CN102603662B - Method for recovering caprolactam technological waste liquid to synthesize flame retardant - Google Patents
Method for recovering caprolactam technological waste liquid to synthesize flame retardant Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 136
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000007788 liquid Substances 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 44
- 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 abstract description 21
- -1 nitrate ions Chemical class 0.000 claims abstract description 29
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims description 37
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 229920000877 Melamine resin Polymers 0.000 abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract 1
- 235000011837 pasties Nutrition 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 28
- 230000000694 effects Effects 0.000 description 19
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 description 6
- 239000006012 monoammonium phosphate Substances 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229920000388 Polyphosphate Polymers 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010805 inorganic waste Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a method for recovering a caprolactam technological waste liquid to synthesize a flame retardant. The method includes: a polymerization step, in which melamine and a technological waste liquid containing phosphate ions and nitrate ions are mixed so as to bring the phosphate ions and nitrate ions in the caprolactam technological waste liquid and the melamine into a polymerization reaction to generate a phosphate and a nitrate, thus obtaining a flame retardant raw liquid; and a purification step, in which the nitrate in the flame retardant raw liquid is removed so as to obtain a the flame retardant in coarse liquid nitrate, in order to obtain a pasty flame retardant. The method for recovering a caprolactam technological waste liquid to synthesize a flame retardant of the invention can use the recovered waste liquid to substitute a high purity phosphorus compound so as to reduce the raw material and energy consumption of the high purity phosphorus compound during preparation, thus reaching the efficacy of saving raw materials and energy.
Description
Technical field
The invention relates to a kind of method of synthetic fire retardant, particularly a kind of method that reclaims the synthetic fire retardant of caprolactam technology waste liquid.
Background technology
Traditional fire retardant is that halogen is fire retardant, this halogen is fire retardant is easily to produce Dioxins (Dioxin) to accumulate in environment with furans (Furan) after burning, not only ecotope is caused to severe contamination excessive accumulation and increase carcinogenic risk in organism even.Therefore, present stage is progressively to replace it with non-halogen flame retardant, this non-halogen flame retardant is roughly divided into phosphorus flame retardant and the large class of inorganic flame retardant two, wherein, inorganic flame retardant is to utilize mineral compound (for example: aluminium hydroxide, magnesium hydroxide ... etc.) crystal water that disengages when cracking of burning reduce burning temperature to reach fire-retardant effect, but, in the time that material combustion temperature is high this inorganic flame retardant in a large number interpolation can there is good flame retardant resistance, so, can improve the cost burden of fire retardant, and the problem of its resin generation consistency of easily adding with frie retardant coating institute wish or because of excessive interpolation, affect bonding force and the intensity of resin, cause film easily to chap, and be restricted on frie retardant coating uses.
Based on above-mentioned shortcoming, most of dealers are that phosphorus flame retardant good taking resistance to fuel efficiency rate and that Biodegradable is high is as developing focus, utilize phosphorus series compound dehydration in the time of burning to produce fine and close carbon-coating to reach fire-retardant effect, wherein, again taking melamine phosphate (melamine phosphate), melamine pyrophosphate (melamine pyrophosphate) and melamine polyphosphate (melamine polyphosphate) as common phosphorus flame retardant, and existing method in order to synthetic these phosphorus flame retardants is as described below:
1, with phosphoric acid and the common stoichiometric number hour of trimeric cyanamide of commercially available high density (approximately 85%), to obtain melamine phosphate (melamine phosphate).Then, again this melamine phosphate is carried out to high-temperature roasting with 250 to 300 degree left and right Celsius, make this melamine phosphate convert melamine pyrophosphate to, and under long effect, this melamine pyrophosphate is to convert gradually melamine polyphosphate to.Please refer to chemical equation 1, as follows:
Wherein, n, m >=2 (chemical equation 1)
But, this existing method in order to synthetic this phosphorus flame retardant is only can obtain melamine phosphate because phosphoric acid reacts with trimeric cyanamide, and the flame retardant effect of this melamine phosphate is poor, therefore, must carry out high-temperature roasting to this melamine phosphate, to obtain trimeric cyanamide Jiao (gathering) phosphoric acid salt with better flame retardant effect, so, easily under high temperature action, consume a large amount of energy, and improve the cost burden of fire retardant building-up process.
2, respectively for example, with the phosphorus series compound (: phosphoric acid, orthophosphoric acid salt, pyrophosphate salt or polymeric phosphate) of high density (approximately 85%) and the common stoichiometric number hour of trimeric cyanamide, to obtain respectively melamine phosphate, melamine pyrophosphate and melamine polyphosphate.Please refer to chemical equation 2, as follows:
(chemical equation 2)
But, in this existing method in order to synthetic this phosphorus flame retardant, for example, be with the phosphorus series compound (: phosphoric acid, orthophosphoric acid salt, pyrophosphate salt or polymeric phosphate) of trimeric cyanamide effect the compound that purity is higher, therefore, must be via extra technological reaction and purifying, can obtain the high purity phosphorus series compound with better reaction efficiency, so, be easily to cause high purity phosphorus series compound in raw material and the energy consume of preparation process, even increase the cost burden of fire retardant building-up process.
Because above-mentioned shortcoming, the method for this existing synthetic fire retardant still has necessity of being improved really.
summary of the invention
Main purpose of the present invention is the above-mentioned shortcoming of improvement, a kind of method that reclaims the synthetic fire retardant of caprolactam technology waste liquid is provided, it is to replace high purity phosphorus series compound with Recycling of waste liquid, to reduce high purity phosphorus series compound in raw material and the energy consume of preparation process.
Of the present invention time an object is to provide a kind of method that reclaims the synthetic fire retardant of caprolactam technology waste liquid, is directly to obtain preferably fire retardant of flame retardant effect, to reduce the cost burden of fire retardant building-up process.
A further object of the present invention is to provide a kind of method that reclaims the synthetic fire retardant of caprolactam technology waste liquid, is the large quantity of exhaust gas that can avoid high-temperature roasting to disengage, to reduce atmospheric pollution and to reduce the injury that environment is caused.
For reaching aforementioned goal of the invention, the technology contents that the present invention uses includes:
A kind of method that reclaims the synthetic fire retardant of caprolactam technology waste liquid, it is to comprise: a polymerization procedure, that the caprolactam technology waste liquid that trimeric cyanamide and is included to phosphate anion and nitrate ion mixes, make phosphate anion and nitrate ion and trimeric cyanamide generation polyreaction generation phosphoric acid salt and nitrate in this caprolactam technology waste liquid, and obtain the thick liquid of a fire retardant; And a purification step, be the nitrate of removing in the thick liquid of this fire retardant, to obtain a pulpous state fire retardant.
The method of the synthetic fire retardant of recovery caprolactam technology waste liquid of the present invention, it is to replace high purity phosphorus series compound with Recycling of waste liquid, to reduce high purity phosphorus series compound in raw material and the energy consume of preparation process, and then reach effect of conservation and the energy.
Brief description of the drawings
Fig. 1: the reacting flow chart one of the synthetic fire retardant of recovery caprolactam technology waste liquid of the present invention.
Fig. 2: the X-ray diffractometer analysis chart of the synthetic fire retardant of recovery caprolactam technology waste liquid of the present invention.
Fig. 3: the thermogravimetric analyzer analysis chart of the synthetic fire retardant of recovery caprolactam technology waste liquid of the present invention.
Fig. 4: the reacting flow chart two of the synthetic fire retardant of recovery caprolactam technology waste liquid of the present invention.
Fig. 5 a, Fig. 5 b, Fig. 5 c: the result of fire-resistant painting adhesion test of the present invention.
[main element nomenclature]
(the present invention)
S1 polymerization procedure S2 purification step
S3 procedure of processing S4 coating preparation process
Embodiment
For above-mentioned and other object of the present invention, feature and advantage can be become apparent, preferred embodiment of the present invention cited below particularly, and coordinate accompanying drawing, be described in detail below:
Please refer to shown in Fig. 1, the method for the synthetic fire retardant of recovery caprolactam technology waste liquid of preferred embodiment of the present invention, is to comprise a polymerization procedure S1 and a purification step S2.
This polymerization procedure S 1 utilizes a hexanolactam process waste liquor and a trimeric cyanamide to carry out polyreaction, to obtain the thick liquid of a fire retardant.In more detail, this caprolactam technology waste liquid is to be reacted with phosphatic hydroxylamine by pimelinketone to generate the inorganic process waste liquid that the process of cyclohexanone-oxime produces, this caprolactam technology waste liquid through preliminary filter to remove react after catalyst, still include ammonium radical ion (NH
4 +), nitrate ion (NO
3 -), phosphate anion (PO
4 3-), azanol (HONH
2), the composition such as trace metal ion and minor amount of water soluble organism.After utilizing this caprolactam technology waste liquid and trimeric cyanamide evenly to mix, heat up, make nitrate ion and phosphate anion and trimeric cyanamide generation polyreaction in this caprolactam technology waste liquid, to produce the salts such as nitrate and phosphoric acid salt, so, be can obtain this to there is the thick liquid of full-bodied fire retardant.
For example, restrain oneself and add the trimeric cyanamide of 12.6 grams in the reactive tank of lactan process waste liquor in being added with 100, in the present embodiment, this caprolactam technology waste liquid is the azanol of the phosphate anion 0.014mole/kg of nitrate ion, the 1.6mole/kg of ammonium radical ion, the 2.45mole/kg of the hydrogen ion that includes 0.98mole/kg, 3.06mole/kg, and the concentration of this trimeric cyanamide is 99%.After the two is uniformly mixed in this reactive tank, heats up and react 1 to 1.5 hour between 60 to 65 degree Celsius, in the present embodiment, this temperature is select to be first warming up to 62 degree Celsius and in the time of subsequent reactions, control temperature between 60 to 65 degree Celsius, make this two reaction can there is preferably reaction efficiency, and under this condition, react 1 hour comparatively suitable.Treat that ammonium radical ion, nitrate ion, phosphate anion in this caprolactam technology waste liquid react the insoluble salt of generation gradually with trimeric cyanamide, form the solid salt of coagulated state and cannot stir and cause viscosity constantly to promote this reactive tank periphery even, when in process, in this reactive tank, suspension becomes oyster white by light green, be to obtain the thick liquid of this fire retardant reacting completely.The present embodiment is to reach after 60 DEG C in temperature, viscosity progressively rises in time, should be noted during this time and maintain whipped state, could obtain the uniform product of reaction (must strengthen the horsepower stirring when meaning is viscosity rising), otherwise can form fixed thing in suspension surface, and it is large that particle becomes, and reacts more incomplete.And because the thick liquid of this fire retardant is to be reacted generation with trimeric cyanamide by caprolactam technology waste liquid, wherein contain some unknown compositions, response situation is more complicated.Therefore, in the present embodiment, being the viscosity of selecting to control this fire retardant, to be increased to 100cp by 0.1cp above and reach complete polyreaction compared with good, and increase with the treatment capacity of this caprolactam technology waste liquid, and it is to coordinate prolongation with the reaction times of this trimeric cyanamide.
This purification step S2 is solubility unreacted reactant and the reaction impurity of removing in the thick liquid of this fire retardant, to obtain a pulpous state fire retardant.In more detail, the thick liquid of fire retardant that this polymerization procedure S1 reaction is generated filter and again pulp-water wash, to remove other compositions that do not react with trimeric cyanamide in the thick liquid of this fire retardant, and wash away this nitrate ion simultaneously and react the nitrate producing with trimeric cyanamide, obtain whereby the fire retardant of this pulpous state and avoid this nitrate ion in this fire retardant, to form combustion-supporting effect.For example, in filter cake after the thick liquid of this fire retardant filters, add the water of 200ml, the thick liquid of fire retardant that makes this coagulated state is to form pulpous state, again by thick the fire retardant of this pulpous state liquid uniform stirring 15 to 30 minutes, in the present embodiment, be preferably this pulpous state fire retardant uniform stirring 20 minutes, to utilize filter paper to filter, so, repeat the step at least three times that this above-mentioned pulp-water again washes and filter, to remove the nitrate product that contains nitrate ion in the thick liquid of this fire retardant, to obtain the fire retardant of this pulpous state, this fire retardant is the trimeric cyanamide product that contains phosphoric acid salt.
Please refer to shown in Fig. 2, this fire retardant is carried out to Analysis and Identification with X-ray diffractometer, so as to confirming that this fire retardant is the trimeric cyanamide product that contains phosphoric acid salt.To identify taking the synthetic trimeric cyanamide product of following four groups of different modes: A as reagent level monoammonium phosphate react with technical grade trimeric cyanamide generate melamine phosphate, B is reagent level monoammonium phosphate, nitric acid and ammoniacal liquor are according to the phosphate radical of previous embodiment, nitrate radical and ammonium radical ion concentration are reacted the melamine phosphate generating with trimeric cyanamide after mixing, C is after fertilizer grade phosphoric acid mixes with the filtrate (1: 1) of filtering after previous embodiment (inorganic process liquor and trimeric cyanamide) reaction, react again the melamine phosphate generating with technical grade trimeric cyanamide, D is the synthetic fire retardant of recovery caprolactam technology waste liquid of the present invention and trimeric cyanamide.As shown in the figure, trimeric cyanamide product D of the present invention is to have different diffraction values from the melamine phosphate of other A, B and C reaction gained, the diffraction angle (2 θ) that the results are shown in of D is the diffraction crest that 8.3,16.6,17.8,18.8 and 27.2 places all have melamine pyrophosphate, accordingly, be to learn that the major ingredient of this fire retardant is melamine pyrophosphate.
Please refer to shown in Fig. 3, this fire retardant is carried out to Analysis and Identification with thermogravimetric analyzer (TGA), as shown in the figure, by aqueous vapor, thermolysis is caused the weight loss producing before 100° centigrade, and this aqueous vapor can thoroughly be removed while spending in being warming up to Celsius 200.Therefore, the present invention utilizes caprolactam technology waste liquid to reclaim synthetic fire retardant, to have obvious weight loss between 200 to 800 degree Celsius, and the remaining weight in the time that Celsius 790 spend reaches 4.708%, and trimeric cyanamide almost decomposes completely in the time that Celsius 360 spend, at high temperature complete oxidation and gasification, without remaining weight.Whereby, the major ingredient that confirms this fire retardant is really for melamine pyrophosphate but not unreacted trimeric cyanamide.
Learnt by the above results, the method for the synthetic fire retardant of recovery caprolactam technology waste liquid of the present invention is to obtain the fire retardant that contains melamine pyrophosphate, and this melamine pyrophosphate cording has preferably flame retardant effect.By the inorganic waste liquids of this caprolactam technology be can be directly and trimeric cyanamide generate melamine pyrophosphate, and need, with the melamine phosphate process high-temperature roasting that highly purified phosphoric acid and trimeric cyanamide generated, this melamine phosphate be heated and just can be converted into melamine pyrophosphate.So, the waste liquid that not only can produce this caprolactam technology carries out recycling, to reduce the synthetic required raw materials cost expending of fire retardant, and energy consume and the caused atmospheric pollution of torrefaction waste gas of further avoiding high-temperature roasting to cause.
In addition, interior of building is increasingly strict to fp requirement now, interior decoration, compartment material used, and with the steel construction in building, various countries all have all kinds of fire safety rules.Especially the fire protection requirement to public building and building, makes the purposes of all kinds of fire-retardant materials and frie retardant coating, is subject to great attention.The fire prevention of current indoor application and steel construction, large more options are born the harmful ability of fire in case fiery coating improves material, especially after 911 terrified attacks, allow people recognize steel softening problem under 550 degree high temperature Celsius, the foamed phenomenon producing in the time being subject to fire by expanding fire-proof paint, the volumetric expansion that makes this frie retardant coating is original decades of times, so, can delay heat energy to reach steel structure, wall, timber ... wait the speed of subsurface material, and the carbon-coating that utilizes this frie retardant coating surface is to completely cut off contacting between combustiblematerials and air, making this combustiblematerials surface become difficulty fires or does not fire and stop fire to occur.
Because this expanding fire-proof paint is to produce foamed phenomenon, and form fine and close carbon-coating in the surface of this combustiblematerials, with effectively intercept this air contact with combustiblematerials and produce burning phenomenon.Therefore, in the present embodiment, rear another operation one procedure of processing S3 and a coating preparation process S4 (please refer to shown in Fig. 4) that can select in this purification step S2, or by direct this coating preparation process of selection operation S4 after this purification step S2, further the fire retardant after above-mentioned purifying is applied to the exploitation of frie retardant coating.
Shown in Fig. 4, this procedure of processing S3 can select the fire retardant that last purification step S2 filtration is obtained to grind, and to obtain a microgranular fire retardant, and the microgranular fire retardant that this operation steps obtains is slurries kenel.In more detail, that the pulpous state fire retardant that filters gained in this purification step S2 is directly added to suitable water, with clarifixator or wet grinding mode, reduce the grain diameter of this pulpous state fire retardant, to obtain the microgranular fire retardant of this slurries kenel, and the size of guaranteeing the microgranular fire retardant of this slurries kenel is to be the screen cloth of 325 orders (mesh) by this pore size, to guarantee that this fire retardant can have the quality that does not affect this fire retardant compared with good mixing particle diameter.For example, to add appropriate water in this pulpous state fire retardant, be preferably 15% to 40% to adjust the concentration of this pulpous state fire retardant, after stirring, the two grinds with clarifixator, and the rotating speed of controlling this clarifixator is preferably the above running of 20000rpm at least 20 minutes, and remove and grind incomplete larger particles, and obtain the microgranular fire retardant of this slurries kenel and guarantee that the size of the microgranular fire retardant of this slurry condition is to be the screen cloth of 325 orders (mesh) by this pore size, and obtain preferably fire retardant.
Moreover this procedure of processing S3 pulverizes after can also selecting this pulpous state fire retardant to filter, dry, to obtain this microgranular fire retardant.In more detail, pulpous state fire retardant after purifying is filtered and dries to remove completely to the moisture of this pulpous state fire retardant, and in the time that this pulpous state fire retardant reaches constant weight, pulverize the fire retardant of this oven dry and obtain this microgranular fire retardant with pulverizer again, and the microgranular fire retardant that this operation steps obtains is powder kenel.For example, under the environment of 55 to 65 degree Celsius, dry this pulpous state fire retardant, and be preferably and select to dry these pulpous state fire retardants with 60 degree Celsius, do not change the composition of this fire retardant to there is drying effect preferably.Wait completing when removing the moisture content of this pulpous state fire retardant and scale and must this pulpous state fire retardant being constant weight, then pulverize this with this pulverizer and continue 15 to 30 seconds through cooling fire retardant.In the present embodiment, be preferably this cooling fire retardant is continued to pulverize 20 seconds, to guarantee that this fire retardant can have the quality that does not affect this fire retardant compared with good mixing particle diameter.So, repeat this above-mentioned pulverizing action at least four times, taking control the particle diameter of this fire retardant be can be by pore size the screen cloth as 325 orders (mesh), and obtain the microgranular fire retardant of the powder kenel with better size.
This coating preparation process S4 is mixed with a membrane-forming agent, a carbon forming agent, a cakingagent and an auxiliary agent in the microgranular fire retardant of the powder kenel that this contains melamine pyrophosphate, carries out the allotment of aqueous fire-proof coating, to obtain a frie retardant coating; Or in the microgranular fire retardant of the slurries kenel that this contains melamine pyrophosphate, add a membrane-forming agent, a carbon forming agent, a cakingagent and an auxiliary agent, carry out the allotment of aqueous fire-proof coating, to obtain a frie retardant coating.In more detail, be in this fire retardant, add to scale a membrane-forming agent (for example: monoammonium phosphate, polyphosphoric acid amine ... etc.), a carbon forming agent (for example: tetramethylolmethane ... etc.), an auxiliary agent (for example: titanium dioxide ... etc.), a cakingagent (for example: resin, polyvinyl acetate (PVA) ... etc.) and water, to obtain a frie retardant coating mixture.Wherein, for example, according to the kenel of this fire retardant and the attribute of more each additive (: wetting ability, hydrophobicity) difference, can select to add appropriate water sequentially to add again this membrane-forming agent, carbon forming agent, auxiliary agent and cakingagent in the microgranular fire retardant of this slurries kenel, or selection is first with after suitable this membrane-forming agent of water mixed dissolution and carbon forming agent, more sequentially add microgranular fire retardant, auxiliary agent and the cakingagent of this powder kenel.
For example, being the microgranular fire retardant that utilizes weight percent meter 2～30% allocates and mixes with the water of 2～30% membrane-forming agent, 3～10% carbon forming agent, 2～10% auxiliary agent, 10～35% cakingagent and 0～50%, and the attribute according to this fire retardant and more each additive is selected the sequencing mixing, to obtain the frie retardant coating mixture with better allotment ratio.In the present embodiment, be preferably after the tetramethylolmethane of selecting prior to the monoammonium phosphate of mixed dissolution 13.65% in the water of weight percent meter 37.54% and 5.8%, sequentially add again microgranular fire retardant, 6.14% titanium dioxide and 23.21% the polyvinyl acetate (PVA) of 13.65% powder kenel, to be deployed into the frie retardant coating with better flameproof effect; Moreover, goodly can also select directly to add 40% water in the microgranular fire retardant of 12.3% slurry condition, sequentially add again 12.3% monoammonium phosphate, 5.23% tetramethylolmethane and 5.23% titanium dioxide, after those additives evenly mix, add 24.61% polyvinyl acetate (PVA), to be deployed into the frie retardant coating with better flameproof effect, and the frie retardant coating of allocating via aforesaid method is to have preferably dispersiveness.
The expanding fire-proof paint warp let-off standard test office that aforesaid operations step is obtained carries out the test of fire resistance, and to learn according to the CNS6532 progression of resistance to combustion test result, this frie retardant coating is the level (referring to table 1) that can reach the secondary of resistance to combustion.And fire retardant of the present invention can progressively decompose under the high temperature in the scene of a fire, and produce non-flammable gas (as nitrogen etc.), reach fire-retardant effect to reduce oxygen concn.Moreover, the present invention selects using monoammonium phosphate as membrane-forming agent, be can increase the expansion multiplying power to 50 times of this expanding fire-proof paint more than, and selecting to replace conventional resins as cakingagent using polyvinyl acetate (PVA), is can promote the consistency between this microgranular fire retardant and cakingagent and increase frie retardant coating in the adhesive ability of base material.Whereby, this expanding fire-proof paint is effectively to intercept the impact of flame on frie retardant coating layer below base material, and reaches preferably heat insulating function.
Table 1
Shown in Fig. 5 a-c, be that fire retardant of the present invention is coated with and invests the surface of combustiblematerials, and test with flame.Learnt by Fig. 5 a, b result, the surface of this combustiblematerials, under the burning of flame, is to produce obvious foamed phenomenon, and does not see the vestige (as shown in 5 figure c) burning in the back side of this combustiblematerials.So, this fire retardant is to form fine and close carbon-coating in the surface of this combustiblematerials, and under the high temperature of flame, progressively decomposes and produce non-flammable gas (as nitrogen etc.), contacts and produces the phenomenon of burning effectively to intercept this air with combustiblematerials.
Accordingly, proved invention is applied to the exploitation of frie retardant coating via the fire retardant that reclaims caprolactam technology waste liquid synthesized, really there is excellent flame retardant effect and can extensively build material and the required fire protection coating of indoor decoration as steel, to reach preferably flameproof effect.
The method of the synthetic fire retardant of recovery caprolactam technology waste liquid of the present invention, it is to replace high purity phosphorus series compound with Recycling of waste liquid, to reduce high purity phosphorus series compound in raw material and the energy consume of preparation process, and then reach effect of conservation and the energy.
The method of the synthetic fire retardant of recovery caprolactam technology waste liquid of the present invention, is directly to obtain preferably fire retardant of flame retardant effect, to reach the effect that reduces fire retardant building-up process cost burden.
Claims (1)
1. a method that reclaims the synthetic fire retardant of caprolactam technology waste liquid, is characterized in that, it comprises:
A polymerization procedure, that trimeric cyanamide is mixed with a kind of caprolactam technology waste liquid that includes phosphate anion and nitrate ion, make phosphate anion and nitrate ion and trimeric cyanamide generation polyreaction generation phosphoric acid salt and nitrate in this caprolactam technology waste liquid, and obtain the thick liquid of fire retardant; And
A purification step, the nitrate of removing in the thick liquid of this fire retardant, to obtain a pulpous state fire retardant, in this caprolactam technology waste liquid, separately include ammonium radical ion, azanol, metal ion and water soluble organic substance, and this caprolactam technology waste liquid is a kind of inorganic process waste liquid.
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| CN108531030B (en) * | 2018-04-16 | 2020-05-22 | 武汉工程大学 | Water-based intumescent fire-retardant coating based on industrial waste liquid recycling and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1385493A (en) * | 2002-04-30 | 2002-12-18 | 合肥精汇化工研究所 | Method for synthesizing environment protective fire-retartant agent MP |
| US20050101707A1 (en) * | 2002-09-06 | 2005-05-12 | Clariant Gmbh | Compacted flame-retardant composition |
| CN1696120A (en) * | 2005-05-13 | 2005-11-16 | 四川大学 | Synthesizing melamine cyanuric acid by using solution of polyamide resin as reaction medium, and preparation method |
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| CN1385493A (en) * | 2002-04-30 | 2002-12-18 | 合肥精汇化工研究所 | Method for synthesizing environment protective fire-retartant agent MP |
| US20050101707A1 (en) * | 2002-09-06 | 2005-05-12 | Clariant Gmbh | Compacted flame-retardant composition |
| CN1696120A (en) * | 2005-05-13 | 2005-11-16 | 四川大学 | Synthesizing melamine cyanuric acid by using solution of polyamide resin as reaction medium, and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| Preparation, properties and characterizations of halogen-free nitrogenephosphorous flame-retarded glass fiber reinforced polyamide 6 composite;Yinghong Chen, et al.;《Polymer Degradation and Stability》;20060421;第91卷;2003-2013 * |
| YinghongChen et al..Preparation |
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