WO2021073198A1 - Continuous production method for amino trimethylene phosphonic acid crystal - Google Patents
Continuous production method for amino trimethylene phosphonic acid crystal Download PDFInfo
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- WO2021073198A1 WO2021073198A1 PCT/CN2020/105781 CN2020105781W WO2021073198A1 WO 2021073198 A1 WO2021073198 A1 WO 2021073198A1 CN 2020105781 W CN2020105781 W CN 2020105781W WO 2021073198 A1 WO2021073198 A1 WO 2021073198A1
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- crystallization
- temperature
- phosphonic acid
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- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000013078 crystal Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000010924 continuous production Methods 0.000 title claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 75
- 230000008025 crystallization Effects 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000012452 mother liquor Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000004821 distillation Methods 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000012263 liquid product Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- -1 aminotrimethylene phosphine Chemical compound 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000004880 explosion Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical group NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000668 effect on calcium Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
Definitions
- the invention belongs to the technical field of fine chemical production, and specifically relates to a continuous production method of amino trimethylene phosphonic acid crystals.
- Amino trimethylene phosphonic acid (referred to as ATMP) is a cathodic corrosion inhibitor, which can dissociate in water to form 6 positive ions and 6 negatively charged ions, which can form a polycyclic ring with Ca 2+ and Mg 2+ in water Chelate. This macromolecular chelate is loosely dispersed in water, which destroys the normal crystallization of calcium and magnesium scale. Therefore, ATMP also has a better effect on calcium sulfate, calcium silicate, calcium carbonate and magnesium silicate in water.
- Good scale inhibitor is an organic phosphonic acid water quality stabilizer.
- ATMP is a non-equivalent chelating agent with good solubility limit effect, which can prevent dozens or hundreds of calcium and magnesium ions by one molecule Produces scale precipitation with sulfate ions, etc.
- ATMP has synergistic effect with other polycarboxylic acid scale inhibitors and shows good compatibility. Therefore, it is widely used in circulating cooling water, oil field water injection and water-containing oil pipelines, printing and dyeing water
- the high-purity ATMP products can also be used in the electroplating industry, metal surface treatment, hydrogen peroxide stabilization and metal ion masking.
- the patent of CN101597305B discloses a process for preparing high-purity solid amino trimethylene phosphonic acid or hydroxyethylene diphosphonic acid. The process combines amino trimethylene phosphonic acid or hydroxyethylene diphosphonic acid with an effective substance content of 68-85%.
- CN103509052B discloses a method for preparing high-purity amino trimethylene phosphonic acid by concentrating and centrifuging from the synthesis of liquid products; CN101143752A adds crystal nucleus sodium acetate in a reaction kettle, stirs, and adds anhydrous crystallization aid Amino trimethylene phosphonate with a content of ⁇ 90% is prepared by treatment processes such as ethanol and dehydration and the preparation process thereof. The inventor disclosed a preparation process suitable for electronic grade solid amino trimethylene phosphonic acid in CN100471860C.
- the present invention provides a production method capable of continuously producing amino trimethylene phosphonic acid crystals.
- the method adopts the natural cooling and crystallization of amino trimethylene phosphonic acid and adopts multi-stage crystallization, which can effectively stabilize product quality, improve equipment utilization and product production capacity, save water and reduce emissions, generate no three wastes, is safe and environmentally friendly, and is beneficial to realization Automatic control and large-scale industrial production.
- a continuous production method of amino trimethylene phosphonic acid crystals specifically includes the following steps:
- the amino trimethylene phosphonic acid liquid with an active content of 50-60% is preheated, gas-liquid separated, and then continuously pumped into the still at a constant speed;
- the mixture material is cooled in the nth-stage crystallization kettle again through cyclic condensation and the temperature of the system is maintained at 20 ⁇ 2°C. After the system is filled with analytical crystals, the mixture material is centrifuged and dried to obtain amino Sanya with an active content of ⁇ 93% Methylphosphonic acid crystal product, the mother liquor obtained from separation is collected and recycled.
- the temperature of the liquid after preheating in the above step (1) ranges from 60 to 100°C. Preferably, the temperature after preheating is from 75 to 90°C.
- the concentration temperature in the above step (2) can be 90-130°C, preferably, the concentration temperature is 100-120°C.
- the preheating separation, concentration and purification described in the above steps (1) and (2) means that the materials are separated and removed by the gas-liquid separator to remove the low-boiling hydrogen chloride, formaldehyde gas and part of the water in the system.
- the high-boiling substances are The bottom of the gas-liquid separator continuously enters the distillation concentrator.
- the lower boiling point components obtained from the separation and purification described in the above step (1) and step (2) can be recycled and used as the raw material for the production of liquid products after being cooled and recovered.
- the temperature of the condensed material in the above step (3) is 60-70°C.
- the mixture material described in the above step (3) realizes automatic material transfer through the PLC automatic interlocking device established between the level gauge set in the 1-n-level crystallization kettle, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle.
- the gradient range of the natural cooling in the 1-n-level crystallization kettle is 5-20°C/level.
- the gradient range of the natural cooling in the 1-21-n-level crystallization kettle is 5 ⁇ 10°C/level
- the gradient range of the natural cooling in the 3-n-level crystallization kettle is 10-20°C/level.
- the stirring speed of the first stage crystallization kettle is 50-150 revolutions/min, and the stirring speed is gradually reduced.
- the mother liquor described in the above step (4) is continuously pumped into the distillation and concentration device to be concentrated and then recycled for successive recrystallization.
- the mother liquor can be directly sold as a liquid product or used as a compound Phosphorus-containing scale and corrosion inhibitor monomer.
- the present invention realizes the continuous crystallization of hydroxyethylene diphosphonic acid crystals and the continuous recycling of mother liquor through the control of the environmental parameters of the crystallization kettles connected in series at various levels, thereby improving production efficiency and stable product quality;
- This method uses gravity sedimentation to separate and purify the liquid products after preheating and distillation and concentration stages, and remove relatively low boiling impurities such as hydrogen chloride, acetic acid and excess water contained in the product, and effectively realize the material recovery. Fast separation and purification, shorten the production cycle;
- the aminotriylene phosphonic acid liquid with an active content of 55.63% was preheated to 85°C by a graphite heater, and hydrogen chloride, formaldehyde gas and a small amount of water vapor in the system were removed by gas-liquid separation. Then, it was continuously fed at a flow rate of 270kg/h. Distillation kettle; when the material is continuously fed for 1 hour until the volume of the material is about one-third of the volume of the kettle body, turn on the distillation kettle and stir, maintain the system temperature at 115 ⁇ 1°C, and quickly distill and concentrate under the negative pressure of -0.05MPa; continuous feeding After 4 hours, the active content of the materials in the distillation kettle was 71.04% and the volume of the materials in the distillation kettle reached the set transfer level.
- the valve at the bottom of the distillation kettle and the transfer pump were automatically turned on, and the material cooled to 60°C by the heat exchanger was calculated as 320kg/
- the flow rate of h is continuously transferred to the first-stage crystallization kettle for crystallization, which is controlled by the PLC automatic interlocking device established between the level gauges set in the crystallization kettles at all levels, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle.
- Step-by-step automatic material transfer is completed between the crystallization kettles connected in series between the first and the fifth stages, the stirring rate is controlled at 80 revolutions/min and the natural temperature gradient of 5-20 °C/level, and the continuous crystallization is carried out step by step; among them, the crystallization of 1 to 4 levels
- the injection time of the solid-liquid mixture in the kettle from the lowest level to the highest level is 2 hours, 2 hours, 2 hours, 2 hours and 3.2 hours respectively; the temperature of the mixture materials in the 1-5 crystallization kettle after natural cooling reaches 54 °C, 50°C, 40°C, 30°C, 20°C, pass circulating cooling water into the interlayer of the crystallization kettle at the last stage, the fifth stage, after cooling to 20 ⁇ 2°C, stir slowly for 2 hours to make the system fully crystallize, the mixture After centrifugation, drying and separation, the amino trimethylene phosphonic acid white and transparent regular crystal product and centrifugal mother liquor are obtained; the centrifugal mother liquor is recycled to the concentration tank
- the aminotriylene phosphonic acid liquid with an active content of 59.47% is preheated to 90°C by a graphite heater, and hydrogen chloride, formaldehyde gas and a small amount of water vapor in the system are removed by gas-liquid separation. Then, it is continuously fed at a flow rate of 255kg/h.
- Distillation kettle when the material is continuously fed for 1 hour until the volume of the material is about one-third of the volume of the kettle body, turn on the distillation kettle and stir, maintain the system temperature at 108 ⁇ 1°C, and quickly distill and concentrate under negative pressure of -0.06MPa; continuous feeding After 4.2 hours, the active content of the materials in the distillation kettle was 72.03% and the volume of the materials in the distillation kettle reached the set transfer level.
- the valve at the bottom of the distillation kettle and the transfer pump were automatically opened, and the material cooled to 70°C by the heat exchanger was pressed at 280kg/
- the flow rate of h is continuously transferred to the first-stage crystallization kettle for crystallization, which is controlled by the PLC automatic interlocking device established between the level gauges set in the crystallization kettles at all levels, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle.
- Step-by-step automatic material transfer is completed between the crystallization kettles connected in series between the first and the fourth stages, the stirring rate is controlled at 140 revolutions/min and the natural temperature gradient of 5-20 °C/level, and the continuous crystallization is carried out step by step; among them, the crystallization of 1 to 4 levels
- the injection time of the solid-liquid mixture in the kettle from the lowest liquid level to the highest liquid level is 2.2 hours, 2.2 hours, 2.2 hours and 2.8 hours respectively; the temperature of the mixture materials in the 1-4 crystallization kettle after natural cooling reaches: 64°C, 59°C, 47°C and 35°C, pass circulating cooling water into the interlayer of the last stage, the fourth stage crystallization kettle, and cool down to 20 ⁇ 2°C, then stir slowly for 2 hours to make the system fully crystallize.
- the mixture is centrifuged and dried. Separately obtain amino trimethylene phosphonic acid white transparent regular crystal product and centrifugal mother liquor; the centrifugal mother liquor is recycled to the concentration tank and reused for continuous crystallization, and the mixed centrifugal mother liquor is recycled until the color is 125Hazen.
- Amino trimethylene phosphonic acid crystal product with a content of 97.49% totals 7065.27 kg, chloride ion content (as Cl-) is 0.52%, product yield is 90.83%, and the mother liquor obtained after separation is 1950.89 kg, and the active content of amino trimethylene phosphonic acid It was 31.52%, and the total yield was 98.94%. There is no explosion phenomenon, the particle size is appropriate, and it is convenient for later centrifugation.
- the aminotriylene phosphonic acid liquid with an active content of 50.92% is preheated to 75°C by a graphite heater, and the hydrogen chloride, formaldehyde gas and a small amount of water vapor in the system are removed by gas-liquid separation. Then, it is continuously fed at a flow rate of 220kg/h.
- Distillation kettle when the material volume is about one-third of the volume of the kettle body, open the distillation kettle and stir, maintain the system temperature at 120 ⁇ 1°C, and quickly distill and concentrate under negative pressure of -0.04MPa; continuous feeding After 4.5 hours, the active content of the materials in the distillation kettle was 70.28% and the volume of the materials in the distillation kettle reached the set transfer level, the valve at the bottom of the distillation kettle and the transfer pump were automatically opened, and the material cooled to 60°C by the heat exchanger was pressed as 250kg/ The flow rate of h is continuously transferred to the first-stage crystallization kettle for crystallization, which is controlled by the PLC automatic interlocking device established between the level gauges set in the crystallization kettles at all levels, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle.
- Step-by-step automatic material transfer is completed between the crystallization kettles connected in series between the first and third stages, the stirring rate is controlled at 120 revolutions/min and the natural temperature gradient of 9-10 °C/level, and continuous crystallization is carried out step by step; among them, the crystallization of 1 to 3 levels
- the injection time of the solid-liquid mixture in the kettle from the lowest liquid level to the highest liquid level is 3 hours, 3 hours and 3.5 hours respectively; the temperature of the mixture material in the 1-3 crystallization kettle after natural cooling is reached: 54°C, 47°C and At 35°C, pass circulating cooling water into the interlayer of the last stage, that is, the third stage crystallization kettle to cool down to 20 ⁇ 2°C, then slowly stir for 2 hours to make the system fully crystallize.
- the mixture is separated by centrifugation and drying to obtain aminotrimethylene.
- White and transparent regular crystal products of phosphonic acid and centrifugal mother liquor the centrifugal mother liquor is recycled to the concentration tank and used for continuous crystallization, and the mixed centrifugal mother liquor is recycled to the color of 130Hazen.
- the active content is 97.72% amino
- the total amount of trimethylene phosphonic acid crystal products is 6138.21kg
- the chloride ion content (calculated as Cl-) is 0.60%
- the product yield is 89.84%
- the mother liquor obtained from separation is 1290.05kg
- the active content of amino trimethylene phosphonic acid is 38.37%.
- the rate is 99.35%.
- the particle size is appropriate, and it is convenient for later centrifugation.
- Comparative example 1 (traditional single-pot concentration crystallization method)
- Example 2 Other operating conditions and process parameters are the same as in Example 2.
- the amino trimethylene phosphonic acid liquid with an activity of 72.04% after distillation and concentration and a temperature of 120 ⁇ 2°C is directly transferred to the first step at a flow rate of 160kg/h without cooling down.
- the crystallization of the first-level crystallization kettle is controlled by the PLC automatic interlocking device established between the level gauges set in the crystallization kettles at all levels, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle. Step by step automatic material transfer is completed between the crystallization kettles, the stirring rate is controlled at 140 revolutions/min and the natural cooling gradient of 10 ⁇ 15°C/level, and continuous crystallization is carried out.
- crystal explosion occurs in the 1 ⁇ 2 crystallization kettle.
- the temperature of the mixture after the natural cooling of the 1st to 4th stage is 106°C, 94°C, 81°C and 70°C respectively.
- the 4th stage crystallization kettle interlayer circulating cooling water is introduced to cool it down to 20°C. Stir slowly for 2 hours to fully crystallize the system.
- the mixture is centrifuged and dried to obtain the amino trimethylene phosphonic acid crystal product and the centrifugal mother liquor, respectively.
- the amino trimethylene phosphonic acid white crystal product with an active content of 91.47% is produced, a total of 952.83. kg, the chloride ion content ( calculated as Cl - ) is 0.53%, the one-time crystallization yield is 80.44%; the separated mother liquor totals 543.84 kg, and the active content is 70.13%.
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Abstract
The present invention provides a continuous production method for an amino trimethylene phosphonic acid crystal. The specific operation method comprises: preheating an amino trimethylene phosphonic acid liquid product having an active content of 50 to 60%, performing a gas-liquid separation, and then continuously pumping same into a distillation tank at a constant speed; when the active content of the material being greater than or equal to 70% after performing distillation and concentration, subjecting the high-temperature material to condensation, and then sequentially completing stage-by-stage automatic feeding between 1 to n stage crystallization tanks connected in head and tail series, and performing stage-by-stage continuous crystallization under conditions of stirring and natural cooling; finally, in the n-stage crystallization tank, cooling the temperature by circulating condensation, and maintaining at a system temperature of 20°C; after sufficient crystallization, separating and drying same so as to obtain the amino trimethylene phosphonic acid crystal product having an active content of greater than or equal to 95%; and collecting and recycling the mother liquor obtained by separation. In the present invention, the closed single-tank crystallization in the traditional method is changed to an assembly line crystallization which is more suitable for industrialization, the final product has a suitable particle size and stable quality, none of the three wastes are generated, and no crystal promoter and crystal nucleus are introduced.
Description
本发明属于精细化学品生产技术领域，具体涉及一种氨基三亚甲基膦酸晶体的连续化生产方法。The invention belongs to the technical field of fine chemical production, and specifically relates to a continuous production method of amino trimethylene phosphonic acid crystals.
氨基三亚甲基膦酸(简称ATMP)为阴极型缓蚀剂，在水中能够解离形成6个正离子和含6个负电荷的离子，可以与水中的Ca
2+、Mg
2+形成多元环螯合物，这个大分子螯合物以松散的方式分散于水中，使钙镁垢的正常结晶遭到破坏，所以ATMP对水中硫酸钙、硅酸钙、碳酸钙和硅酸镁等也具有较好的阻垢作用，是一种有机膦酸型水质稳定剂。与无机聚合磷酸盐相比，缓蚀率强4-7倍；同时，ATMP为非当量的螯合剂，具有良好的溶限效应，可以由一个分子阻止几十个或几百个钙、镁离子与硫酸根离子等产生水垢沉淀，ATMP与其他聚羧酸类水垢抑制剂具有协同增效作用，表现出良好的配伍性能，因此被广泛应用于循环冷却水，油田注水和含水输油管线，印染用水的防垢，以及锅炉系统软垢的调节剂，纯度较高的ATMP产品还可以用于电镀行业，金属表面处理，过氧化氢稳定和金属离子掩蔽等方面。
Amino trimethylene phosphonic acid (referred to as ATMP) is a cathodic corrosion inhibitor, which can dissociate in water to form 6 positive ions and 6 negatively charged ions, which can form a polycyclic ring with Ca 2+ and Mg 2+ in water Chelate. This macromolecular chelate is loosely dispersed in water, which destroys the normal crystallization of calcium and magnesium scale. Therefore, ATMP also has a better effect on calcium sulfate, calcium silicate, calcium carbonate and magnesium silicate in water. Good scale inhibitor, is an organic phosphonic acid water quality stabilizer. Compared with inorganic polymer phosphate, the corrosion inhibition rate is 4-7 times stronger; at the same time, ATMP is a non-equivalent chelating agent with good solubility limit effect, which can prevent dozens or hundreds of calcium and magnesium ions by one molecule Produces scale precipitation with sulfate ions, etc. ATMP has synergistic effect with other polycarboxylic acid scale inhibitors and shows good compatibility. Therefore, it is widely used in circulating cooling water, oil field water injection and water-containing oil pipelines, printing and dyeing water The high-purity ATMP products can also be used in the electroplating industry, metal surface treatment, hydrogen peroxide stabilization and metal ion masking.
制备纯度高的ATMP，工业上实际生产时，一般采用控制原材料控制杂质含量或进行固体制备的方法提纯，但是由于原料三氯化磷的原始物质磷矿的伴生元素较多，低杂质含量的原料价格昂贵，制得产品成本较高。因此，实际生产时多采用制备固体的方法进行纯度较高的ATMP产品。CN101597305B的专利公开了一种高纯度的固体氨基三亚甲基膦酸或羟基亚乙基二膦酸的制备工艺，该工艺将有效物质含量68～85％的氨基三亚甲基膦酸或羟基亚乙基二膦酸液体温度控制在30～90℃，然后向液体体系中加入冰晶微粒析出晶体，经离心脱水、60～120℃烘干得相应的固体产品。CN103509052B公开了一种从合成液体产品开始，经浓缩、离心制备高纯度氨基三亚甲基膦酸的方法；CN101143752A通过在反应釜中投加晶核乙酸钠、经搅拌、投加助晶剂无水乙醇、脱水等处理工艺制得含量≥90％的氨基三亚甲基膦酸盐及其 制取工艺。本发明人在CN100471860C中公开了一种适用于电子级固体氨基三亚甲基膦酸的制备工艺。To prepare high-purity ATMP, in actual industrial production, the method of controlling the impurity content of raw materials or solid preparation is generally used to purify, but because the raw material of phosphorus trichloride has more associated elements in phosphate rock, raw materials with low impurity content The price is high, and the cost of the prepared product is high. Therefore, in actual production, the method of preparing solids is often used to produce ATMP products with higher purity. The patent of CN101597305B discloses a process for preparing high-purity solid amino trimethylene phosphonic acid or hydroxyethylene diphosphonic acid. The process combines amino trimethylene phosphonic acid or hydroxyethylene diphosphonic acid with an effective substance content of 68-85%. The liquid temperature of the diphosphonic acid is controlled at 30-90°C, then ice crystal particles are added to the liquid system to precipitate crystals, and the corresponding solid products are obtained by centrifugal dehydration and drying at 60-120°C. CN103509052B discloses a method for preparing high-purity amino trimethylene phosphonic acid by concentrating and centrifuging from the synthesis of liquid products; CN101143752A adds crystal nucleus sodium acetate in a reaction kettle, stirs, and adds anhydrous crystallization aid Amino trimethylene phosphonate with a content of ≥90% is prepared by treatment processes such as ethanol and dehydration and the preparation process thereof. The inventor disclosed a preparation process suitable for electronic grade solid amino trimethylene phosphonic acid in CN100471860C.
现有已公开的关于氨基三亚甲基膦酸固体或晶体的制备方法均采用传统的间歇性单釜式操作，不利于各批次间产品质量的稳定；同时，由于结晶过程是多因素影响的缓慢的物理过程，设备占用周期长，大大限制了此类产品的产能规模，严重影响了产品的市场应用和推广。The existing published preparation methods of amino trimethylene phosphonic acid solids or crystals all adopt the traditional intermittent single-pot operation, which is not conducive to the stability of product quality between batches; at the same time, because the crystallization process is affected by multiple factors The slow physical process and the long period of equipment occupation greatly limit the production capacity of such products and seriously affect the market application and promotion of the products.
发明内容Summary of the invention
为解决现有技术中存在的问题和不足，本发明提供一种可连续生产氨基三亚甲基膦酸晶体的生产方法。该方法通过氨基三亚甲基膦酸的自然降温和结晶，采用多级结晶的方式，可有效稳定产品质量、提高设备利用率和产品产能、节水减排、无三废产生，安全环保，利于实现自动化控制和规模化工业生产。In order to solve the problems and deficiencies in the prior art, the present invention provides a production method capable of continuously producing amino trimethylene phosphonic acid crystals. The method adopts the natural cooling and crystallization of amino trimethylene phosphonic acid and adopts multi-stage crystallization, which can effectively stabilize product quality, improve equipment utilization and product production capacity, save water and reduce emissions, generate no three wastes, is safe and environmentally friendly, and is beneficial to realization Automatic control and large-scale industrial production.
本发明具体是通过如下技术方案实现的：The present invention is specifically realized through the following technical solutions:
一种氨基三亚甲基膦酸晶体的连续化生产方法，具体包括如下步骤：A continuous production method of amino trimethylene phosphonic acid crystals specifically includes the following steps:
(1)将活性含量为50～60％的氨基三亚甲基膦酸液体经预热、气液分离后匀速连续打入蒸馏釜；(1) The amino trimethylene phosphonic acid liquid with an active content of 50-60% is preheated, gas-liquid separated, and then continuously pumped into the still at a constant speed;
(2)待蒸馏釜内物料达到釜体容积的三分之一时，开启搅拌并迅速提温，体系建立-0.03～-0.07MPa的负压条件连续进行浓缩提纯；(2) When the material in the distillation kettle reaches one-third of the volume of the kettle body, turn on the stirring and quickly raise the temperature, and the system establishes a negative pressure condition of -0.03～-0.07MPa for continuous concentration and purification;
(3)当浓缩釜内物料体积大于等于釜体容积的四分之三、物料活性含量≥70％时，高温物料经冷却后依次在1～n级首尾串联的结晶釜之间完成逐级自动转料，搅拌和自然降温的条件下，进行逐级连续结晶；(3) When the volume of the material in the thickening kettle is greater than or equal to three-quarters of the volume of the kettle body, and the active content of the material is ≥70%, the high-temperature material will be cooled and automatically completed step by step between the first and last crystallization kettles connected in series. Under the conditions of material transfer, stirring and natural cooling, continuous crystallization is carried out step by step;
(4)混合物料在第n级结晶釜内再次经循环冷凝降温并维持体系温度在20±2℃，使体系充分析晶后，混合物料经离心、干燥，得活性含量≥93％的氨基三亚甲基膦酸晶体产品，分离所得母液经收集循环利用。(4) The mixture material is cooled in the nth-stage crystallization kettle again through cyclic condensation and the temperature of the system is maintained at 20±2℃. After the system is filled with analytical crystals, the mixture material is centrifuged and dried to obtain amino Sanya with an active content of ≥93% Methylphosphonic acid crystal product, the mother liquor obtained from separation is collected and recycled.
上述步骤(1)中所述的预热后液体温度范围为60～100℃，作为优选地，预热后温度为75～90℃。The temperature of the liquid after preheating in the above step (1) ranges from 60 to 100°C. Preferably, the temperature after preheating is from 75 to 90°C.
上述步骤(2)中所述的浓缩温度可以为90～130℃，作为优选地，浓缩温度100～120℃。The concentration temperature in the above step (2) can be 90-130°C, preferably, the concentration temperature is 100-120°C.
上述步骤(1)和(2)中所述的预热分离和浓缩提纯是指物料经气液分离器分离除去产品中夹带的低沸点氯化氢、甲醛气体及体系中的部分水分，高沸点物质经气液分离器底部连续进入蒸馏浓缩釜。The preheating separation, concentration and purification described in the above steps (1) and (2) means that the materials are separated and removed by the gas-liquid separator to remove the low-boiling hydrogen chloride, formaldehyde gas and part of the water in the system. The high-boiling substances are The bottom of the gas-liquid separator continuously enters the distillation concentrator.
上述步骤(1)和步骤(2)所述的分离和提纯所得较低沸点组分经冷却回收后可循环用于生产液体产品的原料。The lower boiling point components obtained from the separation and purification described in the above step (1) and step (2) can be recycled and used as the raw material for the production of liquid products after being cooled and recovered.
上述步骤(3)中所述的冷凝后物料温度为60～70℃。The temperature of the condensed material in the above step (3) is 60-70°C.
上述步骤(3)中所述的混合物料通过1～n级结晶釜设置的液位计与釜顶进料阀门、釜底出料阀门之间的建立的PLC自动联锁装置实现自动转料。The mixture material described in the above step (3) realizes automatic material transfer through the PLC automatic interlocking device established between the level gauge set in the 1-n-level crystallization kettle, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle.
上述步骤(3)中所述的首尾串联的结晶釜数3≤n≤6，作为优选地，n＝4～5。The number of crystallization tanks connected in series in the above step (3) is 3≤n≤6, preferably n=4-5.
上述步骤(3)中所述的1～n级结晶釜内自然降温的梯度范围为5～20℃/级，作为优选地，1-21～n级结晶釜内自然降温的梯度范围为5～10℃/级，3～n级结晶釜内自然降温的梯度范围为10～20℃/级。In the above step (3), the gradient range of the natural cooling in the 1-n-level crystallization kettle is 5-20°C/level. Preferably, the gradient range of the natural cooling in the 1-21-n-level crystallization kettle is 5～ 10℃/level, the gradient range of the natural cooling in the 3-n-level crystallization kettle is 10-20℃/level.
第1级结晶釜搅拌速度50-150转/min，搅拌速度逐级降低。The stirring speed of the first stage crystallization kettle is 50-150 revolutions/min, and the stirring speed is gradually reduced.
上述步骤(4)中所述的母液连续打入蒸馏浓缩装置进行浓缩后循环用于逐级重结晶，当母液连续循环使用至色度≥120Hazen时，母液可作为液体商品直接销售或用作复合型含磷阻垢缓蚀剂单体。The mother liquor described in the above step (4) is continuously pumped into the distillation and concentration device to be concentrated and then recycled for successive recrystallization. When the mother liquor is continuously recycled until the chroma ≥ 120 Hazen, the mother liquor can be directly sold as a liquid product or used as a compound Phosphorus-containing scale and corrosion inhibitor monomer.
本发明的有益作用为：The beneficial effects of the present invention are:
(1)本发明通过对各级串联结晶釜的环境参数的控制，实现了羟基亚乙基二膦酸晶体的工业化流水线连续结晶和母液连续循环利用，提高了生产效率、产品质量稳定；(1) The present invention realizes the continuous crystallization of hydroxyethylene diphosphonic acid crystals and the continuous recycling of mother liquor through the control of the environmental parameters of the crystallization kettles connected in series at various levels, thereby improving production efficiency and stable product quality;
(2)该方法利用重力沉降作用分别对预热后和蒸馏提浓阶段的液体产品进行分离提纯，去除了产品中含有的氯化氢、醋酸等相对低沸点杂质及多余的水分，有效实现了物料的快速分离提纯，缩短生产周期；(2) This method uses gravity sedimentation to separate and purify the liquid products after preheating and distillation and concentration stages, and remove relatively low boiling impurities such as hydrogen chloride, acetic acid and excess water contained in the product, and effectively realize the material recovery. Fast separation and purification, shorten the production cycle;
(3)多级连续结晶过程中实现了5～20℃/级的降温梯度，并采用最后一级冷却降温，实现充分结晶，产品收率可达90％以上；(3) In the multi-stage continuous crystallization process, a temperature drop of 5-20°C/level is achieved, and the final stage of cooling is used to achieve full crystallization, and the product yield can reach more than 90%;
(4)多级连续结晶过程中不使用晶核和促晶剂，不引入新的杂质，最终的产品纯度高；(4) No crystal nucleus and crystal promoting agent are used in the multi-stage continuous crystallization process, no new impurities are introduced, and the final product has high purity;
(5)在母液循环利用的过程利于实现体系物料之间的热交换，有助于结晶体系温度的降低；(5) The process of recycling the mother liquor helps to realize the heat exchange between the system materials and helps to reduce the temperature of the crystallization system;
(6)该方法生产过程无“三废”产生，安全环保、节水减排，利于实现自动化规模生产。(6) This method produces no "three wastes" in the production process, is safe and environmentally friendly, saves water and reduces emissions, and is conducive to the realization of automated mass production.
为了更进一步的说明本发明的意义，下面结合实施例对本发明所涉及的内容进行阐释，但并不对其内容进行限定。In order to further illustrate the significance of the present invention, the content involved in the present invention will be explained below in conjunction with embodiments, but the content is not limited.
实施例1Example 1
将活性含量为55.63％的氨基三亚基叉膦酸液体分别经石墨加热器预热至85℃、气液分离除去体系中氯化氢、甲醛气和少量水蒸气后按照270kg/h的流速匀速连续打入蒸馏釜；连续进料1小时至物料体积约占釜体三分之一容积时，开启蒸馏釜搅拌，维持体系温度115±1℃，-0.05MPa负压条件下迅速外蒸浓缩；连续进料4小时后，蒸馏釜中物料活性含量为71.04％且蒸馏釜内物料体积达到设置转料液位，蒸馏釜底部阀门和转料泵自动开启将经换热器冷却至60℃的物料按320kg/h的流量连续转入第一级结晶釜进行结晶，通过各级结晶釜设置的液位计与釜顶进料阀门、釜底出料阀门之间的建立的PLC自动联锁装置控制，依次在1～5级首尾串联的结晶釜之间完成逐级自动转料、控制搅拌速率为80转/min和5～20℃/级的自然降温梯度，进行逐级连续结晶；其中1～4级结晶釜内固液混合物料从最低液位到最高液位注入时间分别为2小时、2小时、2小时、2小时和3.2小时；1～5级结晶釜内通过自然降温后混合物料温度分别达到54℃、50℃、40℃、30℃、20℃，在最后一级即第5级结晶釜夹层内通入循 环冷却水降温至20±2℃后，缓慢搅拌2小时，使体系充分结晶，混合物料经离心、干燥分离分别得氨基三亚甲基膦酸白色透明状规则晶体产品和离心母液；离心母液循环至浓缩釜重复用于连续结晶，以混合离心母液循环利用至色度为125Hazen计一个生产周期，产出活性含量为96.44％的氨基三亚甲基膦酸晶体产品共计9721.76kg，氯离子含量(以Cl-计)0.47％，产品收率为92.06％，分离所得母液共计2341.65kg，氨基三甲叉膦酸活性含量为30.27％，合计收率为99.02％。无爆析现象，粒度大小合适，方便后期离心。The aminotriylene phosphonic acid liquid with an active content of 55.63% was preheated to 85°C by a graphite heater, and hydrogen chloride, formaldehyde gas and a small amount of water vapor in the system were removed by gas-liquid separation. Then, it was continuously fed at a flow rate of 270kg/h. Distillation kettle; when the material is continuously fed for 1 hour until the volume of the material is about one-third of the volume of the kettle body, turn on the distillation kettle and stir, maintain the system temperature at 115±1℃, and quickly distill and concentrate under the negative pressure of -0.05MPa; continuous feeding After 4 hours, the active content of the materials in the distillation kettle was 71.04% and the volume of the materials in the distillation kettle reached the set transfer level. The valve at the bottom of the distillation kettle and the transfer pump were automatically turned on, and the material cooled to 60°C by the heat exchanger was calculated as 320kg/ The flow rate of h is continuously transferred to the first-stage crystallization kettle for crystallization, which is controlled by the PLC automatic interlocking device established between the level gauges set in the crystallization kettles at all levels, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle. Step-by-step automatic material transfer is completed between the crystallization kettles connected in series between the first and the fifth stages, the stirring rate is controlled at 80 revolutions/min and the natural temperature gradient of 5-20 ℃/level, and the continuous crystallization is carried out step by step; among them, the crystallization of 1 to 4 levels The injection time of the solid-liquid mixture in the kettle from the lowest level to the highest level is 2 hours, 2 hours, 2 hours, 2 hours and 3.2 hours respectively; the temperature of the mixture materials in the 1-5 crystallization kettle after natural cooling reaches 54 ℃, 50℃, 40℃, 30℃, 20℃, pass circulating cooling water into the interlayer of the crystallization kettle at the last stage, the fifth stage, after cooling to 20±2℃, stir slowly for 2 hours to make the system fully crystallize, the mixture After centrifugation, drying and separation, the amino trimethylene phosphonic acid white and transparent regular crystal product and centrifugal mother liquor are obtained; the centrifugal mother liquor is recycled to the concentration tank and used for continuous crystallization, and the mixed centrifugal mother liquor is recycled until the color is 125Hazen. During the cycle, it produced a total of 9721.76 kg of amino trimethylene phosphonic acid crystal products with an active content of 96.44%, a chloride ion content (calculated as Cl-) of 0.47%, a product yield of 92.06%, and a total of 2341.65 kg of mother liquor obtained after separation. The active content of phosphonic acid was 30.27%, and the total yield was 99.02%. There is no explosion phenomenon, the particle size is appropriate, and it is convenient for later centrifugation.
实施例2Example 2
将活性含量为59.47％的氨基三亚基叉膦酸液体分别经石墨加热器预热至90℃、气液分离除去体系中氯化氢、甲醛气和少量水蒸气后按照255kg/h的流速匀速连续打入蒸馏釜；连续进料1小时至物料体积约占釜体三分之一容积时，开启蒸馏釜搅拌，维持体系温度108±1℃，-0.06MPa负压条件下迅速外蒸浓缩；连续进料4.2小时后，蒸馏釜中物料活性含量为72.03％且蒸馏釜内物料体积达到设置转料液位，蒸馏釜底部阀门和转料泵自动开启将经换热器冷却至70℃的物料按280kg/h的流量连续转入第一级结晶釜进行结晶，通过各级结晶釜设置的液位计与釜顶进料阀门、釜底出料阀门之间的建立的PLC自动联锁装置控制，依次在1～4级首尾串联的结晶釜之间完成逐级自动转料、控制搅拌速率为140转/min和5～20℃/级的自然降温梯度，进行逐级连续结晶；其中1～4级结晶釜内固液混合物料从最低液位到最高液位注入时间分别为2.2小时、2.2时、2.2小时和2.8小时；1～4级结晶釜内通过自然降温后混合物料温度分别达到：64℃、59℃、47℃和35℃，在最后一级即第4级结晶釜夹层内通入循环冷却水降温至20±2℃后，缓慢搅拌2小时，使体系充分结晶，混合物料经离心、干燥分离分别得氨基三亚甲基膦酸白色透明状规则晶体产品和离心母液；离心母液循环至浓缩釜重复用于连续结晶，以混合离心母液循环利用至色度为125Hazen计一个生产周期，产出活性含量为97.49％的氨基三亚甲基膦酸晶体产品共计7065.27kg，氯离子含量(以Cl-计)0.52％，产品收率为90.83％，分离所得母液共计1950.89kg，氨基三甲叉膦酸活性含量为31.52％，合计收 率为98.94％。无爆析现象，粒度大小合适，方便后期离心。The aminotriylene phosphonic acid liquid with an active content of 59.47% is preheated to 90℃ by a graphite heater, and hydrogen chloride, formaldehyde gas and a small amount of water vapor in the system are removed by gas-liquid separation. Then, it is continuously fed at a flow rate of 255kg/h. Distillation kettle; when the material is continuously fed for 1 hour until the volume of the material is about one-third of the volume of the kettle body, turn on the distillation kettle and stir, maintain the system temperature at 108±1℃, and quickly distill and concentrate under negative pressure of -0.06MPa; continuous feeding After 4.2 hours, the active content of the materials in the distillation kettle was 72.03% and the volume of the materials in the distillation kettle reached the set transfer level. The valve at the bottom of the distillation kettle and the transfer pump were automatically opened, and the material cooled to 70℃ by the heat exchanger was pressed at 280kg/ The flow rate of h is continuously transferred to the first-stage crystallization kettle for crystallization, which is controlled by the PLC automatic interlocking device established between the level gauges set in the crystallization kettles at all levels, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle. Step-by-step automatic material transfer is completed between the crystallization kettles connected in series between the first and the fourth stages, the stirring rate is controlled at 140 revolutions/min and the natural temperature gradient of 5-20 ℃/level, and the continuous crystallization is carried out step by step; among them, the crystallization of 1 to 4 levels The injection time of the solid-liquid mixture in the kettle from the lowest liquid level to the highest liquid level is 2.2 hours, 2.2 hours, 2.2 hours and 2.8 hours respectively; the temperature of the mixture materials in the 1-4 crystallization kettle after natural cooling reaches: 64℃, 59°C, 47°C and 35°C, pass circulating cooling water into the interlayer of the last stage, the fourth stage crystallization kettle, and cool down to 20±2°C, then stir slowly for 2 hours to make the system fully crystallize. The mixture is centrifuged and dried. Separately obtain amino trimethylene phosphonic acid white transparent regular crystal product and centrifugal mother liquor; the centrifugal mother liquor is recycled to the concentration tank and reused for continuous crystallization, and the mixed centrifugal mother liquor is recycled until the color is 125Hazen. Amino trimethylene phosphonic acid crystal product with a content of 97.49% totals 7065.27 kg, chloride ion content (as Cl-) is 0.52%, product yield is 90.83%, and the mother liquor obtained after separation is 1950.89 kg, and the active content of amino trimethylene phosphonic acid It was 31.52%, and the total yield was 98.94%. There is no explosion phenomenon, the particle size is appropriate, and it is convenient for later centrifugation.
实施例3Example 3
将活性含量为50.92％的氨基三亚基叉膦酸液体分别经石墨加热器预热至75℃、气液分离除去体系中氯化氢、甲醛气和少量水蒸气后按照220kg/h的流速匀速连续打入蒸馏釜；连续进料1.5小时至物料体积约占釜体三分之一容积时，开启蒸馏釜搅拌，维持体系温度120±1℃，-0.04MPa负压条件下迅速外蒸浓缩；连续进料4.5小时后，蒸馏釜中物料活性含量为70.28％且蒸馏釜内物料体积达到设置转料液位，蒸馏釜底部阀门和转料泵自动开启将经换热器冷却至60℃的物料按250kg/h的流量连续转入第一级结晶釜进行结晶，通过各级结晶釜设置的液位计与釜顶进料阀门、釜底出料阀门之间的建立的PLC自动联锁装置控制，依次在1～3级首尾串联的结晶釜之间完成逐级自动转料、控制搅拌速率为120转/min和9～10℃/级的自然降温梯度，进行逐级连续结晶；其中1～3级结晶釜内固液混合物料从最低液位到最高液位注入时间分别为3小时、3小时和3.5小时；1～3级结晶釜内通过自然降温后混合物料温度分别达到：54℃、47℃和35℃，在最后一级即第3级结晶釜夹层内通入循环冷却水降温至20±2℃后，缓慢搅拌2小时，使体系充分结晶，混合物料经离心、干燥分离分别得氨基三亚甲基膦酸白色透明状规则晶体产品和离心母液；离心母液循环至浓缩釜重复用于连续结晶，以混合离心母液循环利用至色度为130Hazen计一个生产周期，产出活性含量为97.72％的氨基三亚甲基膦酸晶体产品共计6138.21kg，氯离子含量(以Cl-计)0.60％，产品收率为89.84％，分离所得母液共计1290.05kg，氨基三甲叉膦酸活性含量为38.37％，合计收率为99.35％。无爆析现象，粒度大小合适，方便后期离心。The aminotriylene phosphonic acid liquid with an active content of 50.92% is preheated to 75°C by a graphite heater, and the hydrogen chloride, formaldehyde gas and a small amount of water vapor in the system are removed by gas-liquid separation. Then, it is continuously fed at a flow rate of 220kg/h. Distillation kettle; when the material volume is about one-third of the volume of the kettle body, open the distillation kettle and stir, maintain the system temperature at 120±1℃, and quickly distill and concentrate under negative pressure of -0.04MPa; continuous feeding After 4.5 hours, the active content of the materials in the distillation kettle was 70.28% and the volume of the materials in the distillation kettle reached the set transfer level, the valve at the bottom of the distillation kettle and the transfer pump were automatically opened, and the material cooled to 60°C by the heat exchanger was pressed as 250kg/ The flow rate of h is continuously transferred to the first-stage crystallization kettle for crystallization, which is controlled by the PLC automatic interlocking device established between the level gauges set in the crystallization kettles at all levels, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle. Step-by-step automatic material transfer is completed between the crystallization kettles connected in series between the first and third stages, the stirring rate is controlled at 120 revolutions/min and the natural temperature gradient of 9-10 ℃/level, and continuous crystallization is carried out step by step; among them, the crystallization of 1 to 3 levels The injection time of the solid-liquid mixture in the kettle from the lowest liquid level to the highest liquid level is 3 hours, 3 hours and 3.5 hours respectively; the temperature of the mixture material in the 1-3 crystallization kettle after natural cooling is reached: 54°C, 47°C and At 35℃, pass circulating cooling water into the interlayer of the last stage, that is, the third stage crystallization kettle to cool down to 20±2℃, then slowly stir for 2 hours to make the system fully crystallize. The mixture is separated by centrifugation and drying to obtain aminotrimethylene. White and transparent regular crystal products of phosphonic acid and centrifugal mother liquor; the centrifugal mother liquor is recycled to the concentration tank and used for continuous crystallization, and the mixed centrifugal mother liquor is recycled to the color of 130Hazen. One production cycle, the active content is 97.72% amino The total amount of trimethylene phosphonic acid crystal products is 6138.21kg, the chloride ion content (calculated as Cl-) is 0.60%, the product yield is 89.84%, the mother liquor obtained from separation is 1290.05kg, and the active content of amino trimethylene phosphonic acid is 38.37%. The rate is 99.35%. There is no explosion phenomenon, the particle size is appropriate, and it is convenient for later centrifugation.
对比例1(传统的单釜式浓缩结晶方法)Comparative example 1 (traditional single-pot concentration crystallization method)
将活性含量为59.47％的氨基三亚甲基膦酸液体2000kg抽入反应釜内，搅拌条件下迅速升温至130℃，体系同时建立-0.04MPa负压迅速外蒸浓缩至活性含量为76.21％，控制搅拌速率为120转/min并加入晶种，通入循环水冷却，按照8～10℃/h的梯度降温至20±2℃，静置陈化 1～2小时后经离心、干燥得活性含量为97.87％的氨基三亚甲基膦酸晶体765.39kg，一次性结晶收率为62.98％，离心母液重复上述操作步骤循环重结晶三次，合计收率为85.32％，氯离子含量(以Cl-计)为0.91％。Pump 2000 kg of amino trimethylene phosphonic acid liquid with an active content of 59.47% into the reaction kettle, and rapidly increase the temperature to 130°C under stirring conditions. At the same time, the system establishes -0.04MPa negative pressure and quickly externally vaporizes and concentrates to an active content of 76.21%. The stirring rate is 120 revolutions/min and seed crystals are added, and circulating water is introduced for cooling. The temperature is lowered to 20±2°C according to a gradient of 8-10°C/h. After standing for 1 to 2 hours, the active content is obtained by centrifugation and drying. 97.87% of the amino trimethylene phosphonic acid crystals are 765.39 kg, the one-time crystallization yield is 62.98%, the centrifugal mother liquor repeats the above operation steps and recrystallizes three times, the total yield is 85.32%, and the chloride ion content (calculated as Cl-) It is 0.91%.
对比例2Comparative example 2
其他操作条件及工艺参数同实施例2，将蒸馏浓缩后的活性为72.04％、温度为120±2℃的氨基三亚甲基膦酸液体按照160kg/h的流量不经过冷却降温直接连续转入第一级结晶釜进行结晶，通过各级结晶釜设置的液位计与釜顶进料阀门、釜底出料阀门之间的建立的PLC自动联锁装置控制，依次在1～4级首尾串联的结晶釜之间完成逐级自动转料、控制搅拌速率为140转/min和10～15℃/级的自然降温梯度，进行逐级连续结晶；其中在1～2级结晶釜内出现晶体暴析的现象，1～4级自然降温后混合物料温度分别为：106℃、94℃、81℃和70℃，在最后一级即第4级结晶釜夹层内通入循环冷却水降温至20℃，缓慢搅拌2小时，使体系充分结晶，混合物料经离心、干燥分离分别得氨基三亚甲基膦酸晶体产品和离心母液，产出活性含量为91.47％的氨基三亚甲基膦酸白色晶体产品共计952.83kg，氯离子含量(以Cl
-计)0.53％，一次性结晶收率为80.44％；分离所得母液共计543.84kg，活性含量为70.13％。
Other operating conditions and process parameters are the same as in Example 2. The amino trimethylene phosphonic acid liquid with an activity of 72.04% after distillation and concentration and a temperature of 120±2°C is directly transferred to the first step at a flow rate of 160kg/h without cooling down. The crystallization of the first-level crystallization kettle is controlled by the PLC automatic interlocking device established between the level gauges set in the crystallization kettles at all levels, the feed valve at the top of the kettle, and the discharge valve at the bottom of the kettle. Step by step automatic material transfer is completed between the crystallization kettles, the stirring rate is controlled at 140 revolutions/min and the natural cooling gradient of 10～15℃/level, and continuous crystallization is carried out. Among them, crystal explosion occurs in the 1～2 crystallization kettle. The temperature of the mixture after the natural cooling of the 1st to 4th stage is 106℃, 94℃, 81℃ and 70℃ respectively. In the last stage, the 4th stage crystallization kettle interlayer, circulating cooling water is introduced to cool it down to 20℃. Stir slowly for 2 hours to fully crystallize the system. The mixture is centrifuged and dried to obtain the amino trimethylene phosphonic acid crystal product and the centrifugal mother liquor, respectively. The amino trimethylene phosphonic acid white crystal product with an active content of 91.47% is produced, a total of 952.83. kg, the chloride ion content ( calculated as Cl - ) is 0.53%, the one-time crystallization yield is 80.44%; the separated mother liquor totals 543.84 kg, and the active content is 70.13%.
对比例3Comparative example 3
控制1～3级结晶釜内搅拌速率均为200转/min，其他操作条件及工艺参数同实施例3，1～2级结晶釜内出现严重暴析现象，析出晶体颗粒小，晶体呈细粉状，得氨基三亚甲基膦酸晶体活性含量为93.39％，氯离子含量(以Cl-计)为0.47％，一次性结晶收率为81.73％。Control the stirring rate in the 1-3 crystallization kettle to be 200 revolutions/min, and other operating conditions and process parameters are the same as in Example 3. Serious explosion phenomenon occurs in the 1-2 crystallization kettle, and the precipitated crystal particles are small and the crystals are fine powder As a result, the active content of amino trimethylene phosphonic acid crystals is 93.39%, the chloride ion content (calculated as Cl-) is 0.47%, and the one-time crystal yield is 81.73%.
对比例4Comparative example 4
控制1～3级结晶釜内搅拌速率均为30转/min，其他操作条件及工艺参数同实施例3，1～2级结晶釜内均出现暴析现象，析出晶体得粒径大小不一且形状不规则，氨基三亚甲基膦酸晶体活性含量为92.70％，氯离子含量(以Cl
-计)为0.35％，一次性结晶收率为75.28％。
Control the stirring rate in the 1~3 crystallization kettle to be 30 revolutions/min. Other operating conditions and process parameters are the same as in Example 3. The explosion phenomenon occurs in the 1 to 2 crystallization kettle, and the crystals are separated and the particle size is different. The shape is irregular, the active content of amino trimethylene phosphonic acid crystals is 92.70%, the chloride ion content ( calculated as Cl - ) is 0.35%, and the one-time crystal yield is 75.28%.
Claims (8)
- 一种氨基三亚甲基膦酸晶体的连续化生产方法，其特征在于，具体包括如下步骤：A continuous production method of amino trimethylene phosphonic acid crystals is characterized in that it specifically includes the following steps:将活性含量为50～60％的氨基三亚甲基膦酸液体经预热、气液分离后匀速连续打入蒸馏釜；开启搅拌并提温，同时，负压下连续进行浓缩提纯；The amino trimethylene phosphonic acid liquid with an active content of 50-60% is preheated, gas-liquid separated, and then continuously pumped into the distillation kettle at a constant speed; stirring is turned on and the temperature is raised, and at the same time, continuous concentration and purification under negative pressure;(3)当浓缩釜内物料活性含量≥70％时，高温物料经冷却后依次在1-n级首尾串联的结晶釜之间完成逐级转料，搅拌和降温的条件下，进行连续结晶；(3) When the active content of the material in the concentration kettle is ≥70%, the high-temperature material is cooled down to complete the step-by-step transfer between the 1-n crystallization kettles in series, and the continuous crystallization is carried out under the conditions of stirring and cooling;(4)混合物料在第n级结晶釜内降温并维持体系温度在20±2℃，使体系充分析晶后，混合物料经分离、干燥处理，得活性含量≥95％的氨基三亚甲基膦酸产品，分离所得母液经收集循环利用。(4) The mixture material is cooled in the nth-stage crystallization kettle and the system temperature is maintained at 20±2℃. After the system is filled with analytical crystals, the mixture material is separated and dried to obtain aminotrimethylene phosphine with an active content of ≥95% Acid product, the mother liquor obtained from separation is collected and recycled.
- 根据权利要求1所述的方法，其特征在于，所述步骤(1)中预热后液体产品温度范围为60～100℃。The method according to claim 1, wherein the temperature of the liquid product after preheating in the step (1) ranges from 60 to 100°C.
- 根据权利要求1所述的方法，其特征在于，所述步骤(2)中外蒸浓缩温度为90～130℃。The method according to claim 1, characterized in that, in the step (2), the temperature of evaporation and concentration is 90-130°C.
- 根据权利要求1所述的方法，其特征在于，所述步骤(3)中经冷凝后物料温度为60～70℃。The method according to claim 1, wherein the temperature of the condensed material in the step (3) is 60-70°C.
- 根据权利要求1所述的方法，其特征在于，所述步骤(3)中首尾串联的结晶釜级数3≤n≤6。The method according to claim 1, characterized in that, in the step (3), the number of crystallization tank stages connected in series end to end is 3≤n≤6.
- 根据权利要求1所述的方法，其特征在于，所述步骤(3)中1～n级结晶釜梯度范围为5～20℃/级。The method according to claim 1, characterized in that, in the step (3), the gradient range of the 1-n-stage crystallization kettle is 5-20°C/level.
- 根据权利要求1所述的方法，其特征在于，所述的各级结晶釜中，1-2级结晶釜降温速度慢，3～n级结晶釜温度自然降温速度，第n级通过循环冷却至20±2℃；搅拌速度50-150转/min，搅拌速度逐级降低。The method according to claim 1, characterized in that, among the crystallization kettles at all levels, the temperature of the 1-2 crystallization kettles is slow, the temperature of the 3 to n crystallization kettles are naturally cooled, and the nth stage is cooled to 20±2℃; The stirring speed is 50-150 revolutions/min, and the stirring speed is gradually reduced.
- 根据权利要求1-7所述，其特征在于，所述步骤(1)和步骤(2)中分离和提纯所得较低沸点组分经冷却回收后可循环用于生产液体产品的原料；所述步骤(4)的母液连续打入蒸馏浓缩装置进行浓缩后循环用于逐级重结晶，当母液连续循环使用至色度≥120Hazen时，母液 可用作复合型含磷阻垢缓蚀剂单体。According to claims 1-7, characterized in that the lower boiling point components obtained from the separation and purification in the step (1) and step (2) can be recycled for the production of liquid products after being cooled and recovered; The mother liquor of step (4) is continuously injected into the distillation and concentration device to be concentrated and then recycled for step-by-step recrystallization. When the mother liquor is continuously recycled until the chroma is greater than or equal to 120 Hazen, the mother liquor can be used as a compound type phosphorus-containing scale and corrosion inhibitor monomer .
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| CN110642887B (en) * | 2019-10-17 | 2021-05-07 | 山东泰和水处理科技股份有限公司 | Continuous production method of hydroxyethylidene diphosphonic acid crystal |
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