the concentration c=0.1v × 102/ (m of DMAPA 3× 2000).
Compared to existing technology, beneficial effect of the present invention is:
1, the present invention utilizes reversible reaction principle in chemistry, the DMAPA in abundant fatty acid and waste liquid is utilized to react, because lipid acid is excessive greatly, reaction is easy to carry out to positive reaction direction, and the temperature in the rate of addition of control DMAPA waste liquid and control by stages reactor, so that the water that water in waste liquid and amidate action generate evaporates in time;
2, the present invention utilizes another kind of thinking to reach the effect of process DMAPA waste liquid, namely utilizes reversible chemical reaction to be consumed by the DMAPA in waste liquid, but not purifies to waste liquid; The present invention can by mass concentration lower than 80% DMAPA liquid waste disposal be mass concentration lower than 0.5% secondary liquid waste, thus reach emission standard;
3, the present invention is without the need to additionally adding equipment, and technology controlling and process is simple, does not need to carry out the troublesome operation such as distilation or secondary rectifying, and the Be very effective of process DMAPA waste liquid.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
Embodiment 1: the DMAPA waste liquid result contrast under the same conditions of different concns different mass
Add 500kg lipid acid in a kettle., slowly stir, heat up fusing, when temperature rises to 105 DEG C, start to drip DMAPA waste liquid, drop in lipid acid by the DMAPA waste liquid of different concns different mass, time for adding is 3h, after dropwising, be warming up to 110 DEG C, continue reaction 3h, collect secondary wastewater and measure DMAPA content, and weigh, result is as shown in table 1.
Table 1: DMAPA content and quality in the secondary wastewater of different concns different mass DMAPA waste liquid
DMAPA liquid waste concentration (%) Waste liquid quality (kg) DMAPA content (%) in secondary wastewater Secondary wastewater quality (kg)
10 60 0.14 54.2
30 60 0.21 44.5
50 60 0.33 24.5
70 60 0.40 24.2
80 60 0.44 19.7
90 60 0.62 14.1
80 70 0.58 23.5
70 80 0.55 33.4
90 50 0.60 12.9
Interpretation of result: as shown in Table 1, a certain amount of DMAPA waste liquid, concentration is lower, and in the secondary wastewater obtained after treatment, DMAPA content is lower; When DMAPA concentration in waste liquid higher than 80% time, the DMAPA concentration after treatment in secondary wastewater can not be down to less than 0.5%, mainly because DMAPA excessive concentration in tear drop process can evaporation section, causes the concentration in secondary wastewater to increase.When in waste liquid, DMAPA content exceedes 10% of lipid acid quality, in secondary wastewater, DMAPA concentration will more than 0.5%, mainly due to DMAPA too high levels, easily by evaporation section.
Embodiment 2: the DMAPA liquid waste disposal Comparative result of same concentrations equal in quality under different dropping temperature
Add 500kg lipid acid in a kettle., slow stirring, heat up fusing, and start the DMAPA waste liquid 60kg dripping concentration 50% at different temperatures, time for adding is 3h, after dropwising, be warming up to 115 DEG C, continue reaction 3h, collect secondary wastewater and measure DMAPA content, and weigh, result is as shown in table 2.
Interpretation of result: as shown in Table 2, when dropping temperature does not just drip advantage lower than when 100 DEG C, mainly because the water in DMAPA waste liquid cannot be discharged in time, during follow-up temperature reaction, cause concentration in secondary wastewater higher due to small part DMAPA can be taken out of when dropping temperature reaches about 120 DEG C water evaporations.When dropping temperature is higher than 120 DEG C, this temperature is close to the boiling point of DMAPA, and dropping process can accelerate the evaporation of DMAPA, thus causes the concentration in secondary wastewater higher.
Table 2: DMAPA content and quality in the secondary wastewater under different dropping temperature
Tear drop temperature (DEG C) DMAPA content (%) in secondary wastewater Secondary wastewater quality (kg)
80 0.66 24.2
90 0.52 24.2
100 0.35 24.3
110 0.33 24.3
120 0.72 24.8
Embodiment 3: the DMAPA liquid waste disposal Comparative result of same concentrations equal in quality under different time for adding
Add 500kg lipid acid in a kettle., slow stirring, heat up fusing, when temperature rises to 110 DEG C, start the DMAPA waste liquid 60kg dripping concentration 50%, time for adding is different, after dropwising, is warming up to 125 DEG C, continue reaction 3h, collect secondary wastewater and measure DMAPA content, and weigh, result is as shown in table 3.
Table 3: DMAPA content and quality in secondary wastewater under different time for adding
Tear drop time (h) DMAPA content (%) in secondary wastewater Secondary wastewater quality (kg)
1 0.61 24.7
2 0.46 24.2
3 0.35 24.3
4 0.30 24.3
5 0.28 24.5
6 0.28 24.6
>6 ≤0.28 24.7-24.9
Interpretation of result: as shown in Table 3, when time for adding is too short, the water in DMAPA waste liquid cannot be discharged in time, during follow-up temperature reaction, because temperature reaches about 120 DEG C, can take small part DMAPA out of and cause concentration in secondary wastewater higher.After the tear drop time is greater than 6h, follow-up result is had no significant effect.
Embodiment 4: the DMAPA liquid waste disposal Comparative result of same concentrations equal in quality at differential responses temperature
Add 500kg lipid acid in a kettle., slow stirring, heat up fusing, when temperature rises to 110 DEG C, start the DMAPA waste liquid 60kg dripping concentration 50%, time for adding is 3h, after dropwising, under differing temps, continue reaction 3h, collect secondary wastewater and measure DMAPA content, and weigh, result is as shown in table 4.
Table 4: DMAPA content and quality in secondary wastewater at differential responses temperature
Temperature of reaction (DEG C) DMAPA content (%) in secondary wastewater Secondary wastewater quality (kg)
105 0.30 23.4
115 0.34 24.2
125 0.40 24.3
135 0.86 24.9
Interpretation of result: as shown in Table 4, when subsequent reactions temperature is about 105 DEG C, because temperature is too low, causes amidate action to carry out smoothly, so secondary wastewater total mass is on the low side.When temperature of reaction arrives 135 DEG C, this temperature, more than the boiling point of DMAPA, causes the part DMAPA in waste liquid to evaporate, thus makes DMAPA concentration in secondary wastewater higher.
Embodiment 5: the DMAPA liquid waste disposal Comparative result of same concentrations equal in quality under the differential responses time
Add 500kg lipid acid in a kettle., slow stirring, heat up fusing, when temperature rises to 105 DEG C, start the DMAPA waste liquid 60kg dripping concentration 50%, time for adding is 3h, after dropwising, is warming up to 110 DEG C, under the differential responses time, collect secondary wastewater and measure DMAPA content, and weigh, result is as shown in table 5.
Table 5: DMAPA content and quality in secondary wastewater under the differential responses time
Reaction times (h) DMAPA content (%) in secondary wastewater Secondary wastewater quality (kg)
1 0.33 23.4
2 0.32 24.1
3 0.33 24.3
4 0.32 24.4
5 0.32 24.5
~0.32 24.5-24.9
Interpretation of result: as shown in Table 5, time too short when reacted, the amidate action of lipid acid and DMAPA is incomplete, causes secondary wastewater quality on the low side; More than after 2h when reacted, amidate action is tending towards complete substantially, and the quality of secondary wastewater tends towards stability.
Above-mentioned embodiment is only the preferred embodiment of the present invention; can not limit the scope of protection of the invention with this, change and the replacement of any unsubstantiality that those skilled in the art does on basis of the present invention all belong to the present invention's scope required for protection.

Claims (4)

1. process the method for a N, N-dimethyl-1,3-propylene diamine waste liquid, it is characterized in that: comprise the following steps: be m by quality 1lipid acid drop in reactor, slowly stir, and be warming up to 100 ~ 110 DEG C, slowly dripping quality is m 2, concentration is the DMAPA waste liquid of wt%, by the temperature to 115 in reactor ~ 125 DEG C after dripping, reacted rear collection secondary liquid waste, detected the content of remaining DMAPA in secondary liquid waste; Wherein, wt%≤80% and m 2× wt%≤m 1× 10%.
2. the method for process N, N-dimethyl-1,3-propylene diamine waste liquid according to claim 1, is characterized in that: the time for adding of described DMAPA waste liquid is 2 ~ 6h.
3. the method for process N, N-dimethyl-1,3-propylene diamine waste liquid according to claim 1, it is characterized in that: after reactor is warming up to 115 ~ 125 DEG C, the reaction times of described DMAPA waste liquid and lipid acid is 2 ~ 5h.
4. the method for process N, N-dimethyl-1,3-propylene diamine waste liquid according to claim 1, is characterized in that: the content of remaining DMAPA measures in accordance with the following steps: weighing m 3g secondary liquid waste, adds deionized water 30ml, adds tetrabromo-mcresolsulfonphthalein-methyl red mixture indicator 2 that volume ratio is 3:1, with the hydrochloric acid standard solution titration of 0.1M, solution is terminal by green to redness, and it is v ml that note consumes volume, calculates the concentration c=0.1v × 102/ (m of DMAPA 3× 2000).
CN201410796500.0A 2014-12-18 2014-12-18 Method for treating N,N-dimethyl-1,3-propane diamine waste liquor Pending CN104557596A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073433A (en) * 2012-12-17 2013-05-01 浙江赞宇科技股份有限公司 Energy-saving recovery technology of 3-dimethylaminopropylamine (DMAPA)
CN103483215A (en) * 2013-09-30 2014-01-01 南京威尔生物化学有限公司 Green production technology of lauramidopropyl dimethylamine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073433A (en) * 2012-12-17 2013-05-01 浙江赞宇科技股份有限公司 Energy-saving recovery technology of 3-dimethylaminopropylamine (DMAPA)
CN103483215A (en) * 2013-09-30 2014-01-01 南京威尔生物化学有限公司 Green production technology of lauramidopropyl dimethylamine

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Application publication date: 20150429