CN104478929A - Production technology of THPO and production equipment thereof - Google Patents

Production technology of THPO and production equipment thereof Download PDF

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Publication number
CN104478929A
CN104478929A CN201410502012.4A CN201410502012A CN104478929A CN 104478929 A CN104478929 A CN 104478929A CN 201410502012 A CN201410502012 A CN 201410502012A CN 104478929 A CN104478929 A CN 104478929A
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tank
pump
spray
thpo
condenser
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CN104478929B (en
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李永刚
王明峰
宋宏图
马会娟
田路
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HUBEI XINGFA PHOSPHORUS CHEMICAL INDUSTRY RESEARCH INSTITUTE Co Ltd
Hubei Xingfa Chemicals Group Co Ltd
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HUBEI XINGFA PHOSPHORUS CHEMICAL INDUSTRY RESEARCH INSTITUTE Co Ltd
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Abstract

The invention relates to a process route for industrial production of THPO by using PH3 as a raw material and a device thereof. The production technology comprises the following steps: introducing PH3 gas into a spray tower, carrying out circulation spray in the spray tower by using a mixed aqueous solution of formaldehyde and an acid solution, adding synthesized THPC or THPS and a catalyst into an enamel reactor, heating and stirring, and slowly adding liquid alkali drop by drop; transferring the materials into a dehydration kettle to carry out dehydration for two times, carrying out reduced pressure distillation, stopping dehydration when material moisture is lower than 2.0%, settling for several days, filtering through a precision filter, barreling and packaging. According to the industrial device and process route for production of THPO, industrial production of THPO is successfully completed for the first time; a by-product PH3 in the production of sodium hypophosphite is utilized comprehensively; equipment investment is little; production is safe and reliable; there is few ''three wastes'' (waste gas, waste water and industrial residue); and the environment is not polluted. The production technology and the production equipment accord with the national green and environmental policy and the strategy of sustainable development.

Description

A kind of production technique of trishydroxymethyl phosphine oxide and production unit
Technical field
The invention belongs to chemical production field, particularly a kind of production technique of the trishydroxymethyl phosphine oxide utilizing phosphine gas to be raw material and production unit.
Background technology
Along with growing to even greater heights of cry of taking precautions against natural calamities fire-retardant in world wide and being gradually improved of flame retardant regulation, safety and environmental protection standard increasingly stringent and plastic prod application increase, by 2014, the whole fire retardant market requirement will reach 2,200,000 tons, and organic phosphorus flame retardant world market capacity is expected to reach 680,000 tons.At present, a lot of or inorganic, the halogen-containing fire retardant of the fire retardant of domestic production and use.But, owing to releasing smog, corrosive gases and toxic gas when halogen containing flame-retardant exists burning.At present, most of Europe country has forbidden the use of halogen flame.American-European countries has started progressively to replace halogen-containing fire retardant with Halogen combustion agent.
At present, the technology of synthesizing trimethylol phosphine oxide, has delivering of a lot of research report and patented technology both at home and abroad.But there is no industrialized unit to go into operation.Owing to lacking reasonable, efficient production unit and operational path, make with PH 3for the energy consumption of Material synthesis THPO is high, production cost is high, and environmental pollution is serious, constrains its plant-scale development.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of with PH 3for production technique and the industrialized unit of Material synthesis THPO, according to this operational path, success completes with PH on this industrialized unit 3for the suitability for industrialized production of Material synthesis THPO.The method for successfully completing the suitability for industrialized production of THPO first, has both enriched flame retardant products structure, can create certain society, economic worth; Fully utilize again the byproduct PH in Sodium hypophosphite production 3, achieve recycling economy, improve added value of product; Equipment investment is little simultaneously, and production safety is reliable, and " three wastes " are few, without any environmental hazard, meet the policy of national green environmental protection and the strategy of Sustainable development.
Provided by the invention with PH 3for operational path and the production equipment of Material synthesis THPO, wherein operational path comprises following step:
Step one: by PH 3gas passes into spray column, and utilize the formalin of 1 ~ 30% and the mixed aqueous solution of 1 ~ 30% acid solution to carry out circulated sprinkling in spray column, gas passes into speed 0.1 ~ 10m 3/ min, circulation fluid temperature is 0 ~ 15 DEG C, temperature of reaction 0 ~ 20 DEG C, the extraction when the concentration of THPC or THPS is 5 ~ 85%, and waste gas utilization oxidizing agent solution absorbs; Preferred formalin concentration is 25 ~ 30%; Preferred acid strength is 15 ~ 18%; Preferred PH 3it is 1 ~ 3m that gas passes into speed 3/ min; Preferred circulation fluid temperature 5 ~ 8 DEG C; Preferred THPC or THPS concentration is 50 ~ 85%; Particularly preferred concentration is 75 ~ 85%; Preferred temperature of reaction is 8 ~ 10 DEG C;
Step 2: by concentration be 5 ~ 85% THPC or the THPS aqueous solution and catalyzer add in reactor, at 25-65 DEG C, add the liquid caustic soda that concentration is 1 ~ 30%; Preferred THPC or THPS concentration is 50-85%, and particularly preferred concentration is 75 ~ 85%; Preferred temperature is 30 ~ 35 DEG C; Preferred alkali concn is 12 ~ 15%; Step 3: when pH is 9.5 ~ 12 time, stops dripping alkali lye; When to be heated to temperature be 55 ~ 90 DEG C, insulation 6 ~ 15h; Preferred pH is 10.5 ~ 11, and preferred temperature is 65 ~ 70 DEG C; Preferred soaking time is 10h;
Step 4: drip the acid solution acid adjustment that concentration is about 1% ~ 30%, when pH is 6.5 ~ 8.0 time, stops dripping acid solution, after stirring 0.5h ~ 2h, is down to room temperature; Preferred acid concentration is 12 ~ 15%; Preferred pH is 7.0 ~ 7.5; Preferred soaking time is 1h;
Step 5: material is transferred to dehydrating kettle and carries out primary dewatering, underpressure distillation, control temperature is at about 50 ~ 85 DEG C; When material moisture content is 5 ~ 20%, stop distillation, once centrifugal desalination when being cooled to about 20 DEG C; Preferred dehydration temperaturre is 65 ~ 70 DEG C, preferred feed moisture content 8 ~ 12%;
Step 6: filtrate is moved to full gear still, add aldehyde removing agent, after stirred at ambient temperature 1 ~ 3h, secondary centrifuging desalination;
Step 7: filtrate is transferred to dehydrating kettle and carries out second dehydration, underpressure distillation, control temperature about 50 ~ 85 DEG C, dewater to material moisture content lower than 2.0% time, stop dehydration; Preferred dehydration temperaturre is 65 ~ 70 DEG C, preferred feed moisture 1.5 ~ 1.8%;
Step 8: material is transferred to crude product tank while hot, sedimentation 1 ~ 5 day, filters through accurate filter, gets product.
In described step one, acid solution is hydrochloric acid or sulfuric acid, and concentration is 1 ~ 30%, and preferred concentration is 15 ~ 18%;
In described step one, formalin concentration is 1 ~ 30%, and preferred concentration is 25 ~ 30%;
In described step one, PH 3the speed that passes into of gas is 0.1 ~ 10m 3/ min, favor speed is 2m 3/ min;
In described step one, circulation fluid temperature is 0 ~ 15 DEG C, and preferable temperature is 5 ~ 8 DEG C;
In described step one, temperature of reaction is 0 ~ 20 DEG C, and preferable temperature is 8 ~ 10 DEG C;
In described step one, THPC or THPS extraction concentration is 5 ~ 85%, and preferred concentration is 50 ~ 85%, and particularly preferably concentration is 75 ~ 85%;
In described step one, tail gas absorption oxygenant includes but not limited to following one or more: the hypochlorite (M is basic metal or alkaline earth metal cation) of metal M, hydrogen peroxide, the vitriol oil.
In described step 2, alkali includes but not limited to following one or more: the oxyhydroxide (M is basic metal or alkaline earth metal cation) of metal M, ammoniacal liquor, sodium carbonate, sodium methylate, sodium ethylate, pyridine, front three ammonia, triethylamines etc., preferred alkali is sodium hydroxide, triethylamine.
In described step 2, catalyzer comprises: palladium, barium sulfate, bariumchloride, single nickel salt, one or more in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, and preferred catalyzer is palladium, barium sulfate.
In described step 2, concentration of lye is 1 ~ 30%, and preferred concentration of lye is 12 ~ 15%.
In described step 2, dripping alkali temperature is 25 ~ 62 DEG C, and preferably dripping alkali temperature is 30 ~ 35 DEG C.
In described step 3, stop the pH adding alkali to be 9.5 ~ 12, preferably stop the pH adding alkali to be 10.5 ~ 11.
In described step 3, temperature of reaction is 55 ~ 90 DEG C, and preferable reaction temperature is 65 ~ 70 DEG C.
In described step 3, soaking time is 6 ~ 15h, and preferred soaking time is 10h.
In described step 4, acid solution comprises: hydrochloric acid, sulfuric acid etc.
In described step 4, acid strength is 1 ~ 30%, and preferred acid strength is 12 ~ 15%.
In described step 4, the pH stopping acid adding is 6.5 ~ 8.0, and preferred pH is 7.0 ~ 7.5.
In described step 4, soaking time is 0.5 ~ 2h, and preferred soaking time is 1h.
In described step 5, primary dewatering temperature is 50 ~ 85 DEG C, and preferred dehydration temperaturre is 65 ~ 70 DEG C.
In described step 5, the material moisture content stopping primary dewatering is 5 ~ 20%, and preferred feed moisture is 8 ~ 12%.
In described step 5, once centrifugal desalination temperature is 20 ~ 25 DEG C.
In described step 6, aldehyde removing agent comprises: S-WAT, potassium sulfite, superoxide (as: hydrogen peroxide, Potassium peroxide, sodium peroxide, copper peroxide, peroxidation perbenzoic acid, peroxydicarbonate etc.), V-Brite Bs etc., preferred aldehyde removing agent is one or more in V-Brite B.
In described step 6, full gear temperature of reaction is 20 ~ 25 DEG C.
In described step 6, the full gear reaction times is 1 ~ 3h, and the preferred full gear reaction times is 2h.
In described step 7, second dehydration temperature is 50 ~ 85 DEG C, and preferred dehydration temperaturre is 65 ~ 70 DEG C.
In described step 7, stop the material moisture content of second dehydration lower than 2%, preferred feed moisture is
1.5~1.8%。
In described step 8,1 ~ 5 day THPO crude product settling time, the preferred settling time is 3 days.
In described step 8, accurate filter order number is 200 ~ 800 orders, and preferred filters order number is 800 orders.
The main device of suitability for industrialized production THPO comprises: spray-absorption system, tail gas absorbing system, vacuum distillation apparatus, synthesis reactor, one-level dehydrating kettle, secondary dehydrating kettle, first-stage centrifugal machine, two-stage centrifugal machine, transfer tank, full gear still, waste water tank, accurate filter, crude product tank, finished pot; Described spray-absorption system comprises three grades of spray-absorption devices, and described tail gas absorbing system comprises secondary device for absorbing tail gas.
Described spray-absorption device comprises: absorption tower body, resorber, condenser, temperature sensor, recycle pump, extraction pump, make-up pump, and raw material supplements tank, extraction receiver; Described absorption tower body lower end is connected with resorber, and described resorber is connected through the sparger of recycle pump with absorption tower body upper end, is filled in described absorption tower by multilayer stopping composition; Described condenser is between recycle pump and sparger, and described temperature sensor is between condenser and sparger; Described raw material supplements tank and is connected with resorber through make-up pump, and described extraction receiver is connected with resorber through extraction pump.
Described spray-absorption device is divided into three grades, PH 3gas enters absorption tower body from one-level spray-absorption device inlet mouth, one-level spray-absorption device venting port is connected with secondary spray-absorption device inlet mouth, secondary spray-absorption device venting port is connected with three grades of spray-absorption device inlet mouths, and three grades of spray-absorption device venting ports are connected with device for absorbing tail gas inlet mouth.
Described spray-absorption device is divided into three grades, raw material supplements tank and is connected with three grades of resorbers through impeller pump, three grades of resorbers are connected with secondary absorber through impeller pump, and secondary absorber is connected with first absorber through impeller pump, and first absorber is connected with extraction receiver through extraction pump.
Described device for absorbing tail gas comprises: absorption tower body, withdrawing can, condenser, recycle pump, extraction pump, make-up pump, and oxygenant supplements tank, byproduct tank; Described absorption tower body lower end is connected with withdrawing can, and described withdrawing can is connected through the sparger of recycle pump with absorption tower body upper end, is filled in described absorption tower by multilayer stopping composition; Described condenser is between recycle pump and sparger, and described oxygenant supplements tank and is connected with withdrawing can through make-up pump, and described byproduct tank is connected with withdrawing can through extraction pump.
Described device for absorbing tail gas is divided into secondary, and one-level device for absorbing tail gas inlet mouth is connected with three grades of spray-absorption device venting ports, and secondary device for absorbing tail gas inlet mouth is connected with one-level device for absorbing tail gas venting port, the emptying of secondary device for absorbing tail gas venting port.
Described device for absorbing tail gas is divided into secondary, and oxygenant supplements tank and is connected with secondary recovery tank through impeller pump, and secondary recovery tank is connected with one-level withdrawing can through impeller pump, and one-level withdrawing can is connected with byproduct tank through extraction pump.
Described vacuum system comprises: tank, water-circulating pump, water jet pump, condenser, vacuum buffer tank etc.; Described tank lower accepting water recycle pump, described water-circulating pump connects with water jet pump through pipeline, and described water jet pump lower linking tube road is connected with tank, and side is connected with vacuum buffer tank by pipeline, described condenser, between water jet pump and tank, is connected by pipeline.
Described synthesis reactor connects sour test tank, alkali test tank, raw material test tank, under connect one-level dehydrating kettle;
Described one-level dehydrating kettle connects condenser, under connect first-stage centrifugal machine, described condenser is connected with waste water tank, and described waste water tank is connected with vacuum system.
Transfer tank is connect under described first-stage centrifugal machine.
Described transfer tank is connected with full gear still.
Two-stage centrifugal machine is connect under described full gear still.
Secondary dehydrating kettle is connect under described two-stage centrifugal machine.
Described secondary dehydrating kettle connects condenser, under connect crude product tank, described condenser is connected with waste water tank, and described waste water tank is connected with vacuum system.
Described crude product tank connects compressed nitrogen, under be connected with accurate filter, described accurate filter is connected with finished pot.
Each device described above is connected by conventional chemical pipeline.
The invention has the beneficial effects as follows: for successfully completing with PH 3for the suitability for industrialized production of Material synthesis THPO, there is larger social benefit and economic worth.Fully utilize the byproduct PH in Sodium hypophosphite production 3, achieve recycling economy, improve added value of product.Adopt secondary device for absorbing tail gas, both without any poisonous, obnoxious flavour discharge, environmental protection, had had and had created certain economic worth.
Accompanying drawing explanation
Fig. 1 is PH of the present invention 3for the production system schematic diagram of the trishydroxymethyl phosphine oxide of raw material.
Fig. 2 is exhaust gas recovery system schematic diagram of the present invention.
Fig. 3 is vacuum system schematic diagram of the present invention.
Fig. 4 is spray-absorption device schematic diagram of the present invention.
Fig. 5 is device for absorbing tail gas schematic diagram of the present invention.
Embodiment
Embodiment 1
1) by PH 3gas is with 1 ~ 3m 3/ min passes into spray column, the mixed aqueous solution of formaldehyde (25% ~ 30%) and hydrochloric acid (12% ~ 15%) is utilized to carry out circulated sprinkling in spray column, temperature of reaction 8 ~ 10 DEG C, controlled circulation liquid temp is at 5 ~ 8 DEG C, the extraction when the concentration of Tetrakis hydroxymethyl phosphonium chloride (THPC) is 75 ~ 85%, waste gas utilization chlorine bleach liquor absorbs, and byproduct sodium hypophosphite is sold;
2) by the above-mentioned synthetic 400L 80%THPC aqueous solution and 80g catalyzer (40g diatomite, 0.008g palladium, 40g barium sulfate) add in 1000L enamel reaction still, heated and stirred, slowly drips the sodium hydroxide that concentration is 12% when temperature is about 30 DEG C; When pH is 10.5 ~ 11 time, stop dripping alkali; When being slowly warming up to 65 ~ 68 DEG C, insulated and stirred 10h; Then, being the hydrochloric acid of 15% toward slowly dripping concentration in still, when pH is 7.3 ~ 7.5 time, stops dripping acid, after stirring 1h, being down to room temperature;
3) material is transferred to 1000L dehydrating kettle and carries out primary dewatering, underpressure distillation, control temperature in the kettle at about 70 DEG C; When material moisture content is 10 ~ 15%, stops dehydration, carry out once centrifugal desalination when being cooled to about 20 DEG C, gained salt NaCl quality about 100 Kg; Then, filtrate is moved to full gear still, add a certain amount of S-WAT, after stirred at ambient temperature 2h, carry out secondary centrifuging desalination; Filtrate is transferred to 1000L dehydrating kettle and carries out second dehydration, underpressure distillation, control temperature in the kettle at about 70 DEG C, dewater to material moisture content lower than 1.5% time, stop dehydration; Material is transferred to crude product tank while hot, sedimentation 3 days, through 800 order accurate filters filter, gained trishydroxymethyl phosphine oxide (THPO) about 255Kg, product purity more than 98%, yield more than 90%.
Embodiment 2
1) by PH 3gas is with 1 ~ 3m 3/ min passes into spray column, the mixed aqueous solution of formaldehyde (25% ~ 30%) and hydrochloric acid (12% ~ 15%) is utilized to carry out circulated sprinkling in spray column, temperature of reaction 8 ~ 10 DEG C, controlled circulation liquid temp is at 5 ~ 8 DEG C, the extraction when the concentration of Tetrakis hydroxymethyl phosphonium chloride (THPC) is 75 ~ 85%, waste gas utilization chlorine bleach liquor absorbs, and byproduct sodium hypophosphite is sold;
2) add in 1000L enamel reaction still by the above-mentioned synthetic 400L 80%THPC aqueous solution and 80g catalyzer (2g palladium), heated and stirred, slowly drips the sodium hydroxide that concentration is 12% when temperature is about 30 DEG C; When pH is 10.5 ~ 11 time, stop dripping alkali; When being slowly warming up to 65 ~ 68 DEG C, insulated and stirred 10h; Then, being the hydrochloric acid of 15% toward slowly dripping concentration in still, when pH is 7.3 ~ 7.5 time, stops dripping acid, after stirring 1h, being down to room temperature;
3) treatment step is identical with upper, gained trishydroxymethyl phosphine oxide (THPO) about 230Kg, product purity more than 95%, yield more than 80%.
Embodiment 3
1) by PH 3gas is with 1 ~ 3m 3/ min passes into spray column, the mixed aqueous solution of formaldehyde (25% ~ 30%) and hydrochloric acid (12% ~ 15%) is utilized to carry out circulated sprinkling in spray column, temperature of reaction 8 ~ 10 DEG C, controlled circulation liquid temp is at 5 ~ 8 DEG C, the extraction when the concentration of Tetrakis hydroxymethyl phosphonium chloride (THPC) is 75 ~ 85%, waste gas utilization chlorine bleach liquor absorbs, and byproduct sodium hypophosphite is sold;
2) add in 1000L enamel reaction still by the above-mentioned synthetic 400L 80%THPC aqueous solution and 80g catalyzer (1g palladium, 20g barium sulfate), heated and stirred, slowly drips the sodium hydroxide that concentration is 12% when temperature is about 30 DEG C; When pH is 10.5 ~ 11 time, stop dripping alkali; When being slowly warming up to 65 ~ 68 DEG C, insulated and stirred 10h; Then, being the hydrochloric acid of 15% toward slowly dripping concentration in still, when pH is 7.3 ~ 7.5 time, stops dripping acid, after stirring 1h, being down to room temperature;
3) treatment step is identical with upper, gained trishydroxymethyl phosphine oxide (THPO) about 245Kg, product purity more than 97%, yield more than 85%.
Embodiment 4
A kind of device of trishydroxymethyl phosphine oxide (THPO) suitability for industrialized production, this device mainly comprises: spray-absorption system, tail gas absorbing system, vacuum system, finished product synthesis system; Described spray-absorption system is in series at least three grades of spray-absorption devices, and described tail gas absorbing system is that at least secondary device for absorbing tail gas is in series;
Described spray-absorption device comprises: absorption tower body, resorber, condenser, temperature sensor, recycle pump, extraction pump, make-up pump, and raw material supplements tank, extraction receiver; Absorption tower body lower end is connected with resorber, and resorber is connected through the sparger of recycle pump with absorption tower body upper end, is filled in absorption tower by multilayer stopping composition; Condenser is between recycle pump and sparger, and temperature sensor is between condenser and sparger; Raw material supplements tank and is connected with resorber through make-up pump, and extraction receiver is connected with resorber through extraction pump;
Described device for absorbing tail gas comprises: absorption tower body, withdrawing can, condenser, recycle pump, extraction pump, make-up pump, and oxygenant supplements tank, byproduct tank; Described absorption tower body lower end is connected with withdrawing can, and described withdrawing can is connected through the sparger of recycle pump with absorption tower body upper end, is filled in described absorption tower by multilayer stopping composition; Described condenser is between recycle pump and sparger, and described oxygenant supplements tank and is connected with withdrawing can through make-up pump, and described byproduct tank is connected with withdrawing can through extraction pump;
Described vacuum system comprises: tank, water-circulating pump, water jet pump, condenser, vacuum buffer tank etc.; Described tank lower accepting water recycle pump, described water-circulating pump connects with water jet pump through pipeline, and described water jet pump lower linking tube road is connected with tank, and side is connected with vacuum buffer tank by pipeline, described condenser, between water jet pump and tank, is connected by pipeline;
Finished product synthesis system comprises: synthesis reactor, full gear still, one-level dehydrating kettle, secondary dehydrating kettle, first-stage centrifugal machine, two-stage centrifugal machine, transfer tank, condenser, waste water tank, waste water processing station, THPO crude product tank, accurate filter, THPO finished pot, described synthesis reactor connects sour test tank, alkali test tank, raw material test tank, under connect one-level dehydrating kettle; One-level dehydrating kettle connects condenser, under connect first-stage centrifugal machine, described condenser is connected with waste water tank, and described waste water tank is connected with vacuum system; Transfer tank is connect under first-stage centrifugal machine, transfer tank is connected with full gear still, connect two-stage centrifugal machine under full gear still, under two-stage centrifugal machine, connect secondary dehydrating kettle, secondary dehydrating kettle connects condenser, under connect crude product tank, described condenser is connected with waste water tank, and described waste water tank is connected with vacuum system, and crude product tank connects compressed nitrogen, under be connected with accurate filter, described accurate filter is connected with finished pot.
Described spray-absorption device is divided into three grades, PH 3gas enters absorption tower body from one-level spray-absorption device inlet mouth, one-level spray-absorption device venting port is connected with secondary spray-absorption device inlet mouth, secondary spray-absorption device venting port is connected with three grades of spray-absorption device inlet mouths, and three grades of spray-absorption device venting ports are connected with device for absorbing tail gas inlet mouth.
Described spray-absorption device is divided into three grades, raw material supplements tank and is connected with three grades of resorbers through impeller pump, three grades of resorbers are connected with secondary absorber through impeller pump, and secondary absorber is connected with first absorber through impeller pump, and first absorber is connected with extraction receiver through extraction pump.
Described device for absorbing tail gas is divided into secondary, and one-level device for absorbing tail gas inlet mouth is connected with three grades of spray-absorption device venting ports, and secondary device for absorbing tail gas inlet mouth is connected with one-level device for absorbing tail gas venting port, the emptying of secondary device for absorbing tail gas venting port; Described device for absorbing tail gas is divided into secondary, and oxygenant supplements tank and is connected with secondary recovery tank through impeller pump, and secondary recovery tank is connected with one-level withdrawing can through impeller pump, and one-level withdrawing can is connected with byproduct tank through extraction pump.

Claims (10)

1. a production technique for trishydroxymethyl phosphine oxide (THPO), is characterized in that, comprise the steps:
1) by PH 3gas is with 0.1 ~ 10m 3the speed of/min passes into spray column, in spray column, the mixed aqueous solution of the formalin of 1 ~ 30% and 1 ~ 30% hydrochloric acid or sulfuric acid is carried out circulated sprinkling as spray liquid in spray column, circulation fluid temperature is 0 ~ 15 DEG C, temperature of reaction 0 ~ 20 DEG C, the extraction when the concentration of THPC or THPS is 5 ~ 85%, waste gas utilization oxidizing agent solution absorbs;
2) by concentration be 5 ~ 85% THPC or the THPS aqueous solution and catalyzer add in reactor, at 25-65 DEG C, add the liquid caustic soda that concentration is 1 ~ 30%;
3) when pH is 9.5 ~ 12 time, stop dripping alkali lye; When to be heated to temperature be 55 ~ 90 DEG C, insulation 6 ~ 15h;
4) drip concentration be about 1% ~ 30% hydrochloric acid or sulfuric acid carry out acid adjustment, when pH is 6.5 ~ 8.0 time, stop dripping acid solution, after stirring 0.5h ~ 2h, be down to room temperature;
5) material is transferred to dehydrating kettle and carries out primary dewatering, underpressure distillation, control temperature is at about 50 ~ 85 DEG C; When material moisture content is 5 ~ 20%, stop distillation, once centrifugal desalination when being cooled to about 20 DEG C;
6) filtrate is moved to full gear still, add aldehyde removing agent, stir 1 ~ 3h at 20-25 DEG C after, secondary centrifuging desalination;
7) filtrate is transferred to dehydrating kettle and carries out second dehydration, underpressure distillation, control temperature about 50 ~ 85 DEG C, dewater to material moisture content lower than 2.0% time, stop dehydration;
8) material is transferred to crude product tank while hot, sedimentation 1 ~ 5 day, is filtered to 200-800 order through accurate filter, gets product.
2. a production technique for trishydroxymethyl phosphine oxide (THPO), is characterized in that, comprise the steps:
1) by PH 3gas passes into spray column, and utilize the formalin of 25 ~ 30% and the mixed aqueous solution of 15 ~ 18% hydrochloric acid or sulfuric acid to carry out circulated sprinkling in spray column, gas passes into speed 2m 3/ min, circulation fluid temperature is 5 ~ 8 DEG C, temperature of reaction 8 ~ 10 DEG C, the extraction when the concentration of THPC or THPS is 75 ~ 85%, and waste gas utilization oxidizing agent solution absorbs;
2) by concentration be 75 ~ 85% THPC or the THPS aqueous solution and catalyzer add in reactor, at 30 ~ 35 DEG C, add the liquid caustic soda that concentration is 12 ~ 15%;
3) when pH is 10.5 ~ 11 time, stop dripping alkali lye; When to be heated to temperature be 65 ~ 70 DEG C, insulation 10h;
4) drip concentration be about 12 ~ 15% hydrochloric acid or sulfuric acid carry out acid adjustment, when pH is 7.0 ~ 7.5 time, stop dripping acid solution, after stirring 1h, be down to room temperature;
5) material is transferred to dehydrating kettle and carries out primary dewatering, underpressure distillation, control temperature is at about 65 ~ 70 DEG C; When material moisture content is 8 ~ 12%, stop distillation, once centrifugal desalination when being cooled to about 20 DEG C;
6) filtrate is moved to full gear still, add aldehyde removing agent, stir 2h at 20-25 DEG C after, secondary centrifuging desalination;
7) filtrate is transferred to dehydrating kettle and carries out second dehydration, underpressure distillation, control temperature about 65 ~ 70 DEG C, when dewatering to material moisture content 1.5 ~ 1.8%, stop dehydration;
8) material is transferred to crude product tank while hot, sedimentation 3 days, is filtered to 800 orders through accurate filter, gets product.
3. the production technique of trishydroxymethyl phosphine oxide (THPO) as claimed in claim 1 or 2, it is characterized in that, in step 1) in, described oxygenant includes but not limited to following one or more: the hypochlorite (M is basic metal or alkaline earth metal cation) of metal M, hydrogen peroxide, the vitriol oil.
4. the production technique of trishydroxymethyl phosphine oxide (THPO) as claimed in claim 1 or 2, it is characterized in that, in step 2) in, described liquid caustic soda includes but not limited to following one or more: the oxyhydroxide (M is basic metal or alkaline earth metal cation) of metal M, ammoniacal liquor, sodium carbonate, sodium methylate, sodium ethylate, pyridine, front three ammonia, triethylamine.
5. the production technique of trishydroxymethyl phosphine oxide (THPO) as claimed in claim 1 or 2, is characterized in that, in step 2) in, described catalyzer comprises: palladium, barium sulfate, bariumchloride, single nickel salt, one or more in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
6. the production technique of trishydroxymethyl phosphine oxide (THPO) as claimed in claim 1 or 2, it is characterized in that, in step 6) in, described aldehyde removing agent comprises: S-WAT, potassium sulfite, hydrogen peroxide, Potassium peroxide, sodium peroxide, copper peroxide, peroxidation perbenzoic acid, peroxydicarbonate, one or more in V-Brite B.
7. adopt the device of production technique suitability for industrialized production trishydroxymethyl phosphine oxide (THPO) described in any one of right 1-6, it is characterized in that, this device mainly comprises: spray-absorption system, tail gas absorbing system, vacuum system, finished product synthesis system; Described spray-absorption system is in series at least three grades of spray-absorption devices, and described tail gas absorbing system is that at least secondary device for absorbing tail gas is in series;
Described spray-absorption device comprises: absorption tower body, resorber, condenser, temperature sensor, recycle pump, extraction pump, make-up pump, and raw material supplements tank, extraction receiver; Absorption tower body lower end is connected with resorber, and resorber is connected through the sparger of recycle pump with absorption tower body upper end, is filled in absorption tower by multilayer stopping composition; Condenser is between recycle pump and sparger, and temperature sensor is between condenser and sparger; Raw material supplements tank and is connected with resorber through make-up pump, and extraction receiver is connected with resorber through extraction pump;
Described device for absorbing tail gas comprises: absorption tower body, withdrawing can, condenser, recycle pump, extraction pump, make-up pump, and oxygenant supplements tank, byproduct tank; Described absorption tower body lower end is connected with withdrawing can, and described withdrawing can is connected through the sparger of recycle pump with absorption tower body upper end, is filled in described absorption tower by multilayer stopping composition; Described condenser is between recycle pump and sparger, and described oxygenant supplements tank and is connected with withdrawing can through make-up pump, and described byproduct tank is connected with withdrawing can through extraction pump;
Described vacuum system comprises: tank, water-circulating pump, water jet pump, condenser, vacuum buffer tank etc.; Described tank lower accepting water recycle pump, described water-circulating pump connects with water jet pump through pipeline, and described water jet pump lower linking tube road is connected with tank, and side is connected with vacuum buffer tank by pipeline, described condenser, between water jet pump and tank, is connected by pipeline;
Finished product synthesis system comprises: synthesis reactor, full gear still, one-level dehydrating kettle, secondary dehydrating kettle, first-stage centrifugal machine, two-stage centrifugal machine, transfer tank, condenser, waste water tank, waste water processing station, THPO crude product tank, accurate filter, THPO finished pot, described synthesis reactor connects sour test tank, alkali test tank, raw material test tank, under connect one-level dehydrating kettle; One-level dehydrating kettle connects condenser, under connect first-stage centrifugal machine, described condenser is connected with waste water tank, and described waste water tank is connected with vacuum system; Transfer tank is connect under first-stage centrifugal machine, transfer tank is connected with full gear still, connect two-stage centrifugal machine under full gear still, under two-stage centrifugal machine, connect secondary dehydrating kettle, secondary dehydrating kettle connects condenser, under connect crude product tank, described condenser is connected with waste water tank, and described waste water tank is connected with vacuum system, and crude product tank connects compressed nitrogen, under be connected with accurate filter, described accurate filter is connected with finished pot.
8. production equipment as claimed in claim 7, is characterized in that: described spray-absorption device is divided into three grades, PH 3gas enters absorption tower body from one-level spray-absorption device inlet mouth, one-level spray-absorption device venting port is connected with secondary spray-absorption device inlet mouth, secondary spray-absorption device venting port is connected with three grades of spray-absorption device inlet mouths, and three grades of spray-absorption device venting ports are connected with device for absorbing tail gas inlet mouth.
9. production equipment as claimed in claim 7, it is characterized in that: described spray-absorption device is divided into three grades, raw material supplements tank and is connected with three grades of resorbers through impeller pump, three grades of resorbers are connected with secondary absorber through impeller pump, secondary absorber is connected with first absorber through impeller pump, and first absorber is connected with extraction receiver through extraction pump.
10. production equipment as claimed in claim 7, it is characterized in that: described device for absorbing tail gas is divided into secondary, one-level device for absorbing tail gas inlet mouth is connected with three grades of spray-absorption device venting ports, secondary device for absorbing tail gas inlet mouth is connected with one-level device for absorbing tail gas venting port, the emptying of secondary device for absorbing tail gas venting port; Described device for absorbing tail gas is divided into secondary, and oxygenant supplements tank and is connected with secondary recovery tank through impeller pump, and secondary recovery tank is connected with one-level withdrawing can through impeller pump, and one-level withdrawing can is connected with byproduct tank through extraction pump.
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