Background
Dimethyldiallylammonium Chloride (abbreviated as DMDAAC) is a quaternary ammonium salt monomer containing two unsaturated double bonds, and is mainly used for participating in free radical polymerization to prepare homopolymers and copolymers thereof. The molecular structures of the homopolymer and the copolymer have the advantages of high relative density of positive charges carried on a macromolecular chain, good water solubility, easy control of relative molecular mass, high efficiency, no toxicity and the like, and are widely applied to the fields of papermaking, oil exploitation, spinning, printing and dyeing, daily chemicals, water treatment, electronic chemicals and the like.
As soon as 60 s in the 20 th century, since Dr.George B button in the United states synthesized DMDAAC, Calgon and Nalco chemical in the United states successively improved the synthesis method and put it into industrial production. The current methods for synthesizing monomers can be summarized into a one-step method and a two-step method according to the operation process. The one-step synthesis is that tertiary amine generated by tertiary amination of dimethylamine and chloropropene directly reacts with chloropropene without separation to generate DMDAAC. The two-step method is that dimethylamine reacts with chloropropene to generate tertiary amine under the alkaline condition, and the tertiary amine obtained after distillation is reacted with chloropropene in acetone to generate DMDAAC after distillation separation. In the monomer synthesis process, whether a one-step method or a two-step method is adopted, the monomer solution obtained by synthesis inevitably contains impurity components such as tertiary amine, dimethylamine hydrochloride, tertiary amine hydrochloride, allyl alcohol and the like. These impurities may affect the quality level and application range of the DMDAAC-based polymer.
In particular, the presence of formaldehyde as a by-product has also been detected in the monomers of DMDAAC synthesized industrially, since in the products of polymers based on DMDAAC, formaldehyde is more or less contained, and therefore the widespread use thereof is subject to numerous restrictions, particularly the partial product export hindered by the fact that the content of formaldehyde in trace amounts does not reach standards. The formaldehyde source for the product is generally considered to be mostly from the monomer synthesis process. In recent years, many documents report methods for removing formaldehyde from plant wastewater, and no document is reported about the method for removing trace formaldehyde from DMDAAC monomer.
At present, the methods for treating wastewater containing a small amount of formaldehyde mainly comprise an oxidation method, a stripping method, a biological treatment method, a nucleophilic addition method of sodium bisulfite and the like. However, these methods have some disadvantages, such as expensive oxidation method equipment and treatment cost, the blow-off method is only suitable for pretreatment of high-concentration formaldehyde wastewater, the biological treatment method is only suitable for treatment of low-concentration formaldehyde wastewater (the content is less than or equal to 0.1 percent), and the nucleophilic addition method of sodium bisulfite is only suitable for advanced treatment of formaldehyde-containing wastewater. Due to the disadvantages of each of the above methods, and the characteristics of the DMDAAC monomer, none of the above methods solves the problem of reducing the amount of formaldehyde in a trace amount contained in the DMDAAC monomer.
In the literature (georgi, georey, royal, Anle, plum sea, Jiangxu, Zhanlian beam. test research on detoxification pretreatment of formaldehyde-containing wastewater [ J ] environmental engineering, 2015,33(S1): 263-266.) pretreatment is carried out on high-concentration formaldehyde wastewater by adopting a sodium bisulfite method. The initial formaldehyde concentration is 2595.69mg/L, the reaction temperature is 20 ℃, the pH value is 6.2, the molar ratio of sodium bisulfite to formaldehyde is 1:1, the reaction lasts for 10min, and the removal rate of formaldehyde in the wastewater reaches more than 99%. However, sodium bisulfite in this process affects the polymerization activity of the monomer DMDAAC and is therefore not suitable for removing formaldehyde from DMDAAC monomer.
Chinese patent CN1335271A discloses a formaldehyde wastewater treatment process, which comprises atomizing formaldehyde wastewater, spraying the atomized formaldehyde wastewater on furnace slag just coming out of a boiler, and cracking the formaldehyde wastewater into CO when encountering high temperature and oxygen2And H2And O, discharging into the atmosphere, and adsorbing the residual trace formaldehyde by porous furnace slag. This method is not suitable for the treatment of formaldehyde in DMDAAC monomers.
Chinese patent CN101497617 discloses a method for producing urotropine by using formaldehyde-containing wastewater, wherein ammonia is added into the wastewater containing 0.5-5.0% of formaldehyde by mass fraction, the temperature is 10-90 ℃, the preferred temperature is 40-60 ℃, and the urotropine dilute solution is obtained by stirring and reacting. Filtering to remove solid component, filtering viscous liquid of dilute solution of urotropine with active carbon, filtering with filter membrane to remove impurities and floccule, treating with membrane, and discharging or using in industrial circulating water. The method is used for treating wastewater with formaldehyde concentration of 0.5-5.0% (5000-50000 mg/L), so that the method is not suitable for treating trace formaldehyde and trace formaldehyde in a DMDAAC monomer.
In summary, no literature report on the formaldehyde removal method in DMDAAC monomer is found so far. The problem that the DMDAAC monomer contains trace and trace formaldehyde is solved, the core competitiveness of DMDAAC monomer production enterprises is increased, the sales range of polymer products based on DMDAAC can be expanded, and the influence of the enterprises is enlarged, so that the problem is urgently solved.
Disclosure of Invention
The invention aims to provide a method for reducing trace and trace formaldehyde in an industrial DMDAAC monomer solution.
The technical solution for realizing the purpose of the invention is as follows: a method for reducing trace and trace formaldehyde contained in an industrial monomer DMDAAC solution comprises the steps of putting dehydrated activated carbon into a closed methylamine or dimethylamine atmosphere for fumigation to obtain modified activated carbon; adding a certain amount of modified activated carbon into an industrial monomer DMDAAC solution with the mass fraction of 20% -65% at the temperature of 35-60 ℃ under the stirring condition for adsorption and reaction for 1.0-4.0 h, and filtering the reaction solution while the reaction solution is hot to obtain the DMDAAC monomer solution, wherein the formaldehyde content is reduced by 50% -80%.
Preferably, the mass content of the DMDAAC in the industrial monomer DMDAAC solution is 20-65%, and the concentration of trace formaldehyde contained in the solution is 50-200 mg/L.
Preferably, the modified activated carbon is modified by drying the activated carbon at 110-120 ℃ for more than 2.0h, fully dehydrating, and quickly fumigating in a sealed methylamine or dimethylamine atmosphere for more than 0.5h, wherein the activated carbon is wood, bamboo, coal powder activated carbon or fruit shell activated carbon with the particle size of less than 75 microns.
Preferably, the addition amount of the modified activated carbon accounts for 0.1-2.0 wt% of the total mass of the industrial monomer DMDAAC solution.
Preferably, the temperature of the adsorption and reaction is 35-60 ℃.
Compared with the prior art, the invention has the following remarkable advantages:
(1) according to the adsorption principle of the activated carbon, the activated carbon (modified activated carbon) is adopted for the first time to adsorb formaldehyde in the industrial monomer DMDAAC solution, and the method can reduce the content of formaldehyde in the DMDAAC monomer, is simple and convenient to operate and can be popularized in a DMDAAC factory on a large scale on the premise of not influencing the polymerization activity of the DMDAAC monomer.
(2) According to the principle that the formaldehyde containing carbonyl polar groups can be condensed with-N-H bonds to generate derivatives of ammonia and then removed, the dried activated carbon is kept for more than 0.5H in methylamine or dimethylamine atmosphere to form an activated formaldehyde adsorbate, and finally the adsorption performance of the activated carbon on formaldehyde is improved through the combined action of chemical adsorption and physical adsorption.
(3) After the formaldehyde in the DMDAAC monomer is treated by the formaldehyde reduction method, the formaldehyde content in the obtained DMDAAC monomer solution can be reduced by 50-80%, and the lowest formaldehyde content in the monomer DMDAAC solution can reach about 10 mg/L.
Detailed Description
The technique of the present invention will be described below with reference to examples.
The technical solution for realizing the purpose of the invention is as follows:
the invention relates to a method for reducing formaldehyde contained in industrial monomer DMDAAC. Drying the activated carbon at the temperature of 110-120 ℃ for more than 2.0h, fully dehydrating, and quickly putting the activated carbon in a sealed methylamine or dimethylamine atmosphere for fumigating for more than 0.5h to obtain the modified activated carbon. Adding a certain amount of modified activated carbon into an industrial monomer DMDAAC solution with the mass fraction of 20% -65% at the temperature of 35-60 ℃ under the stirring condition for adsorption and reaction for 1.0-4.0 h, filtering the reaction solution while the reaction solution is hot to obtain a DMDAAC monomer solution, wherein the formaldehyde content in the DMDAAC monomer can be reduced by 50% -80%.
Example 1
Firstly, drying wooden powdery activated carbon with the particle size of less than 75 microns at the temperature of 110 ℃ for more than 2.0h, and fully dehydrating;
secondly, quickly putting the fully dehydrated activated carbon obtained in the first step into a closed methylamine atmosphere for fumigation for 0.5h for modification to obtain modified wood powdery activated carbon;
feeding a DMDAAC monomer solution with the monomer mass fraction of 20% into a reactor with a stirring device, wherein the formaldehyde content in the DMDAAC monomer solution is 50 mg/L;
fourthly, adding modified wood powdery activated carbon accounting for 0.1 percent of the total mass fraction into the DMDAAC solution to obtain reaction liquid;
fifthly, heating the reaction solution to 50.0 +/-1.0 ℃, and reacting for 4.0h under the condition of stirring;
and sixthly, filtering the reaction solution while the reaction solution is hot to obtain a DMDAAC filtrate, wherein the concentration of formaldehyde in the DMDAAC filtrate is 25mg/L, and the content of formaldehyde in the DMDAAC monomer can be reduced by 50%.
Example 2
Firstly, drying wooden powdery activated carbon with the particle size of less than 75 microns at the temperature of 110 ℃ for more than 2.0h, and fully dehydrating;
secondly, quickly putting the fully dehydrated activated carbon obtained in the first step into a sealed dimethylamine atmosphere for fumigation for 0.5h for modification to obtain modified wood powdery activated carbon;
feeding a DMDAAC monomer solution with the monomer mass fraction of 20% into a reactor with a stirring device, wherein the formaldehyde content in the DMDAAC monomer solution is 50 mg/L;
fourthly, adding modified wood powdery activated carbon accounting for 0.1 percent of the total mass fraction into the DMDAAC solution to obtain reaction liquid;
fifthly, heating the reaction solution to 50.0 +/-1.0 ℃, and reacting for 4.0h under the condition of stirring;
and sixthly, filtering the reaction solution while the reaction solution is hot to obtain a DMDAAC filtrate, wherein the concentration of formaldehyde in the DMDAAC filtrate is 18mg/L, and the content of formaldehyde in the DMDAAC monomer can be reduced by 64%.
Example 3
Firstly, drying wooden powdery activated carbon with the particle size of less than 75 microns at the temperature of 110 ℃ for more than 2.0h, and fully dehydrating;
secondly, quickly putting the fully dehydrated activated carbon obtained in the first step into a sealed dimethylamine atmosphere for fumigation for 0.5h for modification to obtain modified wood powdery activated carbon;
feeding a DMDAAC monomer solution with the monomer mass fraction of 20% into a reactor with a stirring device, wherein the formaldehyde content in the DMDAAC monomer solution is 50 mg/L;
fourthly, adding modified wood powdery activated carbon accounting for 1.3 percent of the total mass fraction into the DMDAAC solution to obtain reaction liquid;
fifthly, heating the reaction solution to 50.0 +/-1.0 ℃, and reacting for 4.0h under the condition of stirring;
and sixthly, filtering the reaction solution while the reaction solution is hot to obtain a DMDAAC filtrate, wherein the concentration of formaldehyde in the DMDAAC filtrate is 10mg/L, and the content of formaldehyde in the DMDAAC monomer can be reduced by 80%.
Example 4
Firstly, drying wooden powdery activated carbon with the particle size of less than 75 microns at the temperature of 110 ℃ for more than 2.0h, and fully dehydrating;
secondly, quickly putting the fully dehydrated activated carbon obtained in the first step into a sealed dimethylamine atmosphere for fumigation for 0.5h for modification to obtain modified wood powdery activated carbon;
feeding a DMDAAC monomer solution with the monomer mass fraction of 20% into a reactor with a stirring device, wherein the formaldehyde content in the DMDAAC monomer solution is 50 mg/L;
fourthly, adding modified wood powdery activated carbon accounting for 2.0 percent of the total mass fraction into the DMDAAC solution to obtain reaction liquid;
fifthly, heating the reaction solution to 50.0 +/-1.0 ℃, and reacting for 4.0h under the condition of stirring;
and sixthly, filtering the reaction solution while the reaction solution is hot to obtain a DMDAAC filtrate, wherein the concentration of formaldehyde in the DMDAAC filtrate is 13mg/L, and the content of formaldehyde in the DMDAAC monomer can be reduced by 74%.
Example 5
Firstly, drying wooden powdery activated carbon with the particle size of less than 75 microns at the temperature of 110 ℃ for more than 2.0h, and fully dehydrating;
secondly, quickly putting the fully dehydrated activated carbon obtained in the first step into a sealed dimethylamine atmosphere for fumigation for 0.5h for modification to obtain modified wood powdery activated carbon;
feeding a DMDAAC monomer solution with the monomer mass fraction of 20% into a reactor with a stirring device, wherein the formaldehyde content in the DMDAAC monomer solution is 50 mg/L;
fourthly, adding modified wood powdery activated carbon accounting for 1.3 percent of the total mass fraction into the DMDAAC solution to obtain reaction liquid;
fifthly, heating the reaction solution to 50.0 +/-1.0 ℃, and reacting for 1.0h under the condition of stirring;
and sixthly, filtering the reaction solution while the reaction solution is hot to obtain a DMDAAC filtrate, wherein the concentration of formaldehyde in the DMDAAC filtrate is 25mg/L, and the content of formaldehyde in the DMDAAC monomer can be reduced by 50%.
Example 6
Firstly, drying wooden powdery activated carbon with the particle size of less than 75 microns at the temperature of 110 ℃ for more than 2.0h, and fully dehydrating;
secondly, quickly putting the fully dehydrated activated carbon obtained in the first step into a sealed dimethylamine atmosphere for fumigation for 0.5h for modification to obtain modified wood powdery activated carbon;
feeding a DMDAAC monomer solution with the monomer mass fraction of 20% into a reactor with a stirring device, wherein the formaldehyde content in the DMDAAC monomer solution is 50 mg/L;
fourthly, adding modified wood powdery activated carbon accounting for 1.3 percent of the total mass fraction into the DMDAAC solution to obtain reaction liquid;
fifthly, heating the reaction solution to 50.0 +/-1.0 ℃, and reacting for 3.0h under the condition of stirring;
and sixthly, filtering the reaction solution while the reaction solution is hot to obtain a DMDAAC filtrate, wherein the concentration of formaldehyde in the DMDAAC filtrate is 15mg/L, and the content of formaldehyde in the DMDAAC monomer can be reduced by 70%.
Example 7
Firstly, drying wooden powdery activated carbon with the particle size of less than 75 microns at the temperature of 110 ℃ for more than 2.0h, and fully dehydrating;
secondly, quickly putting the fully dehydrated activated carbon obtained in the first step into a sealed dimethylamine atmosphere for fumigation for 0.5h for modification to obtain modified wood powdery activated carbon;
feeding a DMDAAC monomer solution with the monomer mass fraction of 20% into a reactor with a stirring device, wherein the formaldehyde content in the DMDAAC monomer solution is 50 mg/L;
fourthly, adding modified wood powdery activated carbon accounting for 1.3 percent of the total mass fraction into the DMDAAC solution to obtain reaction liquid;
fifthly, heating the reaction solution to 35.0 +/-1.0 ℃, and reacting for 4.0h under the condition of stirring;
and sixthly, filtering the reaction solution while the reaction solution is hot to obtain a DMDAAC filtrate, wherein the concentration of formaldehyde in the DMDAAC filtrate is 30mg/L, and the content of formaldehyde in the DMDAAC monomer can be reduced by 40%.
Example 8
Firstly, drying wooden powdery activated carbon with the particle size of less than 75 microns at the temperature of 110 ℃ for more than 2.0h, and fully dehydrating;
secondly, quickly putting the fully dehydrated activated carbon obtained in the first step into a sealed dimethylamine atmosphere for fumigation for 0.5h for modification to obtain modified wood powdery activated carbon;
feeding a DMDAAC monomer solution with the monomer mass fraction of 20% into a reactor with a stirring device, wherein the formaldehyde content in the DMDAAC monomer solution is 50 mg/L;
fourthly, adding modified wood powdery activated carbon accounting for 1.3 percent of the total mass fraction into the DMDAAC solution to obtain reaction liquid;
fifthly, heating the reaction solution to 60.0 +/-1.0 ℃, and reacting for 4.0h under the condition of stirring;
and sixthly, filtering the reaction solution while the reaction solution is hot to obtain a DMDAAC filtrate, wherein the concentration of formaldehyde in the DMDAAC filtrate is 20mg/L, and the content of formaldehyde in the DMDAAC monomer can be reduced by 60%.
Comparative example 1
Firstly, feeding a DMDAAC monomer solution with the monomer mass fraction of 20% into a reactor with a stirring device, wherein the formaldehyde content in the DMDAAC monomer solution is 50 mg/L;
secondly, adding unactivated wood powdery activated carbon accounting for 1.3 percent of the total mass fraction into the DMDAAC solution to obtain reaction liquid;
thirdly, heating the reaction solution to 50.0 +/-1.0 ℃, and reacting for 4.0h under the condition of stirring;
and fourthly, filtering the reaction solution while the reaction solution is hot to obtain DMDAAC filtrate, wherein the formaldehyde concentration of the DMDAAC filtrate is 35mg/L, and the formaldehyde content in the DMDAAC monomer can be reduced by 30%.
Table 1 below is a summary of the various process parameters versus test results in the examples and comparative examples.
TABLE 1
Name (R)
|
DMDAAC /%
|
Formaldehyde content/(mg.L)-1)
|
Activated carbon addition/%)
|
Species of
|
Reaction t/h
|
Reaction T/. degree.C
|
Residual concentration of formaldehyde/(mg.L)-1)
|
Reduction rate/%)
|
Range of
|
20-65
|
50-200
|
0.1~2.0
|
Wood, coal, fruit and bamboo
|
1~4
|
35~60
|
Greater than 10
|
50-80
|
Example 1
|
20
|
50
|
0.1
|
Methylamine-wood
|
4
|
50
|
25
|
50
|
Example 2
|
20
|
50
|
0.1
|
Dimethylamine-wood
|
4
|
50
|
18
|
64
|
Example 3
|
20
|
50
|
1.3
|
Dimethylamine wood
|
4
|
50
|
10
|
80
|
Example 4
|
20
|
50
|
2
|
Dimethylamine-wood
|
4
|
50
|
13
|
74
|
Example 5
|
20
|
50
|
1.3
|
Dimethylamine wood
|
1
|
50
|
25
|
50
|
Example 6
|
20
|
50
|
1.3
|
Dimethylamine wood
|
3
|
50
|
15
|
70
|
Example 7
|
20
|
50
|
1.3
|
Dimethylamine wood
|
4
|
35
|
30
|
40
|
Example 8
|
20
|
50
|
1.3
|
Dimethylamine wood
|
4
|
60
|
20
|
60
|
Comparative example 1
|
20
|
50
|
1.3
|
Non-activated wood
|
4
|
50
|
35
|
30 |