CN104230989B - A kind of catalytic oxidation synthesis technique and equipment of trihydroxy methyl phosphine oxide - Google Patents
A kind of catalytic oxidation synthesis technique and equipment of trihydroxy methyl phosphine oxide Download PDFInfo
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- CN104230989B CN104230989B CN201410499804.0A CN201410499804A CN104230989B CN 104230989 B CN104230989 B CN 104230989B CN 201410499804 A CN201410499804 A CN 201410499804A CN 104230989 B CN104230989 B CN 104230989B
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Abstract
The present invention relates to catalytic oxidation synthesis technique and the equipment of a kind of trihydroxy methyl phosphine oxide (THPO). By PH3Gas and formaldehyde gas are through drier, and filter, passes into fluid bed by air blast, pass into drying nitrogen protection, PH3Enter fluidized system reaction with formaldehyde, the catalyst of fluid bed appendix solid particle, reaction temperature is-5 ~ 5 DEG C; Be liquid by the tris hydroxymethyl phosphine heating and melting of generation, fluid temperature is 60 ~ 100 DEG C, then liquid THP is transferred in stills for air blowing; In stills for air blowing, add oxidant, reaction temperature is 30 ~ 120 DEG C, is trihydroxy methyl phosphine oxide after stirring reaction 3 ~ 6h. Industrialized unit and the process route of production THPO of the present invention; Catalyst can Reusability, and cost is low; Fully utilize the byproduct PH in Sodium hypophosphite production3; Without " three wastes " discharge, environmentally safe, meets the policy of national green environmental protection and the strategy of sustainable development.
Description
Technical field
The present invention relates to a kind of phosphine gas that utilizes is raw material, and production technology and the production equipment of catalytic oxidation synthesizing trimethylol phosphine oxide, belong to chemical production field.
Background technology
Along with growing to even greater heights of the fire-retardant cry of taking precautions against natural calamities in world wide and being gradually improved of flame retardant regulation, safety and environmental protection standard increasingly stringent and plastic product application increase, by 2014, the whole fire retardant market demand 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 still inorganic, the halogen-containing fire retardants of the fire retardant of domestic production and use. But, while there is burning due to halogen containing flame-retardant, emit smog, corrosive gas and toxic gas. 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 reports and patented technology both at home and abroad. But there is no industrialized unit goes into operation. Reasonable owing to lacking, efficient production equipment and process route, make with PH3For the energy consumption of the synthetic THPO of raw material is high, production cost is high, and environmental pollution is serious, has restricted its plant-scale development.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of catalytic oxidation synthesis technique and equipment of trihydroxy methyl phosphine oxide, according to this process route, success has completed with PH on this industrialized unit3For the suitability for industrialized production of the synthetic THPO of raw material. The method process route is simple, and energy consumption is low, simple to operate; Catalyst can Reusability, and cost is low; Fully utilize the byproduct PH in Sodium hypophosphite production3, realized industry chain of circular economy; Without " three wastes " discharge, environmentally safe, meets the policy of national green environmental protection and the strategy of sustainable development.
Production technology and the process units of the synthetic THPO of catalytic oxidation provided by the invention, wherein process route comprises following step:
Step 1: by PH3Gas and formaldehyde gas pass through respectively drier, and filter passes into fluid bed by air blast, pass into drying nitrogen protection, PH3Enter fluidized system reaction with formaldehyde, the catalyst of fluid bed appendix solid particle, reaction temperature is-5 ~ 5 DEG C.
Step 2: be liquid by tris hydroxymethyl phosphine (THP) heating and melting generating, fluid temperature is 60 ~ 100 DEG C, then liquid THP is transferred in stills for air blowing.
Step 3: add oxidant in stills for air blowing, reaction temperature is 30 ~ 120 DEG C, after stirring reaction 3 ~ 6h, is down to room temperature, obtains trihydroxy methyl phosphine oxide transferred product to finished pot.
In described step 1, PH3Gas, formaldehyde gas and nitrogen must be dried.
In described step 1, reaction temperature is-5 ~ 5 DEG C, and preferable reaction temperature is-3 ~ 0 DEG C.
In described step 1, solid catalyst comprises: Pt, K2[PtCl4]，Ni(NO3)2，NiCl2，NiSO4，Co(NO3)2Deng.
In described step 2, fluid temperature is 60 ~ 100 DEG C, and preferred liquid temperature is 60 ~ 65 DEG C.
In described step 3, oxidant comprises: air, oxygen, peroxide (hydrogen peroxide, potassium peroxide, sodium peroxide, copper dioxide, peroxidating benzoyl peroxide formic acid, peroxide two carbonic esters etc.), alkali [hydroxide (M is alkali metal or alkaline earth metal cation) of metal M, ammoniacal liquor, sodium carbonate, sodium methoxide, caustic alcohol, pyridine, front three ammonia, triethylamine etc.].
In described step 3, reaction temperature is 30 ~ 120 DEG C, and preferable reaction temperature is 30 ~ 60 DEG C; It is 3 ~ 6h that its reaction time is controlled.
The process units of suitability for industrialized production THPO mainly comprises: gas pretreatment device, fluidized system, stills for air blowing, finished pot etc.
Described gas pretreatment device comprises: drier, filter, air blast etc.; Described drier is connected with filter, and described filter is connected with air blast, and described filter is connected with fluid bed air inlet;
Described fluidized system comprises: fluid bed, cyclone separator, screen cloth, air blast etc.; Described fluid bed air inlet is connected with gas pretreatment device, and exhaust outlet is connected with cyclone separator charging aperture, and discharging opening is connected with THP receiver; Described cyclone separator exhaust outlet is through screen cloth, and air blast is connected with fluid bed air inlet, and discharging opening is connected with THP receiver;
Described fluid bed top is divided 2 screen clothes is housed, and places the solid particle catalyst of some in the middle of screen cloth;
Described fluid bed mid portion is equipped with condensation sleeve pipe, under condensation sleeve pipe, thermal insulation layer is housed;
Described cyclone separator solid discharging opening is connected with material receiver;
Described fluid bed bottom is divided into material bin, and material bin is equipped with chuck around, has steam to import and export on chuck;
Described cyclone separator bottom is divided into material bin, and material bin is equipped with chuck around, has steam to import and export on chuck;
Connecting pipe between described discharging port of fluidized bed and THP receiver has heating muff outward;
Connecting pipe between described cyclone separator discharging opening and THP receiver has heating muff outward;
On described synthesis reactor, connect oxidant measuring tank, under connect finished pot;
Above-mentioned each device is connected by conventional chemical pipeline.
The invention has the beneficial effects as follows: be successfully completed with PH3For the suitability for industrialized production of the synthetic THPO of raw material, there is larger social benefit and economic worth; Process route is simple, and energy consumption is low, simple to operate;
Catalyst can Reusability, and cost is low; Fully utilize the byproduct PH in Sodium hypophosphite production3, realize recycling economy, improve added value of product; Without " three wastes " discharge, environmentally safe, meets the policy of national green environmental protection and the strategy of sustainable development.
Brief description of the drawings
Fig. 1 is the production system schematic diagram of a kind of catalytic oxidation synthesizing trimethylol phosphine oxide of the present invention.
Fig. 2 is a kind of fluidized system schematic diagram of the present invention; Wherein 1. fluid beds, 2. cyclone separator, 3. screen cloth, 4. air blast, 5. dry N2Import, 6. air inlet, 7. steam inlet, 8.THP receiver, 9. dry PH3Import, 10. dry formaldehyde import, 11. screen clothes, 12. exhaust outlets, 13. condensation sleeve pipes, 14. thermal insulation layers, 15. steam (vapor) outlets, 16. discharging openings, 17. heating muffs, 18. steam inlets, 19. steam (vapor) outlets, 20. discharging openings.
Detailed description of the invention
Embodiment 1
1) by PH3Gas and formaldehyde gas are through drier, and filter passes into fluid bed by air blast, pass into drying nitrogen protection, fluid bed appendix solid particle catalyst Co (NO3)2And Ni (NO3)2, control 0 DEG C of fluidized-bed temperature, the temperature control of fluidised bed material storehouse is 60 DEG C;
2) liquid 400Kg THP is added in 1000L stills for air blowing, pass into large quantity of air, add thermal agitation, be warming up to 80 DEG C, reaction 5h, is down to room temperature, and material is transferred to finished pot.
Gained THPO430Kg, product purity is more than 99%, and yield is more than 95%.
Embodiment 2
1) by PH3Gas and formaldehyde gas are through drier, and filter passes into fluid bed by air blast, pass into drying nitrogen protection, fluid bed appendix solid particle catalyst Co (NO3)2And Ni (NO3)2, control 0 DEG C of fluidized-bed temperature, the temperature control of fluidised bed material storehouse is 60 DEG C;
2) liquid 400Kg THP is added in 1000L stills for air blowing, slowly add at normal temperatures 438Kg25% hydrogen peroxide, react after 2 hours, be warming up to 40-50 insulation 1 hour, be down to room temperature, material is transferred to precipitation still and removes out moisture content. Gained THPO435Kg, product purity is more than 95%, and yield is more than 91.5%.
Embodiment 3
1) by PH3Gas and formaldehyde gas are through drier, and filter passes into fluid bed by air blast, pass into drying nitrogen protection, fluid bed appendix solid particle catalyst Co (NO3)2And Ni (NO3)2, control 0 DEG C of fluidized-bed temperature, the temperature control of fluidised bed material storehouse is 60 DEG C;
2) liquid 400Kg THP is added in 1000L stills for air blowing, slowly pass at normal temperatures oxygen, add thermal agitation, be warming up to 60 DEG C, reaction 5h, is down to room temperature, and material is transferred to finished pot. Gained THPO430Kg, product purity is more than 97%, and yield is more than 93%.
Embodiment 4
1) by PH3Gas and formaldehyde gas are through drier, and filter passes into fluid bed by air blast, pass into drying nitrogen protection, fluid bed appendix solid particle catalyst Co (NO3)2And Ni (NO3)2, control 0 DEG C of fluidized-bed temperature, the temperature control of fluidised bed material storehouse is 60 DEG C;
2) liquid 400Kg THP is added in 1000L stills for air blowing, slowly add at normal temperatures 400Kg30% hydrogen peroxide, add thermal agitation, be warming up to 50 DEG C, reaction 5h, proceeds to 1000L precipitation still and deviates from moisture between 1-1.5%, is down to room temperature, and material is transferred to finished pot. Gained THPO435Kg, product purity is more than 97%, and yield is more than 92%.
Embodiment 5
1) by PH3Gas and formaldehyde gas are through drier, and filter passes into fluid bed by air blast, pass into drying nitrogen protection, fluid bed appendix solid particle catalyst K2[PtCl4] and Ni (NO3)2, control 0 DEG C of fluidized-bed temperature, the temperature control of fluidised bed material storehouse is 60 DEG C;
2) liquid 400Kg THP is added in 1000L stills for air blowing, pass into large quantity of air, add thermal agitation, be warming up to 80 DEG C, reaction 5h, is down to room temperature, and material is transferred to finished pot. Gained THPO432Kg, product purity is more than 99%, and yield is more than 95%.
Claims (1)
1. a catalytic oxidation synthesis technique for trihydroxy methyl phosphine oxide, is characterized in that, comprises the steps:
1) by PH3Gas and formaldehyde gas pass into fluid bed through drier, filter by air blast, pass into drying nitrogen protection, fluid bed appendix solid particle catalyst Co (NO3)2And Ni (NO3)2, control 0 DEG C of fluidized-bed temperature, the temperature control of fluidised bed material storehouse is 60 DEG C;
2) liquid 400Kg tris hydroxymethyl phosphine is added in 1000L stills for air blowing, pass into large quantity of air, add thermal agitation, be warming up to 80 DEG C, reaction 5h, is down to room temperature, and material is transferred to finished pot, can obtain trihydroxy methyl phosphine oxide,
Each material by weight, PH3Gas 80-300 part, formaldehyde 100-500 part, catalyst 10-20 part, oxidant 80-500 part;
In above-mentioned technical process, catalytic oxidation synthesis device used, specifically comprises gas pretreatment device, fluidized system, stills for air blowing, finished pot, gas pretreatment device is connected with fluidized system, fluidized system is connected with stills for air blowing, connects oxidant measuring tank on stills for air blowing, under connect finished pot;
Described fluidized system comprises fluid bed, cyclone separator, screen cloth, air blast, fluid bed air inlet is connected with gas pretreatment device, fluid bed exhaust outlet is connected with cyclone separator charging aperture, and cyclone separator bottom discharge mouth is connected with tris hydroxymethyl phosphine receiver; The exhaust outlet at described cyclone separator top is through screen cloth, and air blast is connected with fluid bed air inlet, and the discharging opening of the bottom of fluid bed is connected with tris hydroxymethyl phosphine receiver;
Described fluid bed top is divided 2 screen clothes is housed, and the centre of 2 screen clothes can arrange solid particle catalyst; Described fluid bed mid portion is equipped with condensation sleeve pipe, and thermal insulation layer is equipped with in condensation sleeve pipe bottom; Fluid bed bottom is material bin, and material bin bottom and sidewall are provided with chuck, and chuck bottom arranges steam and imports and exports;
Described cyclone separator bottom is divided into material bin, and material bin bottom and sidewall are provided with chuck, and chuck bottom is provided with steam and imports and exports;
Connecting pipe between the discharging opening of the bottom of described fluid bed and tris hydroxymethyl phosphine receiver has heating muff outward; Connecting pipe between described cyclone separator bottom discharge mouth and tris hydroxymethyl phosphine receiver has heating muff outward;
Gas pretreatment device comprises drier, filter, air blast, and drier is connected with filter, and filter is connected with air blast, and filter is connected with fluid bed air inlet.
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| FR2954319B1 (en) * | 2009-12-22 | 2012-01-20 | Febex S A | PROCESS FOR PREPARING THPX |
| CN103980313A (en) * | 2014-05-23 | 2014-08-13 | 厦门大学 | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof |
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