CN114230608A - Production process of reactive flame retardant THPO - Google Patents
Production process of reactive flame retardant THPO Download PDFInfo
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- CN114230608A CN114230608A CN202111485654.4A CN202111485654A CN114230608A CN 114230608 A CN114230608 A CN 114230608A CN 202111485654 A CN202111485654 A CN 202111485654A CN 114230608 A CN114230608 A CN 114230608A
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- nanofiltration
- thpo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- SXXLKZCNJHJYFL-UHFFFAOYSA-N 4,5,6,7-tetrahydro-[1,2]oxazolo[4,5-c]pyridin-5-ium-3-olate Chemical compound C1CNCC2=C1ONC2=O SXXLKZCNJHJYFL-UHFFFAOYSA-N 0.000 title claims abstract 10
- 101000799461 Homo sapiens Thrombopoietin Proteins 0.000 title claims abstract 10
- 102100034195 Thrombopoietin Human genes 0.000 title claims abstract 10
- 238000001728 nano-filtration Methods 0.000 claims abstract description 98
- 238000010612 desalination reaction Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000011550 stock solution Substances 0.000 claims description 48
- 239000012528 membrane Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 27
- 230000018044 dehydration Effects 0.000 claims description 21
- 238000006297 dehydration reaction Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000012432 intermediate storage Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 238000011033 desalting Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims 1
- ZGTNBBQKHJMUBI-UHFFFAOYSA-N bis[tetrakis(hydroxymethyl)-lambda5-phosphanyl] sulfate Chemical compound OCP(CO)(CO)(CO)OS(=O)(=O)OP(CO)(CO)(CO)CO ZGTNBBQKHJMUBI-UHFFFAOYSA-N 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 230000008020 evaporation Effects 0.000 abstract description 8
- 239000010409 thin film Substances 0.000 abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 6
- 238000006757 chemical reactions by type Methods 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 3
- 238000011027 product recovery Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- XBIKWYOQJVTUEC-UHFFFAOYSA-N phosphorosomethanetriol Chemical compound OC(O)(O)P=O XBIKWYOQJVTUEC-UHFFFAOYSA-N 0.000 description 69
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- 102000015863 Nuclear Factor 90 Proteins Human genes 0.000 description 4
- 108010010424 Nuclear Factor 90 Proteins Proteins 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- -1 alkaline earth metal cation Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKRWGRQBYLWNKR-UHFFFAOYSA-N OC(O)(O)[PH2]=O Chemical compound OC(O)(O)[PH2]=O DKRWGRQBYLWNKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5304—Acyclic saturated phosphine oxides or thioxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a production process of a reaction type flame retardant THPO, in particular to a purification and refining (comprising desalination, dealdehyding, concentration and the like) method of THPO reaction liquid, which adopts combined processes of nanofiltration desalination, nanofiltration dealdehyding, nanofiltration concentration, thin film evaporation and the like. Compared with the prior art, the method does not need to add a formaldehyde removing agent, and has the advantages of simple process flow, low requirement on equipment materials, investment saving, low operating cost, small occupied area, few control points, simple operation, convenient realization of automatic control, high product recovery rate, small waste water generation amount, stable and reliable product quality and the like.
Description
Technical Field
The invention relates to a production process and a method of a high-purity reaction type flame retardant THPO, belonging to the technical field of preparation of trihydroxymethyl phosphine oxide (THPO).
Background
Halogen flame retardants have been widely used by people since the last 60 s, and phosphorus flame retardants are accelerating to replace bromine flame retardants as the environmental requirements have been increasing.
THPO does not contain halogen elements and conforms to the instruction of RHOS and Reach of European Union; the material does not contain a phosphate ester bond, has excellent hydrolysis resistance, does not influence the storage performance of raw materials, and simultaneously has no corrosivity on a mold in production; the phosphorus content is 22.14 percent and is far higher than that of most organic phosphorus flame retardants; can be used as a reactive flame retardant for flame retardance of polyurethane foam and epoxy resin. The THPO has a structural formula similar to that of glycerol, contains active hydroxymethyl, can be used as an intermediate to synthesize a corresponding flame retardant, and can also be used as an initiator to synthesize flame-retardant polyether instead of glycerol.
The THPO synthesis technology has a plurality of research reports and patent technologies published at home and abroad. At present, no industrial device is put into production. Because of the lack of reasonable and efficient production equipment and process route, the THPO has high production cost and serious environmental pollution, and the industrial development of the THPO is restricted.
Disclosure of Invention
The invention aims to provide a production process and a method of a high-purity reaction type flame retardant THPO, in particular to a purification and refining (comprising desalination, dealdehyding, concentration and the like) method of THPO reaction liquid, which adopts combined processes of nanofiltration desalination, nanofiltration dealdehyding, nanofiltration concentration, thin film evaporation and the like to realize the aim of preparing the high-purity THPO by desalination and dealdehyding under the conditions of shorter process, less equipment and lower operation cost.
The invention adopts the following technical scheme:
a production process and a method of a high-purity reaction type flame retardant THPO comprise the following steps:
step one, adding a liquid caustic soda aqueous solution with the mass concentration of 5-30% into a reaction kettle, and dripping a tetrakis (hydroxymethyl) phosphonium sulfate (THPS) aqueous solution with the mass concentration of 5-85% at the temperature of 25-65 ℃;
stopping dripping the THPS aqueous solution when the pH value is 9.5-12; heating to 55-90 ℃, and keeping the temperature for 6-15 h;
thirdly, dropwise adding sulfuric acid with the mass concentration of about 1-30% for adjusting acid, stopping dropwise adding the acid liquid when the pH value is 6.5-8.0, stirring for 0.5-2 h, and cooling to room temperature;
transferring the material to a dehydration kettle for dehydration, and carrying out reduced pressure distillation, wherein the temperature is controlled to be about 50-85 ℃; stopping distillation when the water content of the material is 5-20%, and centrifugally desalting when the material is cooled to about 20 ℃;
transferring the filtrate to a stock solution tank, adding pure water, diluting into THPO stock solution with the mass concentration of 1-20%, desalting by a nanofiltration desalting system, enabling desalted produced water to enter a dealdehyding stock solution tank, and enabling desalted concentrated water to enter a dehydration kettle for dehydration;
adding pure water into the dealdehyding stock solution tank, diluting the mixture into THPO dealdehyding stock solution with the mass concentration of 0.1-3%, dealdehyding through a nanofiltration dealdehyding system, feeding dealdehyding concentrated water into a concentration tank, and recycling dealdehyding produced water;
step seven, the solution in the concentration tank enters a nanofiltration concentration system for concentration, the produced water is recycled, and the concentrated solution enters an intermediate storage tank;
step eight, feeding the solution in the intermediate storage tank into a film evaporator, performing reduced pressure evaporation dehydration, controlling the temperature to be about 50-100 ℃, stopping dehydration when the moisture of the material is lower than 3.0%, and feeding the slurry into a finished product tank;
and step nine, filtering the finished product tank slurry by using a precision filter and packaging to obtain the finished product THPO.
The base in step one includes but is not limited to one or more of the following: hydroxides of metal M (M is an alkali metal or alkaline earth metal cation), ammonia water, sodium carbonate, sodium methoxide, sodium ethoxide, pyridine, triammonium, triethylamine and the like, and preferred bases are sodium hydroxide, potassium hydroxide and triethylamine.
The concentration of the alkali liquor in the step one is 5-30%, and the concentration of the alkali liquor is preferably 15-20%.
The temperature of the THPS dropping in the step one is 25-65 ℃, and the preferable temperature of the alkali dropping is 30-40 ℃.
The concentration of the THPS in the step one is 5-85%, the preferable concentration is 50-80%, and the particularly preferable concentration is 70-80%.
And the pH value of the THPS water solution which is stopped from being dripped in the step two is 9.5-12, and the pH value of the THPS water solution which is stopped from being dripped is preferably 10.5-11.
The reaction temperature in the second step is 55-90 ℃, and the preferable reaction temperature is 65-70 ℃.
And the heat preservation time in the step two is 6-15 hours, and the preferable heat preservation time is 8-10 hours.
The concentration of the sulfuric acid in the third step is 1-30%, and the preferable concentration of the sulfuric acid is 10-30%.
The pH value of the acid addition stopping in the third step is 6.5-8.0, and the preferable pH value is 7.0-7.5.
The heat preservation time in the third step is 0.5-2 h, and the preferable heat preservation time is 1 h.
The dehydration temperature in the fourth step is 50-85 ℃, and the preferable dehydration temperature is 65-70 ℃.
And in the fourth step, the moisture of the material for stopping dehydration is 5-20%, and the preferred moisture of the material is 8-12%.
And the centrifugal desalting temperature in the fourth step is 20-25 ℃.
The concentration of the THPO stock solution in the step five is 1-20%, and the preferred concentration of the THPO stock solution is 3-5%.
And the nanofiltration desalination system adopts a two-stage or more-stage nanofiltration desalination process for desalination, the molecular weight cut-off range of the adopted nanofiltration membrane is 150-1000 Da, the preferred molecular weight cut-off is 150-300Da, the same nanofiltration membrane can be used for each stage of nanofiltration membrane, different nanofiltration membranes can be used, the nanofiltration desalination operation pressure range is 0.4-5.0 MPa, and the preferred nanofiltration desalination operation pressure range is 3.0-4.0 MPa.
And sixthly, the concentration of the THPO dealdehydizing stock solution is 0-3%, and preferably the concentration of the THPO dealdehydizing stock solution is 0.5-1.5%.
And the nano-filtration aldehyde removal system in the sixth step adopts a two-stage or more than two-stage nano-filtration aldehyde removal process, the interception molecular weight range of the adopted nano-filtration membranes is 80-500 Da, the preferred interception molecular weight is 100-300Da, the same nano-filtration membrane can be used for each stage of nano-filtration membrane, different nano-filtration membranes can also be used, the nano-filtration aldehyde removal operation pressure range is 0.3-2.0 MPa, and the preferred nano-filtration aldehyde removal operation pressure range is 0.8-0.9 MPa.
And the aldehyde-removing water produced in the sixth step can be recycled for preparing liquid alkali or THPS aqueous solution.
And the nanofiltration concentration system in the step seven adopts a two-stage or more nanofiltration concentration process, the interception molecular weight range of the adopted nanofiltration membranes is 80-500 Da, the preferred interception molecular weight is 100-300Da, the same nanofiltration membrane can be used for each stage of nanofiltration membranes, different nanofiltration membranes can be used, the nanofiltration concentration operation pressure range is 1-3.0 MPa, and the preferred nanofiltration concentration operation pressure range is 1.5-2.0 MPa.
And the produced water in the seventh step can be recycled for diluting THPO stock solution or THPO dealdehydizing stock solution.
And eighthly, the reduced pressure evaporation dehydration temperature is 50-100 ℃, and the preferred reduced pressure evaporation dehydration temperature is 70-80 ℃.
And eighthly, the moisture of the material which stops the dehydration is less than 3.0 percent, and the preferable moisture of the material is 1.0-2.0 percent.
The mesh number of the precision filter in the ninth step is 200-1000 meshes, and the preferred mesh number of the filter is 400-800 meshes.
The production process and the method of the high-purity reaction type flame retardant THPO are suitable for purifying and refining the THPO reaction liquid. Compared with the prior art, the method has the advantages of short process flow, low requirement on equipment materials, investment saving, low operating cost, small occupied area, few control points, simple operation, convenient realization of automatic control, high product recovery rate, small amount of waste water, stable and reliable product quality and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
fig. 1 is a schematic diagram of a nanofiltration desalination system.
Fig. 2 is a schematic structural diagram of a nanofiltration dealdehyding system.
Fig. 3 is a schematic diagram of the nanofiltration concentration system.
Detailed Description
Example 1
(1) Preparing a THPO reaction solution: adding 1000 Kg of 19.2% NaOH aqueous solution into a 2000L glass lining reaction kettle, heating and stirring, slowly dripping 75% THPS aqueous solution at the temperature of 30 ℃, and stopping dripping the THPS aqueous solution when the pH value is 10.5-11; slowly heating to 65-68 ℃, and stirring for 10 hours under the condition of heat preservation; then, slowly dripping 25% sulfuric acid water solution into the kettle, stopping dripping acid when the pH value is 7.3-7.5, stirring for 1h, and cooling to room temperature; then transferring the materials to a 2000L dehydration kettle for dehydration, distilling under reduced pressure, and controlling the temperature in the kettle to be about 70 ℃; and when the water content of the material is 10-15%, stopping dewatering, cooling to about 20 ℃, performing centrifugal desalination, wherein the mass of the obtained salt NaCl is about 200 Kg, and the filtrate is reserved.
(2) Transferring THPO reaction liquid to a stock solution tank, adding water to dilute the THPO reaction liquid into 5 percent of THPO stock solution, pressurizing the THPO reaction liquid to 3.5MPa by a booster pump, then entering a nano-filtration desalination system (the nano-filtration desalination system is a two-stage nano-filtration membrane, the interception molecular weight range of each stage of nano-filtration membrane is 150-.
(3) Transferring the solution in the intermediate storage tank into a thin film evaporator through a transfer pump for reduced pressure evaporation dehydration, keeping the temperature of the thin film evaporator at about 75 ℃, and stopping dehydration when the water content of the material is lower than 2.0%; transferring the material to a finished product tank, and then filtering the material by a precision filter of 800 meshes to obtain 510 Kg of high-purity THPO with the purity of 99.1 percent and the yield of 91 percent.
Example 2
(1) The same as in example 1.
(2) Only the THPO reaction solution is transferred to a stock solution tank, and water is added to dilute the THPO reaction solution into 25 percent THPO stock solution. The other steps are the same as in example 1.
(3) The same as in example 1. Obtaining high-purity THPO 476 Kg, the purity is 98.2 percent and the yield is 85 percent.
Example 3
(1) The same as in example 1.
(2) Only the THPO reaction solution is transferred to a stock solution tank, and water is added to dilute the THPO reaction solution into 15 percent THPO stock solution. The other steps are the same as in example 1.
(3) The same as in example 1. Obtain high-purity THPO 493 Kg, the purity of which is 98.7 percent and the yield of which is 88 percent.
Example 4
(1) The same as in example 1.
(2) Only the desalted produced water enters a dealdehydizing stock solution tank, and is diluted into 3.5 percent THPO dealdehydizing stock solution by adding water. The other steps are the same as in example 1.
(3) The same as in example 1. Obtain high-purity THPO 493 Kg, the purity of which is 98.2 percent and the yield of which is 88 percent.
Example 5
(1) The same as in example 1.
(2) Only the desalted produced water enters a dealdehydizing stock solution tank, and is diluted into 2.5 percent THPO dealdehydizing stock solution by adding water. The other steps are the same as in example 1.
(3) The same as in example 1. 499 Kg of high-purity THPO is obtained, the purity is 98.4 percent, and the yield is 89 percent.
Example 6
(1) The same as in example 1.
(2) Only the THPO reaction solution is transferred to a stock solution tank, water is added to dilute the THPO reaction solution into 5 percent of THPO stock solution, the THPO stock solution is pressurized to 3.5MPa by a booster pump and then enters a nanofiltration desalination system (the nanofiltration desalination system is a two-stage nanofiltration membrane, and the molecular weight cut-off range of each stage of nanofiltration membrane is 1000-1200 Da). The other steps are the same as in example 1.
(3) The same as in example 1. The high-purity THPO 488 Kg is obtained, the purity is 95.4 percent, and the yield is 89 percent.
Example 7
(1) The same as in example 1.
(2) Only the THPO reaction solution is transferred to a stock solution tank, water is added to dilute the THPO reaction solution into 5 percent of THPO stock solution, the THPO stock solution is pressurized to 3.5MPa by a booster pump and then enters a nanofiltration desalination system (the nanofiltration desalination system is a two-stage nanofiltration membrane, and the molecular weight cut-off range of each stage of nanofiltration membrane is 200-400 Da). The other steps are the same as in example 1.
(3) The same as in example 1. Obtaining 504 Kg of high-purity THPO with the purity of 97.4 percent and the yield of 90 percent.
Example 8
(1) The same as in example 1.
(2) Only desalted and produced water enters a dealdehyding stock solution box, is diluted into 1 percent THPO dealdehyding stock solution by adding water, is pressurized to 0.8MPa by a booster pump, and then enters a nanofiltration dealdehyding system (the nanofiltration dealdehyding system is a two-stage nanofiltration membrane, and the molecular weight cutoff of each stage of nanofiltration membrane is 400-500 Da). The other steps are the same as in example 1.
(3) The same as in example 1. Obtaining high-purity THPO 504 Kg, the purity is 98.0 percent and the yield is 90 percent.
Example 9
(1) The same as in example 1.
(2) Only desalted and produced water enters a dealdehyding stock solution box, is diluted into 1 percent THPO dealdehyding stock solution by adding water, is pressurized to 0.8MPa by a booster pump, and then enters a nanofiltration dealdehyding system (the nanofiltration dealdehyding system is a two-stage nanofiltration membrane, and the molecular weight cut-off of each stage of nanofiltration membrane is 300-400 Da). The other steps are the same as in example 1.
(3) The same as in example 1. Obtaining high-purity THPO 504 Kg, the purity is 98.5 percent and the yield is 90 percent.
Example 10
(1) The same as in example 1.
(2) Transferring the THPO reaction solution to a stock solution tank, adding water to dilute the THPO reaction solution into 4% of THPO stock solution, pressurizing the THPO stock solution to 3.0MPa by a booster pump, and then feeding the THPO stock solution into a nanofiltration desalination system (the two stages of nanofiltration membranes adopt Dow NF270 nanofiltration membranes); the desalted water enters a dealdehyding stock solution box, is diluted into 0.5 percent THPO dealdehyding stock solution by adding water, is pressurized to 0.9MPa by a booster pump and then enters a nanofiltration dealdehyding system (the two-stage nanofiltration membranes adopt Dow NF90 nanofiltration membranes); the dealdehyding concentrated water enters a concentration box, is pressurized to 2.0MPa by a booster pump and then enters a nanofiltration concentration system (two stages of nanofiltration membranes adopt Dow NF90 nanofiltration membranes), and the concentrated water enters an intermediate storage tank for later use.
(3) Transferring the solution in the intermediate storage tank into a thin film evaporator through a transfer pump for reduced pressure evaporation dehydration, keeping the temperature of the thin film evaporator at about 70 ℃, and stopping dehydration when the water content of the material is lower than 1.5%; the material was transferred to a finishing tank and then filtered through a 800 mesh precision filter to obtain 518 Kg of high purity THPO, 98.6% purity and 92% yield.
Example 11
(1) The same as in example 1.
(2) Transferring the THPO reaction solution to a stock solution tank, adding water to dilute the THPO reaction solution into 6% of THPO stock solution, pressurizing the THPO stock solution to 2.7MPa by a booster pump, and then feeding the THPO stock solution into a nanofiltration desalination system (the two stages of nanofiltration membranes adopt Dow NF270 nanofiltration membranes); the desalted water enters a dealdehyding stock solution box, is diluted into 2.0 percent THPO dealdehyding stock solution by adding water, is pressurized to 0.9MPa by a booster pump and then enters a nanofiltration dealdehyding system (the two-stage nanofiltration membranes adopt Dow NF90 nanofiltration membranes); the dealdehyding concentrated water enters a concentration box, is pressurized to 1.8MPa by a booster pump and then enters a nanofiltration concentration system (two stages of nanofiltration membranes adopt Dow NF90 nanofiltration membranes), and the concentrated water enters an intermediate storage tank for later use.
(3) Transferring the solution in the intermediate storage tank into a thin film evaporator through a transfer pump for reduced pressure evaporation dehydration, keeping the temperature of the thin film evaporator at about 70 ℃, and stopping dehydration when the water content of the material is lower than 2.0%; transferring the material to a finished product tank, and then filtering the material by a 400-mesh precision filter to obtain 500 Kg of high-purity THPO with the purity of 98.4 percent and the yield of 89 percent.
Claims (6)
1. A production process of a reactive flame retardant THPO is characterized by comprising the following steps:
(1) adding the aqueous alkali solution into a reaction kettle, and dropwise adding a tetrakis (hydroxymethyl) phosphonium sulfate aqueous solution; stopping dripping the THPS aqueous solution when the pH is 9.5-12; heating to 55-90 ℃, preserving heat for 6-15 h, adjusting the pH to 6.5-8.0, stirring and cooling to room temperature; transferring the material to a dehydration kettle, dehydrating at 50-85 ℃, distilling under reduced pressure, cooling to normal temperature, centrifuging to remove salt, and keeping filtrate for later use;
(2) transferring the filtrate to a stock solution tank, adding water for dilution, desalting by a nanofiltration desalting system, and enabling desalted produced water to enter a dealdehyding stock solution tank after obtaining a dealdehyding stock solution;
(3) diluting the dealdehyding stock solution tank with water, and dealdehyding through a nanofiltration dealdehyding system, wherein when dealdehyding concentrated water enters a concentration tank, the dealdehyding produced water is recycled;
(4) the solution in the concentration tank enters a nanofiltration concentration system for concentration, the produced water is recycled, and the concentrated water enters an intermediate storage tank;
(5) and (4) evaporating and dehydrating the solution in the intermediate storage tank under reduced pressure until the water content of the material is less than 3.0%, and filtering to obtain THPO.
2. The process for producing the reactive flame retardant THPO according to the claim 1, wherein in the step (1), the aqueous alkali solution comprises but is not limited to one or more of the following: any one of alkali metal or alkaline earth metal hydroxide, ammonia water, sodium carbonate, sodium methoxide, sodium ethoxide, pyridine, triammonium or triethylamine, and the mass concentration of the liquid alkali water solution is 5-30%.
3. The production process of the reactive flame retardant THPO according to the claim 1, wherein in the step (1), the mass concentration of the tetrakis hydroxymethyl phosphonium sulfate aqueous solution is 5-85%.
4. The production process of the reactive flame retardant THPO according to claim 1, wherein in the step (2), the filtrate is diluted by adding water to a mass concentration of 1-20%; the nanofiltration desalination system adopts a two-stage or more nanofiltration desalination process; the molecular weight cut-off range of the adopted nanofiltration membrane is 150-1000 Da, each stage of nanofiltration membrane selectively uses the nanofiltration membrane with the same molecular weight cut-off or uses the nanofiltration membranes with different molecular weight cut-off, and the pressure range of the nanofiltration desalination operation is 0.4-4.0 MPa.
5. The production process of the reactive flame retardant THPO according to claim 1, wherein in the step (3), the dealdehydizing stock solution is diluted by adding water to a mass concentration of 0.1-3%; the nanofiltration dealdehyding system adopts a nanofiltration dealdehyding process with two or more stages; the molecular weight cut-off range of the adopted nanofiltration membrane is 80-1000 Da, each stage of nanofiltration membrane selectively uses the nanofiltration membrane with the same molecular weight cut-off or uses the nanofiltration membranes with different molecular weight cut-off, and the pressure range of the nanofiltration and dealdehyding operation is 0.3-2.0 MPa.
6. The process for producing a reactive flame retardant THPO according to claim 1, wherein in the step (4), the nanofiltration concentration system uses a nanofiltration concentration process of two or more stages; the molecular weight cut-off range of the adopted nanofiltration membrane is 80-1000 Da, each stage of nanofiltration membrane selectively uses the nanofiltration membrane with the same molecular weight cut-off or uses the nanofiltration membranes with different molecular weight cut-off, and the pressure range of nanofiltration concentration operation is 1.0-3.0 MPa.
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| CN116874961A (en) * | 2023-09-06 | 2023-10-13 | 江苏安耐特新材料科技有限公司 | High-flame-retardance thermoplastic plate for aviation interior decoration and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980313A (en) * | 2014-05-23 | 2014-08-13 | 厦门大学 | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof |
| CN104478929A (en) * | 2014-09-26 | 2015-04-01 | 湖北省兴发磷化工研究院有限公司 | Production technology of THPO and production equipment thereof |
| CN113429437A (en) * | 2021-06-30 | 2021-09-24 | 新乡医学院 | Synthesis method of tris (hydroxymethyl) phosphine oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980313A (en) * | 2014-05-23 | 2014-08-13 | 厦门大学 | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof |
| CN104478929A (en) * | 2014-09-26 | 2015-04-01 | 湖北省兴发磷化工研究院有限公司 | Production technology of THPO and production equipment thereof |
| CN113429437A (en) * | 2021-06-30 | 2021-09-24 | 新乡医学院 | Synthesis method of tris (hydroxymethyl) phosphine oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116874961A (en) * | 2023-09-06 | 2023-10-13 | 江苏安耐特新材料科技有限公司 | High-flame-retardance thermoplastic plate for aviation interior decoration and preparation process thereof |
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