CN101560225B - Preparation method of tetrakis hydroxymetyl phosphonium sulfuric-urea polymer - Google Patents

Preparation method of tetrakis hydroxymetyl phosphonium sulfuric-urea polymer Download PDF

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Publication number
CN101560225B
CN101560225B CN2009100273205A CN200910027320A CN101560225B CN 101560225 B CN101560225 B CN 101560225B CN 2009100273205 A CN2009100273205 A CN 2009100273205A CN 200910027320 A CN200910027320 A CN 200910027320A CN 101560225 B CN101560225 B CN 101560225B
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urea
sulfuric acid
still
kettle
phosphine gas
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CN2009100273205A
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CN101560225A (en
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许红兰
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JIANGSU DAN'AI CHEMICAL CO Ltd
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JIANGSU DAN'AI CHEMICAL CO Ltd
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Abstract

The invention relates to a preparation method of tetrakis hydroxymetyl phosphonium sulfuric-urea polymer. The technique process comprises the following steps: phosphine gas is collected and stored after being bathed in an intake washing kettle; deionized water is added into a dosage kettle, then sulphuric acid and formaldehyde is pumped into the dosage kettle to be stirred according to the mol ratio of 1:8.5-8.7; the above mixed liquid is driven into a recycling kettle in which phosphine gas is absorbed by a recycling tower; the feed liquor is pumped into a decoloring kettle, then 2 per mill of active carbon power is added; the feed liquor and urea is pumped into the dosage kettle to be stirred according to the mol ratio of 1.25:1, sodium hudroxide is used for adjusting PH value; tetrakishydroxymetyl phosphonium sulfuric-urea polymer is obtained through fiber filter bag with aperture being 2[mu]m. The method has the advantages that sulphuric acid and formaldehyde is mixed according to the ratio so that sulphuric acid and formaldehyde can fully react while absorbing phosphine gas, and the feed liquor and the urea is mixed according to the mol ratio of 1.25:1 so as to ensure the primary content of tetrakis hydroxymetyl phosphonium sulfuric. The product is enhanced in tenacity and is unlikely to be torn. The fabric has good fire resistance and washing resistance without affecting various initial excellent performances of the fabric. The method has no environmental pollution and can realize zero emission of toxic gas.

Description

The preparation method of tetra methylol sulfuric acid phosphorus-urea initial reduced body
Technical field
The preparation method of the tetra methylol sulfuric acid phosphorus-urea initial reduced body that the present invention relates to, it is the phosphine gas that produces when producing sodium hypophosphite, after adding formaldehyde, sulfuric acid, deionized water and making tetra methylol sulfuric acid phosphorus, add again that caustic soda, the urea method by chemical reaction, physical adsorption makes.Belong to tetra methylol sulfuric acid phosphorus-urea initial reduced body preparing technical field.
Background technology
In the waste gas that prior preparation method is from sodium hypophosphite production course to be produced, collect and also store phosphuret-(t)ed hydrogen; With formaldehyde, sulfuric acid is 8.05~8.10 in molar ratio: 1 is made into the aqueous solution; This aqueous solution is squeezed into the absorption tower with noncorrosive pump, spray downwards, the phosphine gas in the gas tank is sent in the absorption tower, under 40~50 ℃ temperature condition, react synthetic, make the tetra methylol sulfuric acid phosphorus aqueous solution with air delivery pump from cat head; Tetra methylol sulfuric acid phosphorus and urea are pressed 1.05~1.00: 1 molar ratio, under 60~70 ℃ temperature condition, carry out building-up reactions and generate tetra methylol sulfuric acid phosphorus-urea initial reduced body (THPS-Urea).The main deficiency that exists:
(1), among this preparation method, gas is without the air inlet washing still and the washing still washing of giving vent to anger, foreign matter content is higher, the quality product of producing is also relatively poor.
(2), formaldehyde and sulfuric acid mol ratio 8.05~8.10: 1 this be stoichiometric, formaldehyde is volatile in the circulation absorption process, hydroxyl is on the low side, the sulfuric acid surplus, the pH value of product is strongly-acid.
(3), 40 ℃~50 ℃ temperature is too low, speed of response is slower.Reaction is when saturated, and temperature is too low can not complete reaction.
(4), tetra methylol sulfuric acid phosphorus and urea in molar ratio 1.05~1.00: 1, tetra methylol sulfuric acid phosphorus is on the low side, the urea surplus, impurity is too many, temperature is on the low side, polymerization is incomplete, fabric has the not fire-retardant phenomenon in part after handling.
Summary of the invention
The production method of the tetra methylol sulfuric acid phosphorus urea initial reduced body that the present invention proposes is intended to overcome the above-mentioned defective of existing in prior technology, but the higher tetra methylol sulfuric acid phosphorus urea initial reduced body of output quality.
Technical solution of the present invention: this method comprises following processing step:
(1), the phosphine gas that produces when producing sodium hypophosphite is through air inlet washing still washing back collection storage, again phosphine gas is washed still through giving vent to anger and washes laggard recycle column.Gaseous impurities content after washing is lower.
(2), the batching still adds 300 kilograms deionized water, again with sulfuric acid, formaldehyde in molar ratio 1: stir in 8.5-8.7 (according to weather) the suction batching still.This proportioning can complete reaction in absorbing the phosphine gas process.
(3), the mixed solution for preparing is squeezed into recirculating still, under 40 ℃~55 ℃ temperature, absorb phosphine gas through recycle column, when record tetra methylol sulfuric acid phosphorus content 40%, pH value discharging during in 4 left and right sides, the suction concentration kettle is carried out steam jacket at vacuum tightness 0.06Mpa and is heated and concentrate tetra methylol sulfuric acid phosphorus to 75%.This concentration guaranteed with the urea proportioning after the content of tetra methylol sulfuric acid phosphorus-urea initial reduced body.
(4), feed liquid suction decolouring still is added 2 ‰ active carbon powder, through the secondary decolourization adsorption filtration, remove impurity like this, feed liquid is pure.
(5), feed liquid and urea mol ratio suction in 1.25: 1 batching still stirs, regulate pH value 5~6 with caustic soda, heat 70 ℃~80 ℃, be incubated polymerization in 7-8 hour, via hole diameter 2um fiber filter bag is prepared into the high-quality tetra methylol sulfuric acid phosphorus-urea initial reduced body of main content 67%~69%.
Advantage of the present invention: phosphine gas is through the air inlet washing and the washing of giving vent to anger, and gas purity is higher, reduces foreign matter content.Sulfuric acid, formaldehyde is by this proportioning, could complete reaction when absorbing phosphuret-(t)ed hydrogen, and tetra methylol sulfuric acid phosphorus circulation content is 40%, sulfuric acid, formaldehyde, phosphine gas complete reaction just in time in the feed liquid.Concentrate content to 75%, this concentration and urea mol ratio 1.25: 1 (drawing after manufacturing experimently repeatedly) have guaranteed the main content of tetra methylol sulfuric acid phosphorus.Original tetra methylol sulfuric acid phosphorus pH value is lower about 4, adds caustic soda and transfers pH value 5-6, can strengthen the product toughness, is difficult for tearing.Tetra methylol sulfuric acid phosphorus-urea initial reduced body have only when temperature at 70 ℃~80 ℃, and 7-8 hour ability tetra methylol sulfuric acid phosphorus of insulation could with the complete polymerization of urea, reach flame retardant effect.Guarantee the quality of tetra methylol sulfuric acid phosphorus-urea initial reduced body, the fabrics flame resistance excellent performance after this handles, good hand touch, wash resistant does not influence the original various premium propertiess of fabric.Has environmentally safe equally.Formaldehyde, sulfuric acid thoroughly absorbs phosphuret-(t)ed hydrogen.Realize the toxic gas zero release.
Description of drawings
Accompanying drawing 1 is technical process of the present invention.
Embodiment
Embodiment 1:
1, with phosphine gas after the washing of air inlet washing still, collect basin, wash into recycle column through the washing still of giving vent to anger again.
2, the batching still adds 300 kilograms deionized water, suction sulfuric acid while stirring, suction formaldehyde behind the still internal cooling (pressing formaldehyde and sulfuric acid mol ratio 8.5: 1).
3, feed liquid is squeezed into recirculating still, when temperature 〉=40 ℃, open air valve and recycle pump, chuck is progressively heated to 55 ℃ of pass gas check valves, and feed liquid absorbs phosphine gas when chemical examination records main content 40%, and basin is advanced in discharging.
4, when the circulation feed liquid has two stills, the suction concentration kettle, vacuum is when 0.06Mpa, and chuck is heated, the discharging still that advances to decolour when concentrating content chemical examination tetra methylol sulfuric acid phosphorus content to 75%.
5, feed liquid adds 2 ‰ active carbon powder while stirring in the decolouring still, and after 1 hour, vacuum filtration carries out secondary filtration after finishing again.
6, quantitative because of urea, will tetra methylol sulfuric acid phosphorus and urea suction in 1.25: 1 in molar ratio batching still in stir, add caustic soda and regulate the PH chemical examination and record 5, heating adds quantitative urea, when continuing to be heated to 70 ℃ ℃ when temperature to 40 ℃, the steam off valve was incubated after 7 hours, opened water quench.Chemically examine qualified back via hole diameter 2um fiber filter bag filtration packing.
Embodiment 2:
1, with phosphine gas after the washing of air inlet washing still, collect basin, wash into recycle column through the washing still of giving vent to anger again.
2, the batching still adds 300 kilograms deionized water, suction sulfuric acid while stirring, suction formaldehyde behind the still internal cooling (pressing formaldehyde and sulfuric acid mol ratio 8.7: 1).
3, feed liquid is squeezed into recirculating still, when temperature 〉=40 ℃, open air valve and recycle pump, chuck is progressively heated to 55 ℃ of pass gas check valves, and feed liquid absorbs phosphine gas when chemical examination records main content 40%, and basin is advanced in discharging.
4, when the circulation feed liquid has two stills, the suction concentration kettle, vacuum is when 0.06Mpa, and chuck is heated, the discharging still that advances to decolour when concentrating content chemical examination tetra methylol sulfuric acid phosphorus content to 75%.
5, feed liquid adds 2 ‰ active carbon powder while stirring in the decolouring still, and after 1 hour, vacuum filtration carries out secondary filtration after finishing again.
6, quantitative because of urea, will tetra methylol sulfuric acid phosphorus and urea suction in 1.25: 1 in molar ratio batching still in stir, add caustic soda and regulate the PH chemical examination and record 6, heating adds quantitative urea, when continuing to be heated to 80 ℃ when temperature to 40 ℃, the steam off valve was incubated after 8 hours, opened water quench.Chemically examine qualified back via hole diameter 2um fiber filter bag filtration packing.
Detect through the logical laboratory, mark standard Shanghai of country:
Sequence number Project Index
1 Main content ≥67%
2 Density 1.375-1.450
3 PH 5-6

Claims (1)

1. the preparation method of tetra methylol sulfuric acid phosphorus-urea initial reduced body is characterized in that this method comprises following processing step:
(1), the phosphine gas that produces when producing sodium hypophosphite is through air inlet washing still washing back collection storage, again phosphine gas washed laggard recycle column through the washing still of giving vent to anger, the gaseous impurities content after washing is lower;
(2), the batching still adds 300 kilograms deionized water, again with sulfuric acid, formaldehyde in molar ratio 1: stir in the 8.5-8.7 suction batching still, this proportioning can complete reaction in absorbing the phosphine gas process;
(3), the mixed solution for preparing is squeezed into recirculating still, under 40 ℃~55 ℃ temperature, absorb phosphine gas through recycle column, when record tetra methylol sulfuric acid phosphorus content 40%, the discharging 4 time of pH value, the suction concentration kettle, carry out steam jacket at vacuum tightness 0.06MPa and heat and concentrate tetra methylol sulfuric acid phosphorus to 75%, this concentration guaranteed with the urea proportioning after the content of tetra methylol sulfuric acid phosphorus-urea initial reduced body;
(4), feed liquid suction decolouring still is added 2 ‰ active carbon powder, through the secondary decolourization adsorption filtration, remove impurity, feed liquid is pure;
(5), feed liquid and urea mol ratio suction in 1.25: 1 batching still stirs, regulate pH value 5~6 with caustic soda, heat 70 ℃~80 ℃, be incubated polymerization in 7-8 hour, it is tetra methylol sulfuric acid phosphorus-urea initial reduced body of 67%~69% that via hole diameter 2um fiber filter bag is prepared into main content.
CN2009100273205A 2009-05-27 2009-05-27 Preparation method of tetrakis hydroxymetyl phosphonium sulfuric-urea polymer Expired - Fee Related CN101560225B (en)

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Publication number Priority date Publication date Assignee Title
CN102180904B (en) * 2011-03-10 2013-09-18 常熟新特化工有限公司 Preparation method for tetrakis hydroxymetyl phosphonium sulfuric
CN102180907A (en) * 2011-03-10 2011-09-14 常熟新特化工有限公司 Preparation method of tetrakis(hydroxymethyl)phosphonium sulfate urea precondensate
CN103603193B (en) * 2013-11-18 2016-11-09 河北名世锦簇纺织有限公司 A kind of flame retardant fabric

Citations (3)

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Publication number Priority date Publication date Assignee Title
US4265945A (en) * 1979-04-06 1981-05-05 The United States Of America As Represented By The Secretary Of Agriculture Quaternary ureidomethyl phosphonium salts
CN101134763A (en) * 2007-10-08 2008-03-05 江苏康祥集团公司 Method for preparing tetra hydroxymethyl phosphorus trichloride-urea primary condensed polymer
CN101333228A (en) * 2008-07-30 2008-12-31 江苏康祥集团公司 Method for preparing THPC-Urea using phosphine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265945A (en) * 1979-04-06 1981-05-05 The United States Of America As Represented By The Secretary Of Agriculture Quaternary ureidomethyl phosphonium salts
CN101134763A (en) * 2007-10-08 2008-03-05 江苏康祥集团公司 Method for preparing tetra hydroxymethyl phosphorus trichloride-urea primary condensed polymer
CN101333228A (en) * 2008-07-30 2008-12-31 江苏康祥集团公司 Method for preparing THPC-Urea using phosphine

Non-Patent Citations (2)

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Title
曾昭俊.四羟甲基氯化磷阻燃剂.《江苏化工》.1988,(第1期),第54页. *
王成俊等.次磷酸钠工业生产过程中PH3尾气处理技术.《天津化工》.2003,第17卷(第5期),第37-38页. *

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