CN103012656A - Preparation method of macroporous weak-alkaline compound acrylic anion exchange resin - Google Patents

Preparation method of macroporous weak-alkaline compound acrylic anion exchange resin Download PDF

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Publication number
CN103012656A
CN103012656A CN2012104898819A CN201210489881A CN103012656A CN 103012656 A CN103012656 A CN 103012656A CN 2012104898819 A CN2012104898819 A CN 2012104898819A CN 201210489881 A CN201210489881 A CN 201210489881A CN 103012656 A CN103012656 A CN 103012656A
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Prior art keywords
exchange resin
water
warming
preparation
weight part
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CN2012104898819A
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Chinese (zh)
Inventor
姚能平
梅德华
陈建国
林伟
王海宽
王玉兰
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Anhui Wandong Chemical Co Ltd
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Anhui Wandong Chemical Co Ltd
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Priority to CN2012104898819A priority Critical patent/CN103012656A/en
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Abstract

The invention discloses a preparation method of a macroporous weak-alkaline compound acrylic anion exchange resin. Based on the traditional production process, through reasonable matching of a suspending protective agent, a dispersing agent, a pore-foaming agent and a complexing agent and optimizing processing parameters, the anion exchange resin prepared by the method has the effects of uniform pore distribution and improved exchange capacity. According to the preparation method, the specific surface area of the prepared ion exchange resin is more than 60m<2>/g, the proportion of mesopores larger than 2nm is greater than 50%, and the complete exchange capacity reaches 10.5 mmol/g.

Description

The preparation method of macroreticular weakly base composite acrylic acid series anion exchange resin
Technical field
The invention belongs to a kind of preparation method of ion exchange resin, specifically a kind of preparation method of macroreticular weakly base composite acrylic acid series anion exchange resin.
Background technology
Anion and cation exchange resin is widely used for the fields such as the decolouring of the purification of water treatment, material, concentrated, separation, transformation that substance ion forms, material and catalyzer.Although the exchange capacity of present anion and cation exchange resin has obtained effective raising, pore size distribution is uneven, and the aperture ratio is excessive, and exchange velocity is low.The problems such as exchange capacity deficiency do not satisfy client's requirement.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of macroreticular weakly base composite acrylic acid series anion exchange resin, the present invention is by the improvement of water, so that dispersed, suspension raising, and then reach the exchange capacity that increases ion exchange resin, the effect of even aperture distribution.
Technical scheme of the present invention is as follows:
The preparation method of macroreticular weakly base composite acrylic acid series anion exchange resin is characterized in that may further comprise the steps:
(1), polymerization prepares A material, may further comprise the steps:
Figure 529338DEST_PATH_IMAGE002
Prepare in accordance with regulations the water of following weight part, mixing and stirring;
Deionized water 550-600
Polyvinyl alcohol 22-25
Ethanol 10-15
Diethylenetriamine 15-20
Vitriolate of tartar 45-50
Tripoly phosphate sodium STPP 20-25
Ammonium persulphate 1-2
It is neutral transferring PH with sulfuric acid
Figure 679697DEST_PATH_IMAGE004
Take by weighing the raw material of following weight part, aqueous phase after adding after mixing is adjusted mixing speed depending on the granularity situation;
Methyl acrylate 320-340
Divinylbenzene 50-55
Vinyl cyanide 7-9
200# gasoline 158-163
Ferrocene 8-10
Diisopropyl azodicarboxylate 3-5
Figure 9047DEST_PATH_IMAGE006
Slowly be warming up to 65-69 ℃, note observing spheroid granularity and typing situation;
Figure 332581DEST_PATH_IMAGE008
Heat release during typing, cooling maintains the temperature at 68-70 ℃ after the heat release, be incubated 2-3 hour;
Figure 798197DEST_PATH_IMAGE010
Be warming up to 80-82 ℃ of insulation 3-4h with the 25-40 minutes;
Figure 119457DEST_PATH_IMAGE012
With 92-96 ℃ of insulation of 50-70 minutes intensification 4-5h;
Figure 1350DEST_PATH_IMAGE014
With the hot water wash nodule number all over till limpid to water;
Figure 800679DEST_PATH_IMAGE016
Drain water, oven dry, sub-sieve makes the A material.
(2), amination reaction prepares the B material
Figure 386381DEST_PATH_IMAGE002
Press the row weight part and take by weighing following raw materials according, in clean reactor, add A material and tetraethylene pentamine etc., start stirring;
A expects 380-420
Tetraethylene pentamine 1580-1620
Dimethylbenzene 80-90
EDTA 30-35
Figure 878542DEST_PATH_IMAGE004
Be warming up to 130-135 ℃, insulation reaction 15-18h, the control exchange is qualified greater than 8.0mmol/g in the survey;
Figure 916905DEST_PATH_IMAGE006
After middle control is qualified, take out mother liquor;
Figure 582242DEST_PATH_IMAGE008
Massive laundering is drained to neutral, gets the B material;
(3), methylation reaction prepares resin
Figure 285100DEST_PATH_IMAGE002
The B material is added in the mixing raw material of following weight part, start stirring;
Formic acid 1150-1250
Water 200-240
Formaldehyde 60-65
Citric acid 10-15
Be warming up to 48-50 ℃, kept 20-40 minute;
Drain mother liquor, massive laundering is drained to neutral, washing, dry, discharging.
The present invention is by reasonably combined suspension protective material, dispersion agent, pore-creating agent, complexing agent; Optimizing Process Parameters, so that the anionite-exchange resin of present method preparation, pore size distribution is uneven; the effect that exchange capacity improves, the ion exchange resin specific surface area that the present invention makes can reach 60m 2More than/the g, greater than 50%, complete exchange capacity reaches 10.5mmol/g greater than the mesopore ratio of 2nm.
Embodiment
The preparation method of macroreticular weakly base composite acrylic acid series anion exchange resin may further comprise the steps:
(1), polymerization prepares A material, may further comprise the steps:
Figure 614953DEST_PATH_IMAGE002
Prepare in accordance with regulations the water of following weight (kilogram), mixing and stirring;
Deionized water 550
Polyvinyl alcohol 22
Ethanol 10
Diethylenetriamine 15
Vitriolate of tartar 45
Tripoly phosphate sodium STPP 20
Ammonium persulphate 1
It is neutral transferring PH with sulfuric acid
Take by weighing the raw material of following weight (kilogram), aqueous phase after adding after mixing is adjusted mixing speed depending on the granularity situation;
Methyl acrylate 320
Divinylbenzene 50
Vinyl cyanide 7
200# gasoline 158
Ferrocene 8
Diisopropyl azodicarboxylate 3
Figure 743632DEST_PATH_IMAGE006
Slowly be warming up to 65-69 ℃, note observing spheroid granularity and typing situation;
Figure 22167DEST_PATH_IMAGE008
Heat release during typing, cooling maintains the temperature at 68-70 ℃ after the heat release, be incubated 2-3 hour;
Figure 966989DEST_PATH_IMAGE010
Be warming up to 80-82 ℃ of insulation 3-4h with the 25-40 minutes;
Figure 384720DEST_PATH_IMAGE012
With 92-96 ℃ of insulation of 50-70 minutes intensification 4-5h;
Figure 389585DEST_PATH_IMAGE014
With the hot water wash nodule number all over till limpid to water;
Figure 889836DEST_PATH_IMAGE016
Drain water, oven dry, sub-sieve makes the A material.
(2), amination reaction prepares the B material
Figure 372770DEST_PATH_IMAGE002
Press column weight amount (kilogram) and take by weighing following raw materials according, in clean reactor, add A material and tetraethylene pentamine etc., start stirring;
A material 380
Tetraethylene pentamine 1580
Dimethylbenzene 80
EDTA 30
Figure 907657DEST_PATH_IMAGE004
Be warming up to 130-135 ℃, insulation reaction 15-18h, the control exchange is qualified greater than 8.0mmol/g in the survey;
Figure 817844DEST_PATH_IMAGE006
After middle control is qualified, take out mother liquor;
Figure 805391DEST_PATH_IMAGE008
Massive laundering is drained to neutral, gets the B material;
(3), methylation reaction prepares resin
Figure 92016DEST_PATH_IMAGE002
The B material is added in the mixing raw material of following weight (kilogram), start stirring;
Formic acid 1150
Water 200
Formaldehyde 60
Citric acid 10
Be warming up to 48-50 ℃, kept 20-40 minute;
Figure 825147DEST_PATH_IMAGE006
Drain mother liquor, massive laundering is drained to neutral, washing, dry, discharging.
The ion exchange resin specific surface area that the present invention makes can reach 60m 2More than/the g, greater than 50%, complete exchange capacity reaches 10.5mmol/g greater than the mesopore ratio of 2nm.

Claims (1)

1. the preparation method of macroreticular weakly base composite acrylic acid series anion exchange resin is characterized in that may further comprise the steps:
(1), polymerization prepares A material, may further comprise the steps:
Prepare in accordance with regulations the water of following weight part, mixing and stirring;
Deionized water 550-600
Polyvinyl alcohol 22-25
Ethanol 10-15
Diethylenetriamine 15-20
Vitriolate of tartar 45-50
Tripoly phosphate sodium STPP 20-25
Ammonium persulphate 1-2
It is neutral transferring PH with sulfuric acid
Figure 576663DEST_PATH_IMAGE002
Take by weighing the raw material of following weight part, aqueous phase after adding after mixing is adjusted mixing speed depending on the granularity situation;
Methyl acrylate 320-340
Divinylbenzene 50-55
Vinyl cyanide 7-9
200# gasoline 158-163
Ferrocene 8-10
Diisopropyl azodicarboxylate 3-5
Slowly be warming up to 65-69 ℃, note observing spheroid granularity and typing situation;
Figure 2012104898819100001DEST_PATH_IMAGE003
Heat release during typing, cooling maintains the temperature at 68-70 ℃ after the heat release, be incubated 2-3 hour;
Figure 526034DEST_PATH_IMAGE004
Be warming up to 80-82 ℃ of insulation 3-4h with the 25-40 minutes;
Figure 2012104898819100001DEST_PATH_IMAGE005
With 92-96 ℃ of insulation of 50-70 minutes intensification 4-5h;
Figure 78588DEST_PATH_IMAGE006
With the hot water wash nodule number all over till limpid to water;
Drain water, oven dry, sub-sieve makes the A material;
(2), amination reaction prepares the B material
Press the row weight part and take by weighing following raw materials according, in clean reactor, add A material and tetraethylene pentamine etc., start stirring;
A expects 380-420
Tetraethylene pentamine 1580-1620
Dimethylbenzene 80-90
EDTA 30-35
Figure 748177DEST_PATH_IMAGE002
Be warming up to 130-135 ℃, insulation reaction 15-18h, the control exchange is qualified greater than 8.0mmol/g in the survey;
Figure 376605DEST_PATH_IMAGE008
After middle control is qualified, take out mother liquor;
Massive laundering is drained to neutral, gets the B material;
(3), methylation reaction prepares resin
The B material is added in the mixing raw material of following weight part, start stirring;
Formic acid 1150-1250
Water 200-240
Formaldehyde 60-65
Citric acid 10-15
Figure 612917DEST_PATH_IMAGE002
Be warming up to 48-50 ℃, kept 20-40 minute;
Figure 779456DEST_PATH_IMAGE008
Drain mother liquor, massive laundering is drained to neutral, washing, dry, discharging.
CN2012104898819A 2012-11-27 2012-11-27 Preparation method of macroporous weak-alkaline compound acrylic anion exchange resin Pending CN103012656A (en)

Priority Applications (1)

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CN103012656A true CN103012656A (en) 2013-04-03

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85104153A (en) * 1985-06-03 1986-12-03 核工业部北京第五研究所 The synthetic method of acrylate type weakly basic anionic ionexchange resin
WO2001087483A1 (en) * 2000-05-18 2001-11-22 Mitsubishi Chemical Corporation Anion-exchange resin
CN102234352A (en) * 2011-04-20 2011-11-09 安徽美佳新材料股份有限公司 Preparation method of D213 macroporous strong-basic acrylic cation exchange resin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85104153A (en) * 1985-06-03 1986-12-03 核工业部北京第五研究所 The synthetic method of acrylate type weakly basic anionic ionexchange resin
WO2001087483A1 (en) * 2000-05-18 2001-11-22 Mitsubishi Chemical Corporation Anion-exchange resin
CN102234352A (en) * 2011-04-20 2011-11-09 安徽美佳新材料股份有限公司 Preparation method of D213 macroporous strong-basic acrylic cation exchange resin

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Application publication date: 20130403