CN103709387B - Production method of polyepoxysuccinic acid - Google Patents
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Abstract
A kind of Production method of polyepoxysuccinic acid is with toxilic acid and hydrogen peroxide for main raw material, with having adsorbed WO
4 2-macroporous resin make catalyzer, adopt inhomogeneous reaction technique, under the initiation of calcium hydroxide composite initiator, after pre-treatment, oxidizing reaction, polyreaction, obtain the poly-epoxy succinic acid product that scale inhibition effect is good.
Description
Technical field
The present invention relates to a kind of water conditioner agent, the particularly production method of dirt dispersion agent poly-epoxy succinic acid water conditioner.
Background technology
Poly-epoxy succinic acid (sodium) is a kind of excellent environment-friendly type Scale Inhibitors for Water, and it is successively obtained after hydrolysis, epoxidation, polyreaction by MALEIC ANHYDRIDE.
As far back as the end of the fifties in last century, George and Paul has just had been found that under sodium wolframate makes the condition of catalyzer, and hydrogen peroxide can make toxilic acid generate Epoxysuccinic acid under certain reaction conditions.Concrete reaction is as follows.
Maleic anhydride toxilic acid (salt) Epoxysuccinic acid (salt)
The people such as Hosoi comparatively early compare systematic research to the synthesis of Epoxysuccinic acid, give the scope of proper each reaction conditions (comprising the pH value of reaction system, temperature of reaction, the reaction times), under the reaction conditions of its best, their reaction yield can reach more than 95%.In each reaction conditions, especially pH value is the most important: the too low meeting of pH value impels Epoxysuccinic acid that hydrolysis reaction generation tartrate occurs further, and its reaction process is as follows; PH value is too high, can impel the peroxide decomposition in reaction system, reduces the yield of epoxidation reaction, so the pH value of the best of this reaction is confirmed as between 6 to 10.Higher owing to adopting tungstate to make catalyzer cost, the people such as Hosoi take into account the recycling problem of catalyzer in their research process, after reaction terminates, adopt ion exchange resin from reaction solution, be swapped out catalyzer sodium wolframate, carry out purification and reclaim.The people such as Sato, in order to the tartaric generation of the by product in inhibited reaction, adopt ethanol as solvent, achieve certain effect.
The domestic people of having has carried out some research work in this regard, Institutes Of Technology Of Nanjing Lv Zhi virtue, Dong Wei etc. are on the principal element affecting epoxy succinic acid yield in experiment: reaction times, temperature of reaction, catalyst levels and sodium hydroxide concentration are investigated. obtain the top condition of synthesizing epoxy succsinic acid: reaction times 1h, temperature of reaction about 60 DEG C, catalyst levels is about 1% of maleic anhydride amount of substance, sodium hydroxide is about 2: 1 with maleic anhydride amount ratio, and the yield of Epoxysuccinic acid can reach 96.8%.
Epoxysuccinic acid polymerization reaction take place under the effect of initiator generates poly-epoxy succinic acid (PESA), and reaction process is as follows.
At a certain temperature, adding initiator can impel Epoxysuccinic acid to be polymerized.Someone adopts boron trifluoride as initiator the earliest, but effect is not fine.Now, for this reaction, the good initiator of effect of general application is the calcium hydroxide solid that the people such as Bush study discovery.According to their achievement in research, the add-on of calcium hydroxide solid calculates with molar percentage, and minimum should be 5%, and optimum range should be between 10-85%.The people such as Brown have carried out the development research of the Scale inhibitors of poly-epoxy succinic acid, and, find that the poly-epoxy succinic acid of the polymerization degree between 2-11 is relatively suitable for making Scale inhibitors.The optimum polymerization degree is 2-4, and its scale inhibition effect is best.
Poly-epoxy succinic acid (PESA) is a kind of without nitrogen, non-phosphorus organic compound, and have scale inhibitor double effects concurrently, biodegradability is got well and is applicable to high-alkali, high metal content water system, is a kind of green Water Treatment Chemicals.About with toxilic acid (maleic acid) acid anhydride for raw material, the mixture based on sodium wolframate is catalyzer, and hydrogen peroxide is oxygenant, and sodium hydroxide is the technical study of initiator synthesis poly-epoxy succinic acid, domestic more existing open source literature report, as:
The Liang Baofeng at chemical research center, CNPC Lanzhou; Yang Yue epoxy amber has been delivered: the article of the study on the synthesis of amber acid and polymkeric substance thereof; periodical name: petrochemical technology and application; 01 phase summary in 2008: first with maleic anhydride (MA) for raw material; sodium wolframate is main mixture is catalyzer; hydrogen peroxide is oxygenant; NaOH is initiator, synthesizes Epoxysuccinic acid (ESA); Then with Ca (OH) 2 for initiator, aggregate into poly-epoxy succinic acid (PESA) further, and infrared spectrum characterization carried out to them.The best synthetic technological condition of ESA and PESA is determined by orthogonal experiment.Result shows, the best synthetic technological condition of ESA is: temperature of reaction 60 DEG C, n (MA)/n (NaOH) value 1.0: 2.0, and the reaction times is about 1.5h, the consumption 1.0% of composite catalyst; The best synthetic technological condition of PESA synthesis is: temperature of reaction 85 DEG C, and the reaction times is about 1.5h, and it is 2 times that n [Ca (OH) 2]/n (MA) value 1: 3, Ca (OH) 2 adds lot number; ESA at optimum conditions, PESA yield is respectively 95.7%, 93.7%.
Chinese patent discloses title: the preparation method of poly-epoxy succinic acid and salt thereof, and Application Number (patent): CN03124258.8 applies for (patent right) people: University Of Tianjin, Main classification number: C07C59/305, principal claim: the 1. preparation method of a poly-epoxy succinic acid and salt thereof, the method is 1: 4 ~ 30 by the mol ratio of MALEIC ANHYDRIDE and water, MALEIC ANHYDRIDE is dissolved in water and generates maleic acid, add sodium hydroxide until pH=5 ~ 7, sodium wolframate is added by 0.1 ~ 10% of maleic acid mole number, at 50 ~ 100 DEG C, add aqueous hydrogen peroxide solution continuously, total add-on of hydrogen peroxide is 1.0 ~ 1.2 times of maleic acid mole number, joining day 30min ~ 6h, keep pH=5 ~ 7 with sodium hydroxide simultaneously, generate epoxy sodium succinate, add calcium hydroxide and sodium hydroxide polyase 13 0min ~ 8h at 80 ~ 100 DEG C again, obtain polyepoxy sodium succinate salt, maybe incite somebody to action to obtain the acidified poly-epoxy succinic acid that can obtain of polyepoxy sodium succinate, it is characterized in that, be that 1: 0.01 ~ 0.05 to add calcium hydroxide be catalyzer by epoxy sodium succinate and calcium hydroxide mol ratio, add pH=10 ~ 13 of sodium hydroxide regulation system simultaneously, obtain the low polyepoxy sodium succinate salt of calcium ion content or poly-epoxy succinic acid.
But in the poly-epoxy succinic acid synthesising process research of above-mentioned open source literature report, tungstate catalysts does not have fixed system in system, and thus reaction for some time easily scatters and disappears, and constantly will add, cause cost higher.
Summary of the invention
The object of this invention is to provide a kind of production method of dirt dispersion agent poly-epoxy succinic acid water conditioner, scale inhibition performance is greater than 95%.
A kind of Production method of polyepoxysuccinic acid, for main raw material with maleic anhydride and hydrogen peroxide, by tungstate catalysts, adopt inhomogeneous reaction technique, under the initiation of composite initiator, after pre-treatment, oxidizing reaction, polyreaction, obtain the poly-epoxy succinic acid product meeting scale inhibition effect;
Described maleic anhydride: the mol ratio of hydrogen peroxide is 1:1-1.3;
Described tungstate catalysts has adsorbed WO
4 2-macroporous resin, catalyst levels is the 0.2-1.2% of total inventory;
Described oxidizing reaction adds cis-butenedioic anhydride in the reactor, and add the NaOH solution that weight percent is 50%, adjust ph is 8-8.5, and put into and adsorbed WO
4 2-macroporous resin, in 60-85 DEG C and whipped state downhill reaction system, drip the H of weight content 30%
2o
2, after dropwising, reaction proceeds 1-3h, after reaction terminates, collects reaction solution and resin catalyst;
Described polyreaction is regulated by reaction solution pH to be 8 and temperature 70-95 DEG C, adds the composite initiator of weight content 5-10%, polyreaction 1-3h, the poly-epoxy succinic acid product obtained.
Described has adsorbed WO
4 2-the preparation process of macroporous resin be: select vinylbenzene macroporous resin, embathe clean, exchange with 1N sodium hydroxide, make it after water outlet pH is 8-10, obtain strong basic ion exchange resin with deionized water rinsing; Again with the weight content 5%Na prepared in advance
2wO
4solution soaking or with resin column exchange, make the OH in resin
-by WO
4 2-replaced, obtained having adsorbed WO
4 2-large pore anion resin.
The scale inhibition performance of described poly-epoxy succinic acid product is greater than 85%.
The preparation of described composite initiator mixes in aqueous sodium hydroxide solution saturated limewater being added 50%.
Described vinylbenzene macroporous resin is D209, D296 and D301 macroporous resin.
Resin catalyst 1N sodium hydroxide after above-described oxidizing reaction exchanges again, and alkali cleaning and pickling, adsorbed WO
4 2-after catalyzer, repeated multiple times use, does not affect catalytic effect.
The scale inhibition performance of above-described poly-epoxy succinic acid product is greater than 95%.
Scale-inhibiting properties is (to hinder CaC0
3dirt meter) measuring method:
With deionized water preparation 500mL test solution, wherein containing the poly-epoxy succinic acid water conditioner of a certain amount of (20mg/L), 600mg/LCa
2+with the HC0 of 1200mg/L
3 -(all with CaC0
3meter), regulate pH=7, by this test solution constant temperature l0h in 80 DEG C of water-baths, after being cooled to room temperature, filter, get 10mL filtrate, add 40ml deionized water, the KOH solution of 5mL200g/L, shakes up and adds about 0.1g calcium monocarboxylic acid indicator, with the standard EDTA titration Ca of 0.01mo1/L
2+.Do the test of blank test solution simultaneously.Be calculated as follows scale inhibition performance:
In formula: V
0: the volume of the EDTA standardized solution consumed after the blank test solution test of titration, ml;
V
1: the volume of the EDTA standardized solution consumed before the blank test solution test of titration, ml;
V
2: the volume of the EDTA standardized solution that titration consumes after adding the test solution test of water conditioner, ml.
Beneficial effect of the present invention:
1, this invention exploits the catalyzer of the maleic anhydride epoxidation reaction efficiently, repeatedly reused, under the prerequisite reaching homogeneous catalytic reaction effect, expensive tungstate catalysts can be saved.
2, the initiator in polyreaction adopts sodium hydroxide to replace part calcium hydroxide, makes product scale inhibition effect better.
Embodiment
Embodiment 1
1) select vinylbenzene macroporous resin, embathe clean, exchange with 1N sodium hydroxide, make it after water outlet pH is 8-10, obtain strong basic ion exchange resin with deionized water rinsing; Again with the weight content 5%Na prepared in advance
2wO
4solution soaking, makes the OH in resin
-by WO
4 2-replaced, obtained having adsorbed WO
4 2-large pore anion resin.
2) composite initiator preparation, adds saturated limewater in the aqueous sodium hydroxide solution of 50% and mixes.
3) oxidizing reaction, adds cis-butenedioic anhydride in the reactor, and add the NaOH solution that weight percent is 50%, adjust ph is 8-8.5, and puts into and adsorbed WO
4 2-macroporous resin, macroporous resin consumption is 5% of gross weight, drips the H of weight content 30% in 80 DEG C and whipped state downhill reaction system
2o
2, after dropwising, reaction proceeds 0.5h, after reaction terminates, collects reaction solution and resin catalyst; Described toxilic acid: the part by weight of hydrogen peroxide is 1:1.
4) polyreaction, regulates reaction solution pH to be 8 and temperature 70 C, adds the composite initiator of weight content 5%, polyreaction 1.5h, obtain the poly-epoxy succinic acid product that scale inhibition performance is greater than 95.3%.
Embodiment 2
1) select vinylbenzene macroporous resin, embathe clean, exchange with 1N sodium hydroxide, make it after water outlet pH is 8-10, obtain strong basic ion exchange resin with deionized water rinsing; Again with the weight content 5%Na prepared in advance
2wO
4solution soaking or with resin column exchange, make the OH in resin
-by WO
4 2-replaced, obtained having adsorbed WO
4 2-large pore anion resin.
2) fresh saturated limewater is prepared.
3) oxidizing reaction, adds cis-butenedioic anhydride in the reactor, adds the NaOH solution that weight percent is 50%, and adjust ph is 8.1, and puts into and adsorbed WO
4 2-macroporous resin, macroporous resin consumption is 2% of gross weight, drips the H of weight content 30% in 85 DEG C and whipped state downhill reaction system
2o
2, after dropwising, reaction proceeds 50 minutes, after reaction terminates, collects reaction solution and resin catalyst; Described toxilic acid: the part by weight of hydrogen peroxide is 1:1.
4) polyreaction, regulates reaction solution pH to be 8 and temperature 75 DEG C, adds the fresh saturated limewater of weight content 6%, polyreaction 1.5h, obtain the poly-epoxy succinic acid product that scale inhibition performance is greater than 85.3%.
Embodiment 3
1) select vinylbenzene macroporous resin, embathe clean, exchange with 1N sodium hydroxide, make it after water outlet pH is 8-10, obtain strong basic ion exchange resin with deionized water rinsing; Again with the weight content 5%Na prepared in advance
2wO
4solution soaking or with resin column exchange, make the OH in resin
-by WO
4 2-replaced, obtained having adsorbed WO
4 2-large pore anion resin.
2) composite initiator preparation, adds saturated limewater in the aqueous sodium hydroxide solution of 50% and mixes.
3) oxidizing reaction, adds cis-butenedioic anhydride in the reactor, adds the NaOH solution that weight percent is 50%, and adjust ph is 8.3, and puts into and adsorbed WO
4 2-macroporous resin, macroporous resin consumption is 3% of gross weight, drips the H of weight content 30% in 88 DEG C and whipped state downhill reaction system
2o
2, after dropwising, reaction proceeds 1h, after reaction terminates, collects reaction solution and resin catalyst; Described toxilic acid: the part by weight of hydrogen peroxide is 1:1.
4) polyreaction, regulates reaction solution pH to be 8 and temperature 90 DEG C, adds the composite initiator of weight content 8%, polyreaction 2.5-3h, obtain the poly-epoxy succinic acid product that scale inhibition performance is greater than 95.2%.
Embodiment 4
1) select vinylbenzene macroporous resin, embathe clean, exchange with 1N sodium hydroxide, make it after water outlet pH is 8-10, obtain strong basic ion exchange resin with deionized water rinsing; Again with the weight content 5%Na prepared in advance
2wO
4solution soaking or with resin column exchange, make the OH in resin
-by WO
4 2-replaced, obtained having adsorbed WO
4 2-large pore anion resin.
2) composite initiator preparation, adds saturated limewater in the aqueous sodium hydroxide solution of 50% and mixes.
3) oxidizing reaction, adds cis-butenedioic anhydride in the reactor, adds the NaOH solution that weight percent is 50%, and adjust ph is 8.3, and puts into and adsorbed WO
4 2-macroporous resin, macroporous resin consumption is 4% of gross weight, drips the H of weight content 30% in 90-95 DEG C and whipped state downhill reaction system
2o
2, after dropwising, reaction proceeds 1h, after reaction terminates, collects reaction solution and resin catalyst; Described toxilic acid: the part by weight of hydrogen peroxide is 1:1
4) polyreaction, regulates reaction solution pH to be 8 and temperature 80-95 DEG C, adds the composite initiator of weight content 9%, polyreaction 3h, obtain the poly-epoxy succinic acid product that scale inhibition performance is greater than 93.2%.
Embodiment 5
1) select vinylbenzene macroporous resin, embathe clean, exchange with 1N sodium hydroxide, make it after water outlet pH is 8-10, obtain strong basic ion exchange resin with deionized water rinsing; Again with the weight content 5%Na prepared in advance
2wO
4solution soaking or with resin column exchange, make the OH in resin
-by WO
4 2-replaced, obtained having adsorbed WO
4 2-large pore anion resin.
2) composite initiator preparation, adds saturated limewater in the aqueous sodium hydroxide solution of 50% and mixes.
3) oxidizing reaction, adds cis-butenedioic anhydride in the reactor, and add the NaOH solution that weight percent is 50%, adjust ph is 8-8.5, and puts into and adsorbed WO
4 2-macroporous resin, macroporous resin consumption is the 1-5% of gross weight, drips the H of weight content 30% in 85-90 DEG C and whipped state downhill reaction system
2o
2, after dropwising, reaction proceeds 0.5h, after reaction terminates, collects reaction solution and resin catalyst; Described toxilic acid: the part by weight of hydrogen peroxide is 1:1
4) polyreaction, regulates reaction solution pH to be 8 and temperature 70-75 DEG C, adds the composite initiator of weight content 8-10%, polyreaction 2h, obtain the poly-epoxy succinic acid product that scale inhibition performance is greater than 91.3%.
Embodiment 6
1) select vinylbenzene macroporous resin, embathe clean, exchange with 1N sodium hydroxide, make it after water outlet pH is 8-10, obtain strong basic ion exchange resin with deionized water rinsing; Again with the weight content 5%Na prepared in advance
2wO
4solution soaking or with resin column exchange, make the OH in resin
-by WO
4 2-replaced, obtained having adsorbed WO
4 2-large pore anion resin.
2) composite initiator preparation, adds saturated limewater in the aqueous sodium hydroxide solution of 50% and mixes.
3) oxidizing reaction, adds cis-butenedioic anhydride in the reactor, and add the NaOH solution that weight percent is 50%, adjust ph is 8-8.3, and puts into and adsorbed WO
4 2-macroporous resin, macroporous resin consumption is the 3-5% of gross weight, drips the H of weight content 30% in 85-88 DEG C and whipped state downhill reaction system
2o
2, after dropwising, reaction proceeds 1h, after reaction terminates, collects reaction solution and resin catalyst; Described toxilic acid: the part by weight of hydrogen peroxide is 1:1
4) polyreaction, regulates reaction solution pH to be 8 and temperature 70-95 DEG C, adds the composite initiator of weight content 5-10%, polyreaction 3h, obtain the poly-epoxy succinic acid product that scale inhibition performance is greater than 95.5%.
The embodiment of the present invention the results are shown in following table 1:
Table 1: continuous production six batches of product situations
| Lot number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Product scale inhibition performance % | 95.3 | 85.5 | 95.2 | 93.2 | 91.3 | 95.5 |
Test-results shows, stabilize to 85.5-95.5% with the preparation-obtained product scale inhibition performance of heterogeneous manufacturing condition, prove: select through homogeneous phase single factor test, orthogonal test, resin catalyst, the manufacturing condition of product that 6 embodiments of polymerization starter adjustment obtain is reliable and effective.
Claims (2)
1. a Production method of polyepoxysuccinic acid, it is characterized in that: be for main raw material with maleic anhydride and hydrogen peroxide, by tungstate catalysts, adopt inhomogeneous reaction technique, under the initiation of composite initiator, after pre-treatment, oxidizing reaction, polyreaction, obtain the poly-epoxy succinic acid product meeting scale inhibition effect; Described maleic anhydride: the mol ratio of hydrogen peroxide is 1:1-1.3; Described tungstate catalysts has adsorbed WO
4 2-macroporous resin, catalyst levels is the 0.2-1.2% of total inventory;
Described oxidizing reaction adds maleic anhydride in the reactor, and add the NaOH solution that weight percent is 50%, adjust ph is 8-8.5, and put into and adsorbed WO
4 2-macroporous resin, in 60-85 DEG C and whipped state downhill reaction system, drip the H of weight content 30%
2o
2, after dropwising, reaction proceeds 1-3h, after reaction terminates, collects reaction solution and resin catalyst; Described polyreaction is regulated by reaction solution pH to be 8 and temperature 70-95 DEG C, adds the composite initiator of weight content 5-10%, polyreaction 1-3h, the poly-epoxy succinic acid product obtained;
Described has adsorbed WO
4 2-the preparation process of macroporous resin be: select vinylbenzene macroporous resin, embathe clean, exchange with 1N sodium hydroxide, make it after water outlet pH is 8-10, obtain strong basic ion exchange resin with deionized water rinsing; Again with the weight content 5%Na prepared in advance
2wO
4solution soaking or with resin column exchange, make the OH in resin
-by WO
4 2-replaced, obtained having adsorbed WO
4 2-macroporous resin;
The preparation of described composite initiator mixes in aqueous sodium hydroxide solution saturated limewater being added 50%;
Described vinylbenzene macroporous resin is D209, D296 and D301 macroporous resin.
2. Production method of polyepoxysuccinic acid according to claim 1, is characterized in that: the scale inhibition performance of described poly-epoxy succinic acid product is greater than 85%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524893A (en) * | 2003-02-28 | 2004-09-01 | 赵勇军 | Synthesis of poly epoxy succinate |
| CN101717498A (en) * | 2009-12-16 | 2010-06-02 | 内蒙古天晨科技有限责任公司 | Synthesis method of high-concentration polyepoxysuccinic acid and salt thereof |
| CN102432567A (en) * | 2011-11-07 | 2012-05-02 | 中国科学院青岛生物能源与过程研究所 | Method for preparing epoxy succinate |
-
2013
- 2013-12-19 CN CN201310702492.4A patent/CN103709387B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524893A (en) * | 2003-02-28 | 2004-09-01 | 赵勇军 | Synthesis of poly epoxy succinate |
| CN101717498A (en) * | 2009-12-16 | 2010-06-02 | 内蒙古天晨科技有限责任公司 | Synthesis method of high-concentration polyepoxysuccinic acid and salt thereof |
| CN102432567A (en) * | 2011-11-07 | 2012-05-02 | 中国科学院青岛生物能源与过程研究所 | Method for preparing epoxy succinate |
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Effective date of registration: 20180626 Address after: 530103 Shuangqiao Town, Wuming District, Nanning, the Guangxi Zhuang Autonomous Region. Patentee after: Nanning Taida biological science and Technology Co., Ltd. Address before: 530022 4-2 Gucheng Road, Nanning, the Guangxi Zhuang Autonomous Region Patentee before: Nanning City Chemical Engineering Research and Design Inst. |
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