CN1319876C - Method for preparing biodegradable water treatment agent PECS - Google Patents

Method for preparing biodegradable water treatment agent PECS Download PDF

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CN1319876C
CN1319876C CNB2005101223629A CN200510122362A CN1319876C CN 1319876 C CN1319876 C CN 1319876C CN B2005101223629 A CNB2005101223629 A CN B2005101223629A CN 200510122362 A CN200510122362 A CN 200510122362A CN 1319876 C CN1319876 C CN 1319876C
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epoxy
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CN1789178A (en
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靳晓霞
胡兴刚
孙继
滕厚开
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TIANJIN CHEMICAL RESEARCH & DESIGN INST
China National Offshore Oil Corp CNOOC
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Abstract

The present invention relates to a method for preparing biodegradable water treating agents-ployepoxide sulfonic carboxylic acid. The present invention is characterized in that epoxy chloropropane and bisulphite with molar ratio of 1: 1 to 1: 1.5 are used as raw material and are synthesized into an intermediate compound under the function of phase transfer catalyst isopropanol and nitrogen gas of which the dosages occupy 1% to 20% of the total weight of reactants, the intermediate compound which does not need to be separated is directly polymerized with epoxy succinic acid under the catalytic function of rare earth metal catalysts Ba and Sr of which the dosages occupy 0.1% to 1% of the total weight of the reactants, and polyepoxide sulfonic carboxylic acid solutions or salt solutions are obtained.

Description

A kind of preparation method of biodegradable water treatment agent PECS
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of preparation method of biodegradable environmentally friendly water treatment agent PECS.
Background technology
In water-treatment technology field,, banned use of both at home and abroad greatly because of chromic salt toxicity eventually though early stage chromium system prescription result of use is good.Traditional inorganic phosphate prescription has been because the phosphoric acid salt hydrolysis has caused the eutrophication of water body, with phosphorus be washing composition all at home and abroad the waters caused " red tide " phenomenon, bring great pollution to water resources, the worldwide phosphorus motion that limits has appearred.The phosphorus that accounts at present the principal status of public economy in China's water technology is that the most polymkeric substance in alkaline water treatment formulations and the all-organic formula are still and can't or can only be resolved into simple, nontoxic material by microorganism and fungi on a small quantity, and therefore unrestricted a large amount of these Water Treatment Chemicals of discharging will aggravate serious day by day water resource pollution problem.
Nineteen ninety-five, the U.S. proposed the notion of " Green Chemistry ", promptly used the technology and the method for chemistry, fundamentally reduced or eliminated those production and application to human health or the deleterious raw material of environment, product, by product, solvent and reagent etc.This notion is introduced in water treatment field subsequently, the research boom of green Water Treatment Chemicals and green water technology occurred.Wherein the most valued have poly-aspartic-acid, a poly-epoxy succinic acid etc.These two kinds of medicaments all have the favorable biological degradability energy, but it is because simple in structure, functional group is simple, make the application of product receive restriction, especially the recirculating cooling water system under high-alkali, high hard, high temperature, high pH condition, the corrosion and scale inhibition performance of medicament does not also reach the result of use of multiple copolymer, has therefore limited applying of environmentally friendly dirt dispersion agent.
Propose the epoxy succinic acid salt aqueous solution is added 2-80mol%CaSO at 40-150 ℃ in the German patent DE 4212755 of GIULINI CHEM GMBH (GIUL) application 3Or CaSO 3XH 2O, reaction 8h, precipitation separation filters and obtains novel telomer sulfonation poly-epoxy succinic acid and salt thereof.The n=2-50 of this telomer, M=H maybe can form the positively charged ion of soluble salt; R=H or (replacement) C 1-4Alkyl.Sulfonation poly-epoxy succinic acid and salt thereof are mainly used in the Scale inhibitors of cooling water system, seawater desalination system and the sequestrant in the washing composition.
U.S. Betzdearborn Inc. mentions the corrosion that can suppress water medium carbon steel and iron alloy with the poly-epoxy succinic acid of alkyl or aromatic base modification effectively in the U.S. Pat 5871691 of application in 1999.As inhibiter, the consumption of modified poly-epoxy succinic acid is 0.025-500ppm, and simultaneously it can be arbitrarily and polyacrylate, phosphoric acid, organic phosphine, the composite inhibition fouling of polyvalent metal salt and azole compounds.Typical modified poly-epoxy succinic acid is polymerized by epoxy succinic acid disodium salt and hydroxy-n-(2-sulfoethyl) aspartic acid trisodium salt.
Among the Japanese Patent JP2000117292 with tartrate, oxysuccinic acid or the citric acid of hydroxyl and Epoxysuccinic acid at 50-150 ℃, under certain PH condition, with 1: (3-30) the molar ratio copolymerization forms poly-epoxy succinic acid derivative, and relative molecular mass is 500-2000.This poly-epoxy succinic acid derivative can effectively prevent the deposition of paper mill equipment mesoxalic acid calcium, and the optimum amount in washing lotion is 1-100ppm.
Chinese invention patent application CN1557805A with maleic anhydride through after the basic hydrolysis again epoxidation form the epoxy Succinic Acid, in the presence of diethylenetriamine, form the amido polyepoxysuccinic acid then by the ionic polymerization mode.This polymkeric substance all has good scale inhibition and dispersive ability to the multiple dirt of systems such as recirculated cooling water, feedwater, oil-field water, sea water desalinization.
Introduced a kind of preparation method of poly-epoxy succinic acid derivative among the Chinese invention patent application CN1375467A, be to be that raw material earlier generates 2 under sodium hydroxide, potassium hydroxide, calcium hydroxide or ammoniacal liquor effect with 3-chloro-2-hydroxy-propanesulfonic acid salt, 3-epoxy propanesulfonic acid salt, obtain poly-epoxy sulphur carboxylic acid with poly-epoxy succinic acid copolymerization in the presence of sodium hydroxide, potassium hydroxide, calcium hydroxide or ammoniacal liquor again, as the Scale inhibitors in the Treatment of Industrial Water, inhibiter and dispersion agent.
Summary of the invention
The present invention mainly provides a kind of preparation method of biodegradable water treatment agent PECS.
The preparation method of the environmentally friendly water treatment agent PECS that the present invention proposes, be characterised in that being is 1 with mol ratio: 1-1: 1.5 epoxy chloropropane and hydrosulphite are raw material, it at consumption synthetic intermediate under the effect of the phase-transfer catalyst Virahol of 1-20% of reactant gross weight and nitrogen, intermediate need not separate directly consumption be under the katalysis of rare-earth metal catalyst Ba, Sr of 0.1-1% of reactant gross weight with the Epoxysuccinic acid polymerization, obtain the solution of poly-epoxy sulphur carboxylic acid or salt.Concrete steps are as follows: hydrosulphite is dissolved in water under nitrogen protection, adds the phase-transfer catalyst Virahol, drips epoxy chloropropane under stirring condition, and control reaction temperature is 65-95 ℃, reaction times 1.5-3.0 hour; The alkali that adds the 10-20% of reactant gross weight again, phase-transfer catalyst is reclaimed in underpressure distillation; Add rare-earth metal catalysts such as a certain amount of Ba, Sr then,, with Epoxysuccinic acid polymerization 2-5 hour, obtain the tawny viscous solution of poly-epoxy sulphur carboxylic acid or salt under 70-100 ℃ the condition at pH=10-14.Its structural formula is:
Figure C20051012236200041
M is H or water soluble ion Na in the formula +, K +, NH 4 +Deng; M, n are 1-20.
Among the present invention, the mol ratio of epoxy chloropropane and hydrosulphite is 1: 1-1: 1.5.
Among the present invention, the consumption of phase-transfer catalyst Virahol is the 1-20% of reactant gross weight.
Among the present invention, the consumption of rare-earth metal catalyst Ba, Sr is the 0.1-1% of reactant gross weight.
Preparation in accordance with the present invention, it is further characterized in that the mol ratio of epoxy chloropropane and hydrosulphite is 1: 1.2-1: 1.4, hydrosulphite is potassium, sodium or ammonium salt.
The consumption of phase-transfer catalyst Virahol is the 5-15% of reactant gross weight.
The consumption of rare-earth metal catalyst is the 0.3-0.8% of reactant gross weight, and composition is muriate or nitrate.
Polymeric reaction temperature is 80~90 ℃, and the reaction times is 3~4 hours.
The biodegradable water treatment agent PECS or the salt of the inventive method preparation have good scale inhibition and dispersing property, and the scale inhibitor that can be widely used in fields such as recirculated cooling water, feedwater, oil-field water, film processing is handled.
Embodiment
Embodiment 1
Under agitation in the sodium bisulfite 98g aqueous solution (concentration is 40%), add the 7g Virahol, under 85 ℃ of conditions, drip epoxy chloropropane 25g, 2 hours reaction times.Cool to 40 ℃, the sodium hydroxide 42g of adding 40% under cooling and agitation condition, 15g liquid is removed in underpressure distillation, add 135g Epoxysuccinic acid sodium water solution (concentration is 25%) and 1g bariumchloride again, the control pH value is 14, reaction is 5 hours under 70 ℃ of conditions, obtains the tawny viscous solution that solid content is not less than 30% poly-epoxy sulphur carboxylic acid sodium.
Embodiment 2
Under agitation in the sodium bisulfite 84g aqueous solution (concentration is 40%), add the 20g Virahol, under 65 ℃ of conditions, drip epoxy chloropropane 25g, 3 hours reaction times.Cool to 40 ℃, the sodium hydroxide 42g of adding 40% under cooling and agitation condition, 15g liquid is removed in underpressure distillation, add 135g Epoxysuccinic acid sodium water solution (concentration is 25%) and 1g bariumchloride again, the control pH value is 12, reaction is 4 hours under 80 ℃ of conditions, obtains the tawny viscous solution that solid content is not less than 30% poly-epoxy sulphur carboxylic acid sodium.
Embodiment 3
Under agitation in the sodium bisulfite 80g aqueous solution (concentration is 40%), add the 15g Virahol, under 85 ℃ of conditions, drip epoxy chloropropane 25g, 2 hours reaction times.Cool to 40 ℃, the sodium hydroxide 42g of adding 40% under cooling and agitation condition, 15g liquid is removed in underpressure distillation, add 135g Epoxysuccinic acid sodium water solution (concentration is 25%) and 1g strontium nitrate again, the control pH value is 10, reaction is 3 hours under 90 ℃ of conditions, obtains the tawny viscous solution that solid content is not less than 30% poly-epoxy sulphur carboxylic acid sodium.
Embodiment 4
Under agitation in the Potassium hydrogen sulfite 80g aqueous solution (concentration is 40%), add the 15g Virahol, under 95 ℃ of conditions, drip epoxy chloropropane 25g, 1.5 hours reaction times.Cool to 40 ℃, the potassium hydroxide 58.8g of adding 40% under cooling and agitation condition, 15g liquid is removed in underpressure distillation, add 135g Epoxysuccinic acid sodium water solution (concentration is 25%) and 1g bariumchloride again, the control pH value is 10, reaction is 2 hours under 100 ℃ of conditions, obtains the tawny viscous solution that solid content is not less than 30% poly-epoxy sulphur carboxylic acid potassium.

Claims (5)

1. the preparation method of a biodegradable water treatment agent PECS salt, be characterised in that being is 1 with mol ratio: 1-1: 1.5 epoxy chloropropane and hydrosulphite are raw material, it at consumption synthetic intermediate under the effect of the phase-transfer catalyst Virahol of 1-20% of reactant gross weight and nitrogen, intermediate need not separate directly consumption be under the katalysis of alkaline-earth metal catalyst of 0.1-1% of reactant gross weight with the Epoxysuccinic acid polymerization, the composition of alkaline-earth metal catalyst is muriate or nitrate, alkaline-earth metal wherein is Ba or Sr, obtains the solution of poly-epoxy sulphur carboxylate salt;
Concrete steps are as follows: hydrosulphite is dissolved in water under nitrogen protection, adds the phase-transfer catalyst Virahol, drips epoxy chloropropane under stirring condition, and control reaction temperature is 65-95 ℃, reaction times 1.5-3.0 hour; The alkali that adds the 10-20% of reactant gross weight again, phase-transfer catalyst is reclaimed in underpressure distillation; The alkaline-earth metal catalyst of the 0.1-1% of the reactant gross weight of Jia Ruing at PH=10-14, with Epoxysuccinic acid polymerization 2-5 hour, obtains the tawny viscous solution of poly-epoxy sulphur carboxylate salt under 70-100 ℃ the condition then.
2. preparation method according to claim 1, the mol ratio that it is characterized in that epoxy chloropropane and hydrosulphite is 1: 1.2-1: 1.4, hydrosulphite is potassium, sodium or ammonium salt.
3. preparation method according to claim 1, the consumption that it is characterized in that the phase-transfer catalyst Virahol is the 5-15% of reactant gross weight.
4. preparation method according to claim 1, the consumption that it is characterized in that alkaline-earth metal catalyst is the 0.3-0.8% of reactant gross weight, composition is muriate or nitrate.
5. preparation method according to claim 1 is characterized in that polyreaction control pH value is 12-14, and temperature is 80-90 ℃, and the reaction times is 3-4 hour.
CNB2005101223629A 2005-12-15 2005-12-15 Method for preparing biodegradable water treatment agent PECS Active CN1319876C (en)

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CN104370379B (en) * 2014-10-17 2016-01-20 中国海洋石油总公司 The scale inhibitor of a kind of oil field hot environment water-in-oil system and method for making and purposes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4795585A (en) * 1987-04-24 1989-01-03 General Chemical Corporation Polyvinyl alcohol containing polyaluminum chloride flocculants
US5658487A (en) * 1995-02-17 1997-08-19 Betz Laboratories, Inc. Polymeric dithiocarbamate acid salt compositions and method of use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4795585A (en) * 1987-04-24 1989-01-03 General Chemical Corporation Polyvinyl alcohol containing polyaluminum chloride flocculants
US5658487A (en) * 1995-02-17 1997-08-19 Betz Laboratories, Inc. Polymeric dithiocarbamate acid salt compositions and method of use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
聚环氧磺羧酸的合成及其阻垢性能 胡晓斌等,应用化学,第22卷第1期 2005 *

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