CN106039626A - Preparation method of aqueous film forming foam extinguishing agent - Google Patents

Preparation method of aqueous film forming foam extinguishing agent Download PDF

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Publication number
CN106039626A
CN106039626A CN201610455321.XA CN201610455321A CN106039626A CN 106039626 A CN106039626 A CN 106039626A CN 201610455321 A CN201610455321 A CN 201610455321A CN 106039626 A CN106039626 A CN 106039626A
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sodium
added
preparation
carbonate
fraction
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叶明生
费卫民
王以丹
朱小兵
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Shanghai Waysmos Fine Chemical Co Ltd
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Shanghai Waysmos Fine Chemical Co Ltd
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    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071Foams

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Cosmetics (AREA)

Abstract

The invention relates to a preparation method of an aqueous film forming foam extinguishing agent. The preparation method comprises the steps that triethylamine, ethyl alcohol, carboxylic acid and amino acid are stirred and mixed; tetrafluoride propylene dichloride and sodium fluoride are added; then nanometer titania is added for reacting; then ethidene diamine is added; an ethidene diamine organic layer is taken; reduced pressure distillation is carried out, and carbonate, sodium ethoxide, aluminum fluoride, potassium chloride, tributyl phosphate and n-butyl alcohol are added into a fraction for reacting; then stirring, cooling and filtering are carried out; ethyl alcohol is added into an obtained crystal for dissolving; filter liquor obtained through filtering is distilled; dodecydimethylammonium bronides, lauryl sodium sulfate and bis(2-etnylhexyl) sodium phosphate are added into the obtained fraction to be mixed and stirred; polyoxyethylene and sodium xylene sulfonate are added for stirring and reacting; and then silicone polyether, polyacrylamide, ammonium bicarbonate and propylene glycol monomethyl ether are added to be stirred and mixed evenly. The preparation method of the aqueous film forming foam extinguishing agent is low in cost, good in printing and dyeing effect, low in waste water output and simple in process.

Description

A kind of preparation method of aqueous film-forming foam extinguishing agent
Technical field
The present invention relates to extinguishing chemical technical field, be specifically related to the preparation method of a kind of aqueous film-forming foam extinguishing agent.
Background technology
In the extinguishing chemical being currently used for putting out oil fire, aqueous film-forming foam extinguishing agent is due to its MJPZ and foam Dual fire extinguishing function and there is optimal extinguishing effect, and in aqueous film-forming foam extinguishing agent, the component of more than 97% is water, and this makes In its " cancelling system action " at the international level as the ideal substitute of halon fire agent, become and give priority in the world Extinguishing chemical.
MJPZ extinguishing chemical, mainly by fluorocarbon surfactant efficient water and oil repellence character, drops to the utmost The surface tension of low water, also can reduce the interfacial tension of water-oil so that water can swim on oil simultaneously, reaches to completely cut off oil reservoir With the purpose of air, thus complete physics fire extinguishing procedure.Therefore, fluorocarbon surfactant the most just becomes aqueous film-forming foam extinguishing agent Most important component, it decides the performance of aqueous film-forming foam extinguishing agent and cost, and (fluorocarbon surfactant accounts for AFFF More than the 80% of extinguishing chemical totle drilling cost).From the point of view of in the world tens patents, fluorine carbon in 3 (wt) % type aqueous film-forming foam extinguishing agent The consumption of surfactant is all at 5 (wt) more than %.Owing to the production cost of fluorocarbon surfactant is higher, large usage quantity causes The cost of aqueous film-forming foam extinguishing agent is also the highest, just develops the aqueous film-forming foam extinguishing agent of low consumption fluorocarbon surfactant There is important commercial value.
Summary of the invention
In order to solve the problems referred to above that prior art exists, the invention provides the preparation of a kind of aqueous film-forming foam extinguishing agent Method, low cost, technique is simple.
The technical solution adopted in the present invention is:
The preparation method of a kind of aqueous film-forming foam extinguishing agent, it is characterised in that comprise the following steps:
(1) triethylamine, ethanol, carboxylic acid, aminoacid are stirred in reactor mixing, be passed through noble gas simultaneously, maintain Oxygen volume content in reactor is less than 0.1%, and maintain the pressure in reactor is 1.2-1.8Mpa simultaneously, is-15 in temperature Add tetrafluoro dichloropropane, sodium fluoride at DEG C-15 DEG C, be subsequently adding nano titanium oxide, be warmed up to 25-according to 0.5-1 DEG C/h 50 DEG C, isothermal reaction 5-10 hour, it is subsequently adding ethylenediamine, stratification after stirring, take ethylenediamine organic layer, through 3-6 time Decompression distillation, takes 40-70 DEG C of fraction.
(2) fraction in step (1) is added carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate and positive fourth Alcohol, reacts 2-5 hour at 90-110 DEG C, and then stirring is cooled to 5-20 DEG C, filters, and the crystal obtained adds ethanol and dissolves, mistake The filtrate distillation that filter obtains, takes 100-120 DEG C of fraction.
(3) fraction in step (2) is added Dodecydimethylammonium bronides, sodium lauryl sulphate and two (2-second Base hexyl) sodium phosphate mix and blend, add polyoxyethylene and sodium xylene sulfonate at 40-50 DEG C, stir reaction 1-3 hour, so Rear addition polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether are uniformly mixed.
Triethylamine, ethanol, carboxylic acid, aminoacid, tetrafluoro dichloropropane, sodium fluoride, nanometer titanium dioxide in described step (1) Titanium, the mol ratio of ethylenediamine are 1:1-2:0.5-1:0.5-1:1-2:0.1-0.3:0.01-0.05:2-5, and carboxylic acid is formic acid, second At least one in acid, propanoic acid and n-butyric acie, aminoacid is albumen propylhomoserin, isoleucine, lysine, threonine, tryptophan, benzene At least one in alanine, noble gas is at least one in nitrogen, argon, carbon dioxide.
In described step (2) in carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate, n-butyl alcohol and step (1) The mass ratio of fraction is 0.2-0.5:0.02-0.05:0.02-0.05:0.1-0.5:0.3-0.8:0.1-0.2:1, and carbonate is At least one in potassium carbonate, sodium carbonate and ammonium carbonate.
Dodecydimethylammonium bronides, sodium lauryl sulphate, di-(2-ethylhexyl)phosphoric acid in described step (3) Sodium, polyoxyethylene, sodium xylene sulfonate, polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether and step (2) The mass ratio of middle fraction is: 0.2-0.4:0.1-0.3:0.02-0.04:0.01-0.02:0.05-0.1:0.05-0.1:0. 05- 0.1:0.1-0.2:0.1-0.3:1.
The ethanol that in described step (2), still-process condensation obtains is continuing with.
The invention have the benefit that
1. low cost, in step 1, uses low temperature pressurization catalytic reaction under an inert gas, both can ensure that productivity and Production efficiency, can reduce again the generation of side reaction, improves the utilization rate of supplementary material, uses the abstraction technique of ethylenediamine, can have The reduction separation costs of effect so that whole process costs is substantially reduced.
2. technique is simple, and reaction condition is gentle, and this technique uses low-temperature catalyzed reaction to obtain fluorocarbon surfactant forerunner Body, by extract and separate, reaction obtains fluorocarbon surfactant the most again, is dissolved in other magazins' layout through ethanol, The purified product by distillation again, reaction condition is gentle, and technique is simple.
Detailed description of the invention
Below in conjunction with concrete example, the preparation method of a kind of aqueous film-forming foam extinguishing agent described in the present patent application is entered Line description and explanation are in order to the public is better understood from the technology contents of the present invention rather than to described technology contents Limit, under principle that is identical or that approximate, the improvement carrying out described processing step, improves including reaction condition, agents useful for same And replacement, reach identical purpose, the most all within the present patent application technical scheme required for protection.
Embodiment one
The preparation method of a kind of aqueous film-forming foam extinguishing agent, it is characterised in that comprise the following steps:
(1) triethylamine, ethanol, carboxylic acid, aminoacid are stirred in reactor mixing, be passed through noble gas simultaneously, maintain Oxygen volume content in reactor is less than 0.1%, and maintain the pressure in reactor is 1.5Mpa simultaneously, adds at temperature is 5 DEG C Entering tetrafluoro dichloropropane, sodium fluoride, be subsequently adding nano titanium oxide, be warmed up to 40 DEG C according to 0.8 DEG C/h, isothermal reaction 6 is little Time, it is subsequently adding ethylenediamine, stratification after stirring, take ethylenediamine organic layer, through 4 decompression distillations, take 50 DEG C of fractions.
(2) fraction in step (1) is added carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate and positive fourth Alcohol, reacts 4 hours at 100 DEG C, and then stirring is cooled to 10 DEG C, filters, and the crystal obtained adds ethanol and dissolves, and is filtrated to get Filtrate is distilled, and takes 110 DEG C of fractions.
(3) fraction in step (2) is added Dodecydimethylammonium bronides, sodium lauryl sulphate and two (2-second Base hexyl) sodium phosphate mix and blend, add polyoxyethylene and sodium xylene sulfonate, stirring reaction 2 hours at 50 DEG C, be subsequently adding Polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether are uniformly mixed.
Triethylamine, ethanol, carboxylic acid, aminoacid, tetrafluoro dichloropropane, sodium fluoride, nanometer titanium dioxide in described step (1) Titanium, the mol ratio of ethylenediamine are 1:1.5:0.7:0.7:1.5:0.2:0.04:3, and carboxylic acid is formic acid, and aminoacid is albumen propylhomoserin, Noble gas is nitrogen.
In described step (2) in carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate, n-butyl alcohol and step (1) The mass ratio of fraction is 0.4:0.04:0.04:0.4:0.5:0.13:1, and carbonate is potassium carbonate.
Dodecydimethylammonium bronides, sodium lauryl sulphate, di-(2-ethylhexyl)phosphoric acid in described step (3) Sodium, polyoxyethylene, sodium xylene sulfonate, polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether and step (2) The mass ratio of middle fraction is: 0.3:0.3:0.03:0.014:0.08:0.08:0.08:0.15:0.17:1.
The ethanol that in described step (2), still-process condensation obtains is continuing with.
Embodiment two
The preparation method of a kind of aqueous film-forming foam extinguishing agent, it is characterised in that comprise the following steps:
(1) triethylamine, ethanol, carboxylic acid, aminoacid are stirred in reactor mixing, be passed through noble gas simultaneously, maintain Oxygen volume content in reactor is less than 0.1%, and maintain the pressure in reactor is 1.4Mpa simultaneously, adds at temperature is 5 DEG C Entering tetrafluoro dichloropropane, sodium fluoride, be subsequently adding nano titanium oxide, be warmed up to 40 DEG C according to 0.7 DEG C/h, isothermal reaction 7 is little Time, it is subsequently adding ethylenediamine, stratification after stirring, take ethylenediamine organic layer, through 5 decompression distillations, take 55 DEG C of fractions.
(2) fraction in step (1) is added carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate and positive fourth Alcohol, reacts 3 hours at 105 DEG C, and then stirring is cooled to 10 DEG C, filters, and the crystal obtained adds ethanol and dissolves, and is filtrated to get Filtrate is distilled, and takes 110 DEG C of fractions.
(3) fraction in step (2) is added Dodecydimethylammonium bronides, sodium lauryl sulphate and two (2-second Base hexyl) sodium phosphate mix and blend, add polyoxyethylene and sodium xylene sulfonate, stirring reaction 2 hours at 45 DEG C, be subsequently adding Polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether are uniformly mixed.
Triethylamine, ethanol, carboxylic acid, aminoacid, tetrafluoro dichloropropane, sodium fluoride, nanometer titanium dioxide in described step (1) Titanium, the mol ratio of ethylenediamine are 1:1.8:0.7:0.7:1.5:0.2:0.04:3, and carboxylic acid is acetic acid, and aminoacid is lysine, lazy Property gas is carbon dioxide.
In described step (2) in carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate, n-butyl alcohol and step (1) The mass ratio of fraction is 0.4:0.04:0.03:0.4:0.5:0.15:1, and carbonate is sodium carbonate.
Dodecydimethylammonium bronides, sodium lauryl sulphate, di-(2-ethylhexyl)phosphoric acid in described step (3) Sodium, polyoxyethylene, sodium xylene sulfonate, polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether and step (2) The mass ratio of middle fraction is: 0.3:0.3:0.03:0.014:0.09:0.08:0.08:0.15:0.15:1.
The ethanol that in described step (2), still-process condensation obtains is continuing with.
Embodiment 3
The preparation method of a kind of aqueous film-forming foam extinguishing agent, it is characterised in that comprise the following steps:
(1) triethylamine, ethanol, carboxylic acid, aminoacid are stirred in reactor mixing, be passed through noble gas simultaneously, maintain Oxygen volume content in reactor is less than 0.1%, and maintain the pressure in reactor is 1.4Mpa simultaneously, adds at temperature is 5 DEG C Entering tetrafluoro dichloropropane, sodium fluoride, be subsequently adding nano titanium oxide, be warmed up to 40 DEG C according to 0.7 DEG C/h, isothermal reaction 7 is little Time, it is subsequently adding ethylenediamine, stratification after stirring, take ethylenediamine organic layer, through 5 decompression distillations, take 55 DEG C of fractions.
(2) fraction in step (1) is added carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate and positive fourth Alcohol, reacts 3 hours at 105 DEG C, and then stirring is cooled to 10 DEG C, filters, and the crystal obtained adds ethanol and dissolves, and is filtrated to get Filtrate is distilled, and takes 110 DEG C of fractions.
(3) fraction in step (2) is added Dodecydimethylammonium bronides, sodium lauryl sulphate and two (2-second Base hexyl) sodium phosphate mix and blend, add polyoxyethylene and sodium xylene sulfonate, stirring reaction 2 hours at 45 DEG C, be subsequently adding Polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether are uniformly mixed.
Triethylamine, ethanol, carboxylic acid, aminoacid, tetrafluoro dichloropropane, sodium fluoride, nanometer titanium dioxide in described step (1) Titanium, the mol ratio of ethylenediamine are 1:1.5:0.7:0.7:1.5:0.3:0.04:4, and carboxylic acid is acetic acid, and aminoacid is phenylalanine, Noble gas is carbon dioxide.
In described step (2) in carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate, n-butyl alcohol and step (1) The mass ratio of fraction is 0.4:0.04:0.03:0.4:0.5:0.15:1, and carbonate is ammonium carbonate.
Dodecydimethylammonium bronides, sodium lauryl sulphate, di-(2-ethylhexyl)phosphoric acid in described step (3) Sodium, polyoxyethylene, sodium xylene sulfonate, polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether and step (2) The mass ratio of middle fraction is: 0.2:0.25:0.02:0.014:0.08:0.08:0.08:0.10:0.16:1.
The ethanol that in described step (2), still-process condensation obtains is continuing with.
The present invention is not limited to above-mentioned preferred forms, and anyone can show that under the enlightenment of the present invention other are various The product of form, no matter but in its shape or structure, make any change, every have same as the present application or akin skill Art scheme, within all falling within protection scope of the present invention.

Claims (5)

1. the preparation method of an aqueous film-forming foam extinguishing agent, it is characterised in that comprise the following steps:
(1) triethylamine, ethanol, carboxylic acid, aminoacid are stirred in reactor mixing, be passed through noble gas simultaneously, maintain reaction Oxygen volume content in still is less than 0.1%, and maintain the pressure in reactor is 1.2-1.8Mpa simultaneously, temperature be-15 DEG C- Add tetrafluoro dichloropropane, sodium fluoride at 15 DEG C, be subsequently adding nano titanium oxide, be warmed up to 25-50 according to 0.5-1 DEG C/h DEG C, isothermal reaction 5-10 hour, it is subsequently adding ethylenediamine, stratification after stirring, take ethylenediamine organic layer, subtract through 3-6 time Pressure distillation, takes 40-70 DEG C of fraction.
(2) fraction in step (1) is added carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate and n-butyl alcohol, 90-110 DEG C is reacted 2-5 hour, and then stirring is cooled to 5-20 DEG C, filters, and the crystal obtained adds ethanol and dissolves, and is filtrated to get Filtrate distillation, take 100-120 DEG C of fraction.
(3) fraction in step (2) is added Dodecydimethylammonium bronides, sodium lauryl sulphate and two (2-ethyl hexyls Base) sodium phosphate mix and blend, add polyoxyethylene and sodium xylene sulfonate, stirring reaction 1-3 hour at 40-50 DEG C, then add Enter polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether are uniformly mixed.
The preparation method of a kind of aqueous film-forming foam extinguishing agent the most according to claim 1, it is characterised in that described step (1) triethylamine, ethanol, carboxylic acid, aminoacid, tetrafluoro dichloropropane, sodium fluoride, nano titanium oxide, the mol ratio of ethylenediamine in For 1:1-2:0.5-1:0.5-1:1-2:0.1-0.3:0.01-0.05:2-5, carboxylic acid is in formic acid, acetic acid, propanoic acid and n-butyric acie At least one, aminoacid is at least in albumen propylhomoserin, isoleucine, lysine, threonine, tryptophan, phenylalanine Individual, noble gas is at least one in nitrogen, argon, carbon dioxide.
The preparation method of a kind of aqueous film-forming foam extinguishing agent the most according to claim 1, it is characterised in that described step (2) in, carbonate, Sodium ethylate, aluminium fluoride, potassium chloride, tributyl phosphate, n-butyl alcohol with the mass ratio of fraction in step (1) are 0.2-0.5:0.02-0.05:0.02-0.05:0.1-0.5:0.3-0.8:0.1-0.2:1, carbonate be potassium carbonate, sodium carbonate and At least one in ammonium carbonate.
The preparation method of a kind of aqueous film-forming foam extinguishing agent the most according to claim 1, it is characterised in that described step (3) Dodecydimethylammonium bronides, sodium lauryl sulphate, di-(2-ethylhexyl)phosphoric acid sodium, polyoxyethylene, dimethylbenzene in Sodium sulfonate, polyether silicone, polyacrylamide, ammonium hydrogen carbonate, propylene glycol monomethyl ether with the mass ratio of fraction in step (2) be: 0.2-0.4:0.1-0.3:0.02-0.04:0.01-0.02:0.05-0.1:0.05-0.1:0. 05-0.1:0.1-0.2:0.1- 0.3:1。
The preparation method of a kind of aqueous film-forming foam extinguishing agent the most according to claim 1, it is characterised in that described step (2) ethanol that in, still-process condensation obtains is continuing with.
CN201610455321.XA 2016-06-22 2016-06-22 Preparation method of aqueous film forming foam extinguishing agent Pending CN106039626A (en)

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CN111420340A (en) * 2020-05-13 2020-07-17 洛阳市浪潮消防科技股份有限公司 Green environment-friendly aqueous film-forming foam extinguishing agent

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