CN104478929B - Production technology of THPO and production equipment thereof - Google Patents
Production technology of THPO and production equipment thereof Download PDFInfo
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- CN104478929B CN104478929B CN201410502012.4A CN201410502012A CN104478929B CN 104478929 B CN104478929 B CN 104478929B CN 201410502012 A CN201410502012 A CN 201410502012A CN 104478929 B CN104478929 B CN 104478929B
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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
Technical field
The invention belongs to chemical production field, more particularly to a kind of utilization phosphine gas are aoxidized for the trihydroxy methyl of raw material
The production technology and production equipment of phosphine.
Background technology
With growing to even greater heights for fire-retardant cry of taking precautions against natural calamities in world wide and being gradually improved for flame retardant regulation, safety and environmental protection standard
Increasingly strict and plastic product application increases, and by 2014, the whole fire retardant market demand was up to 2,200,000 tons, organophosphor system
Fire retardant world market capacity is expected to reach 680,000 tons.At present, domestic production and the fire retardant for using are many or inorganic, halogen
The fire retardant of element.But, due to releasing smog, corrosive gas and toxic gas when halogen containing flame-retardant is present to burn.At present, Europe
The most of country in continent has forbidden the use of halogen flame.American-European countries has begun to progressively fire agent substitution containing halogen with Halogen
Fire retardant.
At present, the technology of synthesizing trimethylol phosphine oxide, there is delivering for many research reports and patented technology both at home and abroad.
But there is no industrialized unit to go into operation.Due to lacking reasonable, efficient production equipment and process route so that with PH3For raw material is closed
Into the high energy consumption of THPO, production cost is high, and environmental pollution is serious, constrains its plant-scale development.
The content of the invention
For above-mentioned the deficiencies in the prior art, the invention provides one kind with PH3It is the production technology of Material synthesis THPO
And industrialized unit, according to the process route, succeed and completed with PH on the industrialized unit3It is Material synthesis THPO
Industrialized production.The method has successfully completed the industrialized production of THPO first, has both enriched flame retardant products structure, can
Create certain society, economic worth；The byproduct PH in Sodium hypophosphite production is fully utilized again3, recycling economy is realized,
Improve added value of product；Equipment investment is small simultaneously, production safety reliability, and " three wastes " are few, without any environmental hazard, meet state
The policy and the strategy of sustainable development of family's environmental protection.
The present invention provide with PH3It is the process route and process units of Material synthesis THPO, wherein process route includes
Following steps：
Step one：By PH3Gas is passed through spray column, formalin and 1 ~ 30% acid solution in spray column using 1 ~ 30%
Mixed aqueous solution is circulated spray, and gas is passed through 0.1 ~ 10m of speed3/ min, circulation fluid temperature is 0 ~ 15 DEG C, reaction temperature 0 ~
20 DEG C, produced when the concentration of THPC or THPS is 5 ~ 85%, waste gas utilization oxidizing agent solution absorbs；Preferred formalin
Concentration is 25 ~ 30%；Preferred acid strength is 15 ~ 18%；Preferred PH3It is 1 ~ 3m that gas is passed through speed3/min；Preferably follow
5 ~ 8 DEG C of ring liquid temperature degree；Preferred THPC or THPS concentration is 50 ~ 85%；Particularly preferred concentration is 75 ~ 85%；Preferred reaction
Temperature is 8 ~ 10 DEG C；
Step 2：By concentration for 5 ~ 85% THPC the or THPS aqueous solution and catalyst add reactor in, at 25-65 DEG C
It is lower to 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, stop that alkali lye is added dropwise；Be heated to temperature for 55 ~ 90 DEG C when, be incubated 6 ~ 15h；Preferably
PH is 10.5 ~ 11, and preferred temperature is 65 ~ 70 DEG C；Preferred soaking time is 10h；
Step 4：The acid solution acid adjustment that concentration is for 1% ~ 30% or so is added dropwise, when pH is 6.5 ~ 8.0, stops that acid solution is added dropwise, stir
After mixing 0.5h ~ 2h, room temperature is down to；Preferred acid concentration is 12 ~ 15%；Preferred pH is 7.0 ~ 7.5；Preferred soaking time is
1h；
Step 5：Transferring the material into dehydrating kettle carries out primary dewatering, and vacuum distillation controls temperature at 50 ~ 85 DEG C or so；
When material moisture content is 5 ~ 20%, stop distillation, desalination is once centrifuged when being cooled to 20 DEG C or so；Preferred dehydration temperaturre is 65 ~
70 DEG C, preferred feed moisture content 8 ~ 12%；
Step 6：Filtrate is moved into full gear kettle, aldehyde removing agent is added, after stirring 1 ~ 3h at room temperature, secondary centrifuging desalination；
Step 7：Filtrate is transferred into dehydrating kettle carries out second dehydration, and vacuum distillation controls 50 ~ 85 DEG C or so of temperature, takes off
When water to material moisture content is less than 2.0%, 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, is settled 1 ~ 5 day, filtered through accurate filter, got product.
In the step one, acid solution is hydrochloric acid or sulfuric acid, and concentration is 1 ~ 30%, and preferred concentration is 15 ~ 18%；
In the step one, formalin concentration is 1 ~ 30%, and preferred concentration is 25 ~ 30%；
In the step one, PH3The speed that is passed through of gas is 0.1 ~ 10m3/ min, favor speed is 2m3/ min；
In the step one, circulation fluid temperature is 0 ~ 15 DEG C, and preferable temperature is 5 ~ 8 DEG C；
In the step one, reaction temperature is 0 ~ 20 DEG C, and preferable temperature is 8 ~ 10 DEG C；
In the step one, THPC or THPS extraction concentration is 5 ~ 85%, and preferred concentration is 50 ~ 85%, particularly preferably dense
Spend is 75 ~ 85%；
In the step one, tail gas absorption oxidant includes but is not limited to following one or more：The hypochlorous acid of metal M
Salt（M is alkali metal or alkaline earth metal cation）, hydrogen peroxide, the concentrated sulfuric acid.
In the step 2, alkali includes but is not limited to following one or more：The hydroxide of metal M（M is alkali metal
Or alkaline earth metal cation）, ammoniacal liquor, sodium carbonate, sodium methoxide, caustic alcohol, pyridine, front three ammonia, triethylamine etc., preferred alkali is hydrogen
Sodium oxide molybdena, triethylamine.
In the step 2, catalyst includes：Palladium, barium sulfate, barium chloride, nickel sulfate, one kind in cobalt nitrate or
Various, preferred catalyst is palladium, barium sulfate.
In the step 2, concentration of lye is 1 ~ 30%, and preferably concentration of lye is 12 ~ 15%.
In the step 2, drop alkali temperature is 25 ~ 62 DEG C, and it is 30 ~ 35 DEG C preferably to drip alkali temperature.
In the step 3, stop plus the pH of alkali is 9.5 ~ 12, preferably stop plus the pH of alkali is 10.5 ~ 11.
In the step 3, reaction temperature is 55 ~ 90 DEG C, and preferable reaction temperature is 65 ~ 70 DEG C.
In the step 3, soaking time is 6 ~ 15h, and preferably soaking time is 10h.
In the step 4, acid solution includes：Hydrochloric acid, sulfuric acid etc..
In the step 4, acid strength is 1 ~ 30%, and preferably acid strength is 12 ~ 15%.
In the step 4, the pH for stopping acid adding is 6.5 ~ 8.0, and preferably pH is 7.0 ~ 7.5.
In the step 4, soaking time is 0.5 ~ 2h, and preferably soaking time is 1h.
In the step 5, primary dewatering temperature is 50 ~ 85 DEG C, and preferably dehydration temperaturre is 65 ~ 70 DEG C.
In the step 5, the material moisture content for stopping primary dewatering is 5 ~ 20%, and preferred feed moisture is 8 ~ 12%.
In the step 5, it is 20 ~ 25 DEG C that desalination temperature is once centrifuged.
In the step 6, aldehyde removing agent includes：Sodium sulfite, potassium sulfite, peroxide（Such as：Hydrogen peroxide, peroxidating
Potassium, sodium peroxide, copper dioxide, peroxidating perbenzoic acid, peroxydicarbonate etc.）, sodium dithionite etc., preferably take off
Aldehyde agent is one or more in sodium dithionite.
In the step 6, full gear reaction temperature is 20 ~ 25 DEG C.
In the step 6, the full gear reaction time is 1 ~ 3h, and the preferably full gear reaction time is 2h.
In the step 7, second dehydration temperature is 50 ~ 85 DEG C, and preferably dehydration temperaturre is 65 ~ 70 DEG C.
In the step 7, the material moisture content for stopping second dehydration being less than 2%, and preferred feed moisture is
1.5~1.8%。
In the step 8,1 ~ 5 day THPO crude product sedimentation time, preferably sedimentation time are 3 days.
In the step 8, accurate filter mesh number is 200 ~ 800 mesh, and preferred filters mesh number is 800 mesh.
The main device of industrialized production THPO includes：Spray-absorption system, tail gas absorbing system, vacuum distillation apparatus,
Synthesis reactor, one-level dehydrating kettle, two grades of dehydrating kettles, first-stage centrifugal machine, two-stage centrifugal machine, transfer tank, full gear kettle, waste water tank is accurate
Filter, crude product tank, finished pot；The spray-absorption system includes three-level spray-absorption device, the tail gas absorbing system bag
Include two grades of device for absorbing tail gas.
The spray-absorption device includes：Absorption tower body, absorber, condenser, temperature sensor, circulating pump produces pump,
Make-up pump, raw material supplement tank, produces receiver；The absorption tower body lower end is connected with absorber, and the absorber is by circulating pump
Distributor with absorption tower body upper end is connected, and is filled by multilayer inserts in the absorption tower；The condenser is located at circulating pump
Between distributor, the temperature sensor is located between condenser and distributor；Raw material supplement tank by make-up pump with
Absorber is connected, and the extraction receiver is connected through producing pump with absorber.
The spray-absorption device is divided into three-level, PH3Gas enters absorption tower body from one-level spray-absorption device air inlet,
One-level spray-absorption device exhaust outlet is connected with two grades of spray-absorption device air inlets, two grades of spray-absorption device exhaust outlets and three
Level spray-absorption device air inlet is connected, and three-level spray-absorption device exhaust outlet is connected with device for absorbing tail gas air inlet.
The spray-absorption device is divided into three-level, and raw material supplement tank is connected through centrifugal pump with three-level absorber, and three-level absorbs
Device is connected through centrifugal pump with secondary absorber, and secondary absorber is connected through centrifugal pump with first absorber, and first absorber is through adopting
Go out pump to be connected with extraction receiver.
The device for absorbing tail gas includes：Absorption tower body, recycling can, condenser, circulating pump produces pump, make-up pump, oxidation
Agent supplements tank, byproduct tank；The absorption tower body lower end is connected with recycling can, and the recycling can is by circulating pump and absorption tower body
The distributor of upper end is connected, and is filled by multilayer inserts in the absorption tower；The condenser be located at circulating pump and distributor it
Between, the oxidant supplement tank is connected by make-up pump with recycling can, and the byproduct tank is connected through producing pump with recycling can.
The device for absorbing tail gas is divided into two grades, and one-level device for absorbing tail gas air inlet is vented with three-level spray-absorption device
Mouth is connected, and two grades of device for absorbing tail gas air inlets are connected with one-level device for absorbing tail gas exhaust outlet, two grades of device for absorbing tail gas rows
Gas port is vented.
The device for absorbing tail gas is divided into two grades, and oxidant supplement tank is connected through centrifugal pump with secondary recovery tank, and two grades are returned
Closed cans is connected through centrifugal pump with one-level recycling can, and one-level recycling can is connected through producing pump with byproduct tank.
The vacuum system includes：Tank, water-circulating pump, water stream injection pump, condenser, vacuum buffer tank etc.；The tank
Lower accepting water circulating pump, the water-circulating pump connects through pipeline with water stream injection pump, and the water stream injection pump lower linking tube road is connected with tank,
Side is connected by pipeline with vacuum buffer tank, and the condenser is located between water stream injection pump and tank, is connected by pipeline.
Connect sour measuring tank on the synthesis reactor, alkali measuring tank, raw material measuring tank, under connect one-level dehydrating kettle；
Connect condenser on the one-level dehydrating kettle, under connect first-stage centrifugal machine, the condenser is connected with waste water tank, described useless
Water pot is connected with vacuum system.
Transfer tank is connect under the first-stage centrifugal machine.
The transfer tank is connected with full gear kettle.
Two-stage centrifugal machine is connect under the full gear kettle.
Two grades of dehydrating kettles are connect under the two-stage centrifugal machine.
Connect condenser on two grades of dehydrating kettles, under connect crude product tank, the condenser is connected with waste water tank, the waste water tank
It is connected with vacuum system.
Compressed nitrogen is connect on the crude product tank, lower to be connected with accurate filter, the accurate filter is connected with finished pot.
Each device described above passes through conventional chemical pipeline and is connected.
The beneficial effects of the invention are as follows：Successfully complete with PH3It is the industrialized production of Material synthesis THPO, with larger
Social benefit and economic worth.Fully utilize the byproduct PH in Sodium hypophosphite production3, recycling economy is realized, improve
Added value of product.Using two grades of device for absorbing tail gas, both without any poisonous, pernicious gas discharge, environmental protection has creation one
Fixed economic worth.
Brief description of the drawings
Fig. 1 is PH of the present invention3It is the production system schematic diagram of the trihydroxy methyl 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.
Specific embodiment
Embodiment 1
1）By PH3Gas is with 1 ~ 3m3/ min is passed through spray column, and formaldehyde is utilized in spray column（25%~30%）And hydrochloric acid（12%~
15%）Mixed aqueous solution be circulated spray, 8 ~ 10 DEG C of reaction temperature, control circulation fluid temperature works as tetra methylol at 5 ~ 8 DEG C
Phosphorus chloride（THPC）Concentration be 75 ~ 85% when produce, waste gas utilization liquor natrii hypochloritis absorb, byproduct sodium hypophosphite sell；
2) by above-mentioned synthetic the 400L 80%THPC aqueous solution and 80g catalyst（40g diatomite, 0.008g palladiums,
40g barium sulfate）In addition 1000L enamel reaction stills, heating stirring, temperature is slowly added dropwise concentration when being 30 DEG C or so be 12%
NaOH；When pH is 10.5 ~ 11, stop drop alkali；When being to slowly warm up to 65 ~ 68 DEG C, insulated and stirred 10h；Then, toward in kettle
The hydrochloric acid that concentration is 15% is slowly added dropwise, when pH is 7.3 ~ 7.5, stops drop acid, after stirring 1h, be down to room temperature；
3) transferring the material into 1000L dehydrating kettles carries out primary dewatering, and vacuum distillation controls temperature in the kettle on 70 DEG C of left sides
It is right；When material moisture content is 10 ~ 15%, stop dehydration, desalination, gained salt NaCl are once centrifuged when being cooled to 20 DEG C or so
The Kg of quality about 100；Then, filtrate is moved into full gear kettle, adds a certain amount of sodium sulfite, after stirring 2h at room temperature, carry out two
Secondary centrifugation desalination；Filtrate is transferred into 1000L dehydrating kettles carries out second dehydration, and vacuum distillation controls temperature in the kettle on 70 DEG C of left sides
The right side, when dehydration to material moisture content is less than 1.5%, stops dehydration；Material is transferred to crude product tank while hot, is settled 3 days, through 800 mesh essence
Close filter filtering, gained trihydroxy methyl phosphine oxide（THPO）About 255Kg, product purity more than 98%, yield more than 90%.
Embodiment 2
1）By PH3Gas is with 1 ~ 3m3/ min is passed through spray column, and formaldehyde is utilized in spray column（25%~30%）And hydrochloric acid（12%~
15%）Mixed aqueous solution be circulated spray, 8 ~ 10 DEG C of reaction temperature, control circulation fluid temperature works as tetra methylol at 5 ~ 8 DEG C
Phosphorus chloride（THPC）Concentration be 75 ~ 85% when produce, waste gas utilization liquor natrii hypochloritis absorb, byproduct sodium hypophosphite sell；
2) by above-mentioned synthetic the 400L 80%THPC aqueous solution and 80g catalyst（2g palladiums）Add 1000L enamel
In reactor, heating stirring, temperature is slowly added dropwise the NaOH that concentration is 12% when being 30 DEG C or so；When pH is 10.5 ~ 11
When, stop drop alkali；When being to slowly warm up to 65 ~ 68 DEG C, insulated and stirred 10h；Then, toward being slowly added dropwise the salt that concentration is 15% in kettle
Acid, when pH is 7.3 ~ 7.5, stops drop acid, after stirring 1h, is down to room temperature；
3）Process step is identical with upper, gained trihydroxy methyl phosphine oxide（THPO）About 230Kg, product purity more than 95%,
Yield more than 80%.
Embodiment 3
1）By PH3Gas is with 1 ~ 3m3/ min is passed through spray column, and formaldehyde is utilized in spray column（25%~30%）And hydrochloric acid（12%~
15%）Mixed aqueous solution be circulated spray, 8 ~ 10 DEG C of reaction temperature, control circulation fluid temperature works as tetra methylol at 5 ~ 8 DEG C
Phosphorus chloride（THPC）Concentration be 75 ~ 85% when produce, waste gas utilization liquor natrii hypochloritis absorb, byproduct sodium hypophosphite sell；
2) by above-mentioned synthetic the 400L 80%THPC aqueous solution and 80g catalyst（1g palladiums, 20g barium sulfate）Plus
Enter in 1000L enamel reaction stills, heating stirring, temperature is slowly added dropwise the NaOH that concentration is 12% when being 30 DEG C or so；Work as pH
At 10.5 ~ 11, stop drop alkali；When being to slowly warm up to 65 ~ 68 DEG C, insulated and stirred 10h；Then, toward being slowly added dropwise concentration in kettle
It is 15% hydrochloric acid, when pH is 7.3 ~ 7.5, stops drop acid, after stirring 1h, is down to room temperature；
3）Process step is identical with upper, gained trihydroxy methyl phosphine oxide（THPO）About 245Kg, product purity more than 97%,
Yield more than 85%.
Embodiment 4
A kind of trihydroxy methyl phosphine oxide（THPO）The device of industrialized production, the device mainly includes：Spray-absorption system,
Tail gas absorbing system, vacuum system, finished product synthesis system；The spray-absorption system is at least three-level spray-absorption device series connection
Form, the tail gas absorbing system is that at least two grades device for absorbing tail gas are in series；
The spray-absorption device includes：Absorption tower body, absorber, condenser, temperature sensor, circulating pump produces pump,
Make-up pump, raw material supplement tank, produces receiver；Absorption tower body lower end is connected with absorber, and absorber is by circulating pump and absorption tower
The distributor of body upper end is connected, and is filled by multilayer inserts in absorption tower；Condenser is located between circulating pump and distributor, temperature
Sensor is located between condenser and distributor；Raw material supplement tank is connected by make-up pump with absorber, and extraction receiver is through extraction
Pump is connected with absorber；
The device for absorbing tail gas includes：Absorption tower body, recycling can, condenser, circulating pump produces pump, make-up pump, oxidation
Agent supplements tank, byproduct tank；The absorption tower body lower end is connected with recycling can, and the recycling can is by circulating pump and absorption tower body
The distributor of upper end is connected, and is filled by multilayer inserts in the absorption tower；The condenser be located at circulating pump and distributor it
Between, the oxidant supplement tank is connected by make-up pump with recycling can, and the byproduct tank is connected through producing pump with recycling can；
The vacuum system includes：Tank, water-circulating pump, water stream injection pump, condenser, vacuum buffer tank etc.；The tank
Lower accepting water circulating pump, the water-circulating pump connects through pipeline with water stream injection pump, and the water stream injection pump lower linking tube road is connected with tank,
Side is connected by pipeline with vacuum buffer tank, and the condenser is located between water stream injection pump and tank, is connected by pipeline；
Finished product synthesis system includes：Synthesis reactor, full gear kettle, one-level dehydrating kettle, two grades of dehydrating kettles, first-stage centrifugal machine, two grades
Centrifuge, transfer tank, condenser, waste water tank, waste water processing station, THPO crude product tanks, accurate filter, THPO finished pots are described
Connect sour measuring tank on synthesis reactor, alkali measuring tank, raw material measuring tank, under connect one-level dehydrating kettle；Condenser is connect on one-level dehydrating kettle, under
First-stage centrifugal machine is connect, the condenser is connected with waste water tank, and the waste water tank is connected with vacuum system；In being connect under first-stage centrifugal machine
Turn tank, transfer tank is connected with full gear kettle, two-stage centrifugal machine is connect under full gear kettle, two grades of dehydrating kettles are connect under two-stage centrifugal machine, two grades take off
Connect condenser on water kettle, under connect crude product tank, the condenser is connected with waste water tank, and the waste water tank is connected with vacuum system, slightly
Compressed nitrogen is connect on product tank, lower to be connected with accurate filter, the accurate filter is connected with finished pot.
The spray-absorption device is divided into three-level, PH3Gas enters absorption tower body from one-level spray-absorption device air inlet,
One-level spray-absorption device exhaust outlet is connected with two grades of spray-absorption device air inlets, two grades of spray-absorption device exhaust outlets and three
Level spray-absorption device air inlet is connected, and three-level spray-absorption device exhaust outlet is connected with device for absorbing tail gas air inlet.
The spray-absorption device is divided into three-level, and raw material supplement tank is connected through centrifugal pump with three-level absorber, and three-level absorbs
Device is connected through centrifugal pump with secondary absorber, and secondary absorber is connected through centrifugal pump with first absorber, and first absorber is through adopting
Go out pump to be connected with extraction receiver.
The device for absorbing tail gas is divided into two grades, and one-level device for absorbing tail gas air inlet is vented with three-level spray-absorption device
Mouth is connected, and two grades of device for absorbing tail gas air inlets are connected with one-level device for absorbing tail gas exhaust outlet, two grades of device for absorbing tail gas rows
Gas port is vented；The device for absorbing tail gas is divided into two grades, and oxidant supplement tank is connected through centrifugal pump with secondary recovery tank, and two grades are returned
Closed cans is connected through centrifugal pump with one-level recycling can, and one-level recycling can is connected through producing pump with byproduct tank.
Claims (9)
1. a kind of production technology of trihydroxy methyl phosphine oxide THPO, it is characterised in that comprise the following steps：
（1）By PH3Gas is with 0.1 ~ 10m3The speed of/min is passed through spray column, in spray column by 1 ~ 30% formalin and 1 ~
The mixed aqueous solution of 30% hydrochloric acid or sulfuric acid is circulated spray as spray liquid in spray column, and circulation fluid temperature is 0 ~ 15 DEG C,
0 ~ 20 DEG C of reaction temperature, produces when the concentration of THPC or THPS is 5 ~ 85%, and waste gas utilization oxidizing agent solution absorbs；
（2）By concentration for 5 ~ 85% THPC the or THPS aqueous solution and catalyst add reactor in, added at 25-65 DEG C dense
Spend the alkali lye for 1 ~ 30%；
（3）When pH is 9.5 ~ 12, stop that alkali is added dropwise；Be heated to temperature for 55 ~ 90 DEG C when, be incubated 6 ~ 15h；
（4）The hydrochloric acid or sulfuric acid that concentration is added dropwise for 1% ~ 30% carry out acid adjustment, when pH is 6.5 ~ 8.0, stop that acid solution, stirring is added dropwise
After 0.5h ~ 2h, room temperature is down to；
（5）Transferring the material into dehydrating kettle carries out primary dewatering, and vacuum distillation controls temperature at 50 ~ 85 DEG C；When material moisture content is
When 5 ~ 20%, stop distillation, desalination is once centrifuged when being cooled to 20 DEG C；
（6）Filtrate is moved into full gear kettle, aldehyde removing agent is added, after stirring 1 ~ 3h at 20-25 DEG C, secondary centrifuging desalination is described de-
Aldehyde agent is sodium sulfite, potassium sulfite, hydrogen peroxide, potassium peroxide, sodium peroxide, copper dioxide, perbenzoic acid, peroxide
Two carbonic esters, one or more in sodium dithionite；
（7）Filtrate is transferred into dehydrating kettle carries out second dehydration, and vacuum distillation controls 50 ~ 85 DEG C of temperature, dehydration to material moisture content
During less than 2.0%, stop dehydration；
（8）Material is transferred to crude product tank while hot, is settled 1 ~ 5 day, filtered to 200-800 mesh through accurate filter, got product；
The device of industrialized production trihydroxy methyl phosphorous oxide includes in above-mentioned technique：Spray-absorption system, tail gas absorbing system, very
Empty set is united, finished product synthesis system；The spray-absorption system is that at least three-level spray-absorption device is in series, and the tail gas is inhaled
Receipts system is that at least two grades device for absorbing tail gas are in series；
The spray-absorption device includes：Absorption tower body, absorber, condenser, temperature sensor, circulating pump produces pump, supplement
Pump, raw material supplement tank, produces receiver；Absorption tower body lower end is connected with absorber, and absorber is by circulating pump and absorption tower body
The distributor at end is connected, and is filled by multilayer inserts in absorption tower；Condenser is located between circulating pump and distributor, TEMP
Device is located between condenser and distributor；Raw material supplement tank be connected with absorber by make-up pump, extraction receiver through extraction pump and
Absorber is connected；
The device for absorbing tail gas includes：Absorption tower body, recycling can, condenser, circulating pump produces pump, and make-up pump, oxidant is mended
Fill tank, byproduct tank；The absorption tower body lower end is connected with recycling can, and the recycling can is by circulating pump and absorption tower body upper end
Distributor be connected, filled by multilayer inserts in the absorption tower；The condenser is located between circulating pump and distributor, institute
State oxidant supplement tank to be connected with recycling can by make-up pump, the byproduct tank is connected through producing pump with recycling can；
The vacuum system includes：Tank, water-circulating pump, water stream injection pump, condenser, vacuum buffer tank；The tank lower accepting water
Circulating pump, the water-circulating pump connects through pipeline with water stream injection pump, and the water stream injection pump lower linking tube road is connected with tank, and side leads to
Piping connects with vacuum buffer tank, and the condenser is located between water stream injection pump and tank, is connected by pipeline；
Finished product synthesis system includes：Synthesis reactor, full gear kettle, one-level dehydrating kettle, two grades of dehydrating kettles, first-stage centrifugal machine, two-stage centrifugal
Machine, transfer tank, condenser, waste water tank, waste water processing station, THPO crude product tanks, accurate filter, THPO finished pots, the synthesis
Connect sour measuring tank on kettle, alkali measuring tank, raw material measuring tank, under connect one-level dehydrating kettle；Connect condenser on one-level dehydrating kettle, under connect one
Level centrifuge, the condenser is connected with waste water tank, and the waste water tank is connected with vacuum system；Transfer is connect under first-stage centrifugal machine
Tank, transfer tank is connected with full gear kettle, and two-stage centrifugal machine is connect under full gear kettle, and two grades of dehydrating kettles, two grades of dehydrations are connect under two-stage centrifugal machine
Condenser is connect on kettle, under connect crude product tank, the condenser is connected with waste water tank, and the waste water tank is connected with vacuum system, crude product
Compressed nitrogen is connect on tank, lower to be connected with accurate filter, the accurate filter is connected with finished pot.
2. the production technology of trihydroxy methyl phosphine oxide THPO as claimed in claim 1, it is characterised in that comprise the following steps：
（1）By PH3Gas is passed through spray column, using 25 ~ 30% formalin and 15 ~ 18% hydrochloric acid or sulfuric acid in spray column
Mixed aqueous solution is circulated spray, and gas is passed through speed 2m3/ min, circulation fluid temperature is 5 ~ 8 DEG C, 8 ~ 10 DEG C of reaction temperature,
Produced when the concentration of THPC or THPS is 75 ~ 85%, waste gas utilization oxidizing agent solution absorbs；
（2）By concentration for 75 ~ 85% THPC the or THPS aqueous solution and catalyst add reactor in, added at 30 ~ 35 DEG C dense
Spend the alkali lye for 12 ~ 15%；
（3）When pH is 10.5 ~ 11, stop that alkali lye is added dropwise；Be heated to temperature for 65 ~ 70 DEG C when, be incubated 10h；
（4）The hydrochloric acid or sulfuric acid that concentration is added dropwise for 12 ~ 15% carry out acid adjustment, when pH is 7.0 ~ 7.5, stop that acid solution, stirring is added dropwise
After 1h, room temperature is down to；
（5）Transferring the material into dehydrating kettle carries out primary dewatering, and vacuum distillation controls temperature at 65 ~ 70 DEG C；When material moisture content is
When 8 ~ 12%, stop distillation, desalination is once centrifuged when being cooled to 20 DEG C；
（6）Filtrate is moved into full gear kettle, aldehyde removing agent is added, after stirring 2h at 20-25 DEG C, secondary centrifuging desalination, the full gear
Agent is sodium sulfite, potassium sulfite, hydrogen peroxide, potassium peroxide, sodium peroxide, copper dioxide, perbenzoic acid, peroxide two
Carbonic ester, one or more in sodium dithionite；
（7）Filtrate is transferred into dehydrating kettle carries out second dehydration, and vacuum distillation controls 65 ~ 70 DEG C of temperature, dehydration to material moisture content
When 1.5 ~ 1.8%, stop dehydration；
（8）Material is transferred to crude product tank while hot, is settled 3 days, filtered to 800 mesh through accurate filter, got product.
3. the production technology of trihydroxy methyl phosphine oxide THPO as claimed in claim 1 or 2, it is characterised in that in step (1)
In, the oxidant is following one or more：The hypochlorite of metal M, M is alkali metal or alkaline earth metal cation, double
Oxygen water, the concentrated sulfuric acid.
4. the production technology of trihydroxy methyl phosphine oxide THPO as claimed in claim 1 or 2, it is characterised in that in step (2)
In, the alkali lye is following one or more：The hydroxide of metal M, M is alkali metal or alkaline earth metal cation, ammoniacal liquor,
Sodium carbonate, sodium methoxide, caustic alcohol, pyridine, trimethylamine, triethylamine.
5. the production technology of trihydroxy methyl phosphine oxide THPO as claimed in claim 1 or 2, it is characterised in that in step (2)
In, the catalyst is palladium, barium sulfate, barium chloride, nickel sulfate, one or more in cobalt nitrate.
6. using process units used in the production process of the trihydroxy methyl phosphorous oxide described in right any one of 1-5, its
It is characterised by, the device includes：Spray-absorption system, tail gas absorbing system, vacuum system, finished product synthesis system；The spray
Absorption system is that at least three-level spray-absorption device is in series, and the tail gas absorbing system is at least two grades device for absorbing tail gas
It is in series；
The spray-absorption device includes：Absorption tower body, absorber, condenser, temperature sensor, circulating pump produces pump, supplement
Pump, raw material supplement tank, produces receiver；Absorption tower body lower end is connected with absorber, and absorber is by circulating pump and absorption tower body
The distributor at end is connected, and is filled by multilayer inserts in absorption tower；Condenser is located between circulating pump and distributor, TEMP
Device is located between condenser and distributor；Raw material supplement tank be connected with absorber by make-up pump, extraction receiver through extraction pump and
Absorber is connected；
The device for absorbing tail gas includes：Absorption tower body, recycling can, condenser, circulating pump produces pump, and make-up pump, oxidant is mended
Fill tank, byproduct tank；The absorption tower body lower end is connected with recycling can, and the recycling can is by circulating pump and absorption tower body upper end
Distributor be connected, filled by multilayer inserts in the absorption tower；The condenser is located between circulating pump and distributor, institute
State oxidant supplement tank to be connected with recycling can by make-up pump, the byproduct tank is connected through producing pump with recycling can；
The vacuum system includes：Tank, water-circulating pump, water stream injection pump, condenser, vacuum buffer tank；The tank lower accepting water
Circulating pump, the water-circulating pump connects through pipeline with water stream injection pump, and the water stream injection pump lower linking tube road is connected with tank, and side leads to
Piping connects with vacuum buffer tank, and the condenser is located between water stream injection pump and tank, is connected by pipeline；
Finished product synthesis system includes：Synthesis reactor, full gear kettle, one-level dehydrating kettle, two grades of dehydrating kettles, first-stage centrifugal machine, two-stage centrifugal
Machine, transfer tank, condenser, waste water tank, waste water processing station, THPO crude product tanks, accurate filter, THPO finished pots, the synthesis
Connect sour measuring tank on kettle, alkali measuring tank, raw material measuring tank, under connect one-level dehydrating kettle；Connect condenser on one-level dehydrating kettle, under connect one
Level centrifuge, the condenser is connected with waste water tank, and the waste water tank is connected with vacuum system；Transfer is connect under first-stage centrifugal machine
Tank, transfer tank is connected with full gear kettle, and two-stage centrifugal machine is connect under full gear kettle, and two grades of dehydrating kettles, two grades of dehydrations are connect under two-stage centrifugal machine
Condenser is connect on kettle, under connect crude product tank, the condenser is connected with waste water tank, and the waste water tank is connected with vacuum system, crude product
Compressed nitrogen is connect on tank, lower to be connected with accurate filter, the accurate filter is connected with finished pot.
7. process units as claimed in claim 6, it is characterised in that：The spray-absorption device is divided into three-level, PH3Gas from
One-level spray-absorption device air inlet enters absorption tower body, and one-level spray-absorption device exhaust outlet enters with two grades of spray-absorption devices
Gas port is connected, and two grades of spray-absorption device exhaust outlets are connected with three-level spray-absorption device air inlet, three-level spray-absorption device
Exhaust outlet is connected with device for absorbing tail gas air inlet.
8. process units as claimed in claim 6, it is characterised in that：The spray-absorption device is divided into three-level, raw material supplement
Tank is connected through centrifugal pump with three-level absorber, and three-level absorber is connected through centrifugal pump with secondary absorber, secondary absorber pass through from
Heart pump is connected with first absorber, and first absorber is connected through producing pump with extraction receiver.
9. process units as claimed in claim 6, it is characterised in that：The device for absorbing tail gas is divided into two grades, one-level tail gas
Absorption plant air inlet is connected with three-level spray-absorption device exhaust outlet, and two grades of device for absorbing tail gas air inlets are inhaled with one-level tail gas
Receiving apparatus exhaust outlet is connected, two grades of device for absorbing tail gas exhaust outlet emptying；The device for absorbing tail gas is divided into two grades, and oxidant is mended
Fill tank to be connected with secondary recovery tank through centrifugal pump, secondary recovery tank is connected through centrifugal pump with one-level recycling can, one-level recycling can warp
Extraction pump is connected with byproduct tank.
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| CN117680083A (en) * | 2024-02-04 | 2024-03-12 | 常熟新特化工有限公司 | Preparation process and preparation device of tetrakis (hydroxymethyl) phosphonium sulfate |
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| CN1003301B (en) * | 1986-05-12 | 1989-02-15 | 浙江大学 | Chemical purification of epoxy-ethane |
| CN86103369B (en) * | 1986-05-12 | 1988-01-27 | 浙江大学 | A kind of preparation method of aldehyde removing agent |
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| FR2954319B1 (en) * | 2009-12-22 | 2012-01-20 | Febex S A | PROCESS FOR PREPARING THPX |
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