WO2021088459A1 - Method for producing amino trimethylene phosphonic acid as water treatment agent - Google Patents

Method for producing amino trimethylene phosphonic acid as water treatment agent Download PDF

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WO2021088459A1
WO2021088459A1 PCT/CN2020/109683 CN2020109683W WO2021088459A1 WO 2021088459 A1 WO2021088459 A1 WO 2021088459A1 CN 2020109683 W CN2020109683 W CN 2020109683W WO 2021088459 A1 WO2021088459 A1 WO 2021088459A1
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reactor
kettle
hydrochloric acid
stage
atmp
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PCT/CN2020/109683
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French (fr)
Chinese (zh)
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程终发
刘全华
周响
宋盟盟
王宁宁
陈成效
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山东泰和水处理科技股份有限公司
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    • 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)]

Definitions

  • the invention belongs to the field of chemical engineering, and particularly relates to a method for producing water treatment agent amino trimethylene phosphonic acid.
  • Amino Trimethylene Phosphonic Acid as a water treatment agent is widely used in industrial circulating cooling water systems. It has good scale and corrosion inhibition effects, and has a good effect on inhibiting calcium carbonate, hydrated iron oxide and calcium phosphate. It has a synergistic effect when used in conjunction with other corrosion inhibitors and scale inhibitors.
  • the dosage is 1-20mg/L It can achieve good corrosion and scale inhibition effects when it is time. It is an important scale inhibitor and dispersant, which is widely used in the cooling water treatment of large-scale petrochemical, fertilizer and other production equipment.
  • ATMP has good chemical stability, is not easy to be damaged by acid and alkali, and is not easy to be hydrolyzed.
  • ATMP has three phosphoric acid groups, which have good complexing and liquid enhancement, solubility limit effect, lattice distortion and other properties, and prevent various inorganic salts in water from forming calcium barriers.
  • Organic phosphoric acid is a commonly used water treatment agent in industrial water treatment. It not only has a good chelating ability to many metal ions such as calcium and magnesium, but also is a cathode type corrosion inhibitor.
  • the present invention provides a continuous, green and environmentally friendly water treatment agent amino trimethylene phosphonic acid production method.
  • a production method of water treatment agent amino trimethylene phosphonic acid which specifically includes:
  • the device is: three-stage reactor overflows in series, the third-stage reactor overflows in series with the insulation kettle, the insulation pot is connected in series with the outer steaming kettle, and the condensed reflux of the three reactors, the insulation kettle and the outer steaming kettle are connected to the hydrochloric acid absorption tank.
  • the method is:
  • hydrochloric acid absorption liquid is passed through the hydrochloric acid multi-stage absorption device of the HEDP production line to generate 32% hydrochloric acid for recycling.
  • the series overflow described in step (1) is a gradient series overflow, and the material flows from the overflow port of the kettle to the next stage of the kettle, and the overflow port is provided with a one-way protection device to prevent back suction.
  • step (2) the amount ratio of ammonia water, hydrochloric acid, phosphorous acid and formaldehyde is 1:(1 ⁇ 2):(2 ⁇ 3):(3 ⁇ 4), preferably 1: 1.2:3.0:3.1.
  • the reactor capacity described in step (2) is the internal volume capacity of the reactor from the bottom of the reactor to the overflow port.
  • the time for filling the reactor with the materials described in step (2) is 70 ⁇ 5 min.
  • the certain flow rate described in step (2) is determined by the capacity of the reactor, the filling material time and the ratio of each material. Due to the time, the material ratio has been fixed, and the flow rate is adjusted according to the capacity of the reactor.
  • reaction kettle described in step (2) is continuously stirred at a certain temperature at a temperature of 95-125°C, preferably 110-120°C.
  • the heat preservation time of the heat preservation kettle described in step (3) is preferably 60 ⁇ 5 min.
  • the temperature range of the heat preservation kettle described in step (3) at a certain temperature is 105-120°C, preferably 110-120°C.
  • step (3) it is steamed to a certain concentration of 70-85%, preferably 75-80%.
  • the invention provides an efficient continuous production method.
  • This method realizes continuous feeding and discharging, high utilization rate of equipment and resources, short production cycle, few by-products, and stable quality.
  • This method has simple equipment requirements, simple reaction process, and high equipment utilization.
  • the method has a high primary conversion rate of raw materials, and does not need to separate products and raw materials from the discharged materials, saves working hours and costs, and saves energy and reduces consumption.
  • the hydrochloric acid used in this method can be regarded as a catalyst, can be reused after treatment, no three wastes are generated, and it is green and environmentally friendly.
  • the present invention can effectively promote the industrial scale development of amino trimethylene phosphonic acid.
  • the first-stage reactor is fed to the first-stage reactor at a constant rate at a flow rate of 517L/h of ammonia, 1041L/h of hydrochloric acid, and 2673L/h of phosphorous acid.
  • the time from the beginning of the addition of the materials in the reactor to the beginning of overflow is 70 minutes.
  • the temperature in the reactor is controlled at 118 ⁇ 2°C after 20 minutes of feeding, and the mass fractions of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde are 25%, 32%, 70%, and 40%, respectively.
  • the reactor After the reactor starts to overflow, continue to feed the raw materials at the above flow rate at a constant speed.
  • the materials in the reactor overflow gradually from the first-level reactor to the insulation kettle1.
  • the temperature is controlled to 118 ⁇ 2°C .
  • the material After receiving the material for 60 minutes, the material is transferred to the insulation kettle 2 through the valve control, and the insulation kettle 1 continues to be kept at a temperature of 118 ⁇ 2 °C for 60 minutes, and then transferred to the steaming kettle 1.
  • Insulation kettle 2 After receiving the reaction materials for 20 minutes, the temperature is also controlled at 118 ⁇ 2°C. After receiving the materials for 60 minutes, the materials are transferred to the holding kettle 1, the holding kettle 2 continues to be kept at 118 ⁇ 2°C for 60 minutes, then transfer Enter the steaming kettle 2, and operate in this way.
  • the content of hydrochloric acid is 15.12%, and the content of formaldehyde is 0.80%
  • ATMP active content 50.20%, chloride ( calculated as Cl - ) content 1.31%, iron ( calculated as Fe 2+ ) content 6.90mg/L, color (Hezen) 28.0, ATMP yield (calculated as raw material phosphorous acid) 97.84 %.
  • the first-stage reactor is fed to the first-stage reactor at a constant rate at a flow rate of 517L/h of ammonia, 1041L/h of hydrochloric acid, and 2673L/h of phosphorous acid.
  • the time from the beginning of the addition of the materials in the reactor to the beginning of overflow is about 70 minutes.
  • the temperature in the reactor is controlled at 112 ⁇ 2°C after 20 minutes of feeding, and the mass fractions of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde are 25%, 32%, 70%, and 40%, respectively.
  • the reactor After the reactor begins to overflow, continue to feed the raw materials at the above flow rate at a constant speed.
  • the materials in the reactor gradually overflow from the first-stage reactor to the insulation kettle1.
  • the temperature is controlled at 112 ⁇ 2°C.
  • the material After receiving the material for 60 minutes, the material is transferred to the heat preservation kettle 2 through the valve control, and the heat preservation kettle 1 continues to be kept at a temperature of 112 ⁇ 2 °C for 60 minutes, and then transferred to the steaming kettle 1.
  • Insulation kettle 2 After receiving the reaction materials for 20 minutes, the temperature is also controlled at 112 ⁇ 2°C. After receiving the materials for 60 minutes, the materials are transferred to the holding kettle 1, the holding kettle 2 continues to be kept at 112 ⁇ 2°C for 60 minutes, then transfer Enter the steaming kettle 2, and operate in this way.
  • the content of hydrochloric acid is 14.92%, and the content of formaldehyde is 0.85%
  • the active content of ATMP is 50.5%, the content of chloride (calculated as Cl - ) is 1.27%, the content of iron ( calculated as Fe 2+ ) is 6.65 mg/L, the color (Hezen) is 29.4, and the ATMP yield (calculated as the raw material phosphorous acid) is 96.81 %.
  • the first-stage reactor is fed to the first-stage reactor at a constant rate at a flow rate of 724L/h of ammonia, 1457L/h of hydrochloric acid and 3742L/h of phosphorous aqueous ammonia, hydrochloric acid and phosphorous acid, formaldehyde according to the flow reactor three 2475L / h into a constant speed ratio n formaldehyde, ammonia, hydrochloric acid, phosphorous acid, formaldehyde, ammonia water substance: n hydrochloric acid: phosphorous acid n: n formaldehyde 1:1.2:3.0:3.1.
  • the time from the beginning of adding the materials in the reactor to the beginning of overflow is about 50 minutes.
  • the temperature in the reactor is controlled at 118 ⁇ 2°C after 20 minutes of feeding, and the mass fractions of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde are 25%, 32%, 70%, and 40%, respectively.
  • the reactor After the reactor starts to overflow, continue to feed the raw materials at the above flow rate at a constant speed.
  • the materials in the reactor overflow gradually from the first-level reactor to the insulation kettle1.
  • the temperature is controlled to 118 ⁇ 2°C
  • the insulation kettle 1 After receiving the material for 40 minutes, the material is transferred to the insulation kettle 2 through the valve control, the insulation kettle 1 continues to be kept at a temperature of 118 ⁇ 2 °C for 40 minutes, and then transferred to the steaming kettle 1.
  • Insulation kettle 2 After receiving the reaction materials for 20 minutes, the temperature is also controlled at 118 ⁇ 2°C. After receiving the materials for 40 minutes, the materials are transferred to the holding kettle 1, the holding kettle 2 continues to be kept at 118 ⁇ 2°C for 40 minutes, then transfer Enter the steaming kettle 2, and operate in this way.
  • the content of hydrochloric acid is 15.10%, and the content of formaldehyde is 0.79%
  • the active content of ATMP is 50.20%, the content of chloride ( calculated as Cl - ) is 1.31%, the content of iron ( calculated as Fe 2+ ) is 6.90mg/L, the color (Hezen) is 28.0, and the ATMP yield (calculated as the raw material phosphorous acid) is 93.37 %.
  • the first-stage reactor is fed to the first-stage reactor at a constant rate at a flow rate of 402L/h of ammonia water, 810L/h of hydrochloric acid, and 2079L/h of phosphorous acid. Enter ammonia, hydrochloric acid and phosphorous acid.
  • the three-stage reactor is fed with formaldehyde at a constant rate of 1375L/h.
  • the ratio of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde is n ammonia : n hydrochloric acid : n phosphorous acid : n formaldehyde is 1. : 1.2:3.0:3.1.
  • the time from the beginning of the addition of the materials in the reactor to the beginning of overflow is 90 minutes.
  • the temperature in the reactor is controlled at 118 ⁇ 2°C after 20 minutes of feeding, and the mass fractions of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde are 25%, 32%, 70%, and 40%, respectively.
  • the reactor After the reactor starts to overflow, continue to feed the raw materials at the above flow rate at a constant speed.
  • the materials in the reactor overflow gradually from the first-level reactor to the insulation kettle1.
  • the temperature is controlled to 118 ⁇ 2°C
  • the insulation kettle 1 After receiving the material for 80 minutes, the material is transferred to the insulation kettle 2 through the valve control, the insulation kettle 1 continues to be kept at a temperature of 118 ⁇ 2 °C for 80 minutes, and then transferred to the steaming kettle 1.
  • Insulation kettle 2 After receiving the reaction materials for 20 minutes, the temperature is also controlled at 118 ⁇ 2°C. After receiving the materials for 80 minutes, the materials are transferred to the holding kettle 1, the holding kettle 2 continues to be kept at 118 ⁇ 2°C for 80 minutes, then transfer Enter the steaming kettle 2, and operate in this way.
  • hydrochloric acid The content of hydrochloric acid is 15.08%, and the content of formaldehyde is 0.81%
  • the active content of ATMP is 50.18%, the content of chloride ( calculated as Cl - ) is 1.32%, the content of iron ( calculated as Fe 2+ ) is 6.95mg/L, the color (Hezen) is 29.2, and the yield of ATMP (calculated as the raw material phosphorous acid) is 97.93 %.
  • the tubular reactor is a graphite U-shaped tubular reactor with a diameter of 60cm and a length of 50cm. The reaction is performed in an oil bath at 115°C.
  • the mixed liquid obtained from the reaction enters the spray absorption tower, and is sprayed from the top of the tower to contact with rising steam at a flow rate of 1000L/h and a temperature of 160°C.
  • the aqueous solution of amino trimethylene phosphonic acid enters the bottom storage tank, and the raw material chlorine that has not been reacted
  • the ammonium chloride, formaldehyde and the generated hydrogen chloride enter the rectification device from the top of the tower for rectification and separation.
  • the active content of ATMP is 50.21%, the content of chloride ( calculated as Cl - ) is 1.42%, the content of iron ( calculated as Fe 2+ ) is 6.91mg/L, the color (Hezen) is 29.0, and the ATMP yield (calculated as the raw material phosphorous acid) is 87.65 %.

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Abstract

Disclosed is a method for producing amino trimethylene phosphonic acid as a water treatment agent. Specifically, ammonia solution, phosphorous acid, hydrochloric acid, and formaldehyde in certain proportions are added to a reactor at a constant rate and subjected to processes comprising gradient overflow, heat preservation, steaming, dilution, etc., to obtain a high-purity ATMP aqueous solution. The method achieves continuous production by means of a simple approach, that of continuous feeding of liquid raw materials and continuous discharging, thereby significantly shortening the production cycle. By means of controlling the reaction conditions, the present method achieves a conversion rate of ATMP ≥98% without the need to separate raw materials, thereby reducing labor hours and costs. Hydrochloric acid is used as a catalyst in the present method and can be reused after treatment. Accordingly, the method does not produce waste gas, wastewater or waste residues, and is therefore environmentally friendly.

Description

一种水处理剂氨基三甲叉膦酸的生产方法Method for producing water treatment agent amino trimethylene phosphonic acid 技术领域Technical field
本发明属于化工领域，特别是涉及一种水处理剂氨基三甲叉膦酸的生产方法。The invention belongs to the field of chemical engineering, and particularly relates to a method for producing water treatment agent amino trimethylene phosphonic acid.
背景技术Background technique
氨基三甲叉膦酸(ATMP)作为一种水处理剂广泛应用于工业循环冷却水***中。它具有良好的阻垢和缓蚀作用，对抑制碳酸钙、水合氧化铁和磷酸钙有良好的效果，与其他缓蚀剂和阻垢剂配合使用，具有协同药效，用量为1～20mg/L时就能达到良好的缓蚀阻垢效果，是一种重要的阻垢分散剂，广泛应用于大型石化、化肥等生产装置的冷却水处理。ATMP有较好的化学稳定性，不易被酸、碱破坏，也不易水解。从结构上看，ATMP有三个磷酸基团，具有很好地络合增液，溶限效应，晶格畸变等性能，并阻止水中各种无机盐类形成阻钙。有机磷酸是工业水处理中常用的水处理剂，不仅对钙、镁等许多金属离子具有很好的螯合能力，而且还是一种阴极型缓蚀剂。Amino Trimethylene Phosphonic Acid (ATMP) as a water treatment agent is widely used in industrial circulating cooling water systems. It has good scale and corrosion inhibition effects, and has a good effect on inhibiting calcium carbonate, hydrated iron oxide and calcium phosphate. It has a synergistic effect when used in conjunction with other corrosion inhibitors and scale inhibitors. The dosage is 1-20mg/L It can achieve good corrosion and scale inhibition effects when it is time. It is an important scale inhibitor and dispersant, which is widely used in the cooling water treatment of large-scale petrochemical, fertilizer and other production equipment. ATMP has good chemical stability, is not easy to be damaged by acid and alkali, and is not easy to be hydrolyzed. From the structural point of view, ATMP has three phosphoric acid groups, which have good complexing and liquid enhancement, solubility limit effect, lattice distortion and other properties, and prevent various inorganic salts in water from forming calcium barriers. Organic phosphoric acid is a commonly used water treatment agent in industrial water treatment. It not only has a good chelating ability to many metal ions such as calcium and magnesium, but also is a cathode type corrosion inhibitor.
目前，关于ATMP的生产方法，国内外文献均有大量报道。国内现有方法普遍用氯化铵、亚磷酸和甲醛为原料生成氨基三甲叉膦酸。此法生产周期长，且附带产生大量的低含量盐酸，处理成本较高。中国专利CN103275121B公开了一种以氯化铵、亚磷酸、甲醛为原料，采用喷淋方式反应，连续投料，连续出料，未反应的原料用精馏装置分离收集再次利用。此法虽然实现了连续化，但由于一次反应率低，未反应原料的分离耗时耗能，且副产较多，不利于其工业化规模发展。At present, there are a large number of reports in domestic and foreign literature on the production method of ATMP. The existing domestic methods generally use ammonium chloride, phosphorous acid and formaldehyde as raw materials to generate amino trimethylene phosphonic acid. This method has a long production cycle, and incidentally produces a large amount of low-content hydrochloric acid, and the processing cost is high. Chinese patent CN103275121B discloses a method of using ammonium chloride, phosphorous acid, and formaldehyde as raw materials, adopting spraying method to react, continuous feeding, continuous discharging, and unreacted raw materials are separated and collected by a rectification device for reuse. Although this method achieves continuity, due to the low primary reaction rate, the separation of unreacted raw materials is time-consuming and energy-consuming, and there are many by-products, which is not conducive to its industrial scale development.
发明内容：Summary of the invention:
为了克服上述现有技术的不足，本发明提供了一种可连续化、绿色环保的水处理剂氨基三甲叉膦酸的生产方法。In order to overcome the above shortcomings of the prior art, the present invention provides a continuous, green and environmentally friendly water treatment agent amino trimethylene phosphonic acid production method.
一种水处理剂氨基三甲叉膦酸的生产方法，具体包括：A production method of water treatment agent amino trimethylene phosphonic acid, which specifically includes:
装置为：三级反应釜串联溢流，第3级反应釜与保温釜串联溢流，保温釜与外蒸釜串联，三 反应釜、保温釜、外蒸釜的冷凝回流与盐酸吸收罐相连。The device is: three-stage reactor overflows in series, the third-stage reactor overflows in series with the insulation kettle, the insulation pot is connected in series with the outer steaming kettle, and the condensed reflux of the three reactors, the insulation kettle and the outer steaming kettle are connected to the hydrochloric acid absorption tank.
方法为：The method is:
(1)第1到3级反应釜加入一定量的ATMP底料，开启搅拌，温度升至100℃后，一级反应釜按一定流量泵入氨水、盐酸和亚磷酸。三级反应釜按一定流量泵入甲醛，反应釜在一定温度下持续搅拌，物料填充满反应釜后开始溢流，物料从一级反应釜逐级溢流至保温釜，甲醛气体从三级反应釜以气体方式逐级鼓至一级反应釜。(1) Add a certain amount of ATMP bottom material to the first to third stage reactors, turn on the stirring, and after the temperature rises to 100°C, the first stage reactor is pumped into ammonia, hydrochloric acid and phosphorous acid at a certain flow rate. The three-stage reactor is pumped into formaldehyde at a certain flow rate, and the reactor is continuously stirred at a certain temperature. After filling the reactor, the material overflows. The material overflows from the first-stage reactor to the holding tank, and the formaldehyde gas reacts from the third stage. The kettle is drummed step by step to the first-level reaction kettle in a gaseous manner.
(2)保温釜在接收物料60±5min后，换保温釜接收物料，接收完物料的保温釜在一定温度下保温一段时间，将物料转入冲蒸釜中用蒸气冲蒸至一定浓度后，稀释转料到ATMP收集罐。(2) After 60±5 minutes of receiving the material in the holding kettle, change the holding kettle to receive the material. After receiving the material, the holding kettle is kept at a certain temperature for a period of time. After the material is transferred to the steaming kettle and steamed to a certain concentration, The diluted material is transferred to the ATMP collection tank.
(3)盐酸吸收液经HEDP生产线的盐酸多级吸收装置，生成32％盐酸循环使用。(3) The hydrochloric acid absorption liquid is passed through the hydrochloric acid multi-stage absorption device of the HEDP production line to generate 32% hydrochloric acid for recycling.
其中，步骤(1)中所述的串联溢流为梯度串联溢流，物料由釜的溢流口流向下一级釜，溢流口设有单向保护装置，防止倒吸。Wherein, the series overflow described in step (1) is a gradient series overflow, and the material flows from the overflow port of the kettle to the next stage of the kettle, and the overflow port is provided with a one-way protection device to prevent back suction.
其中，步骤(2)中所述的投放物料氨水、盐酸、亚磷酸和甲醛的物质的量比为1：(1～2)：(2～3)：(3～4)，优选为1：1.2：3.0：3.1。Wherein, in step (2), the amount ratio of ammonia water, hydrochloric acid, phosphorous acid and formaldehyde is 1:(1～2):(2～3):(3～4), preferably 1: 1.2:3.0:3.1.
其中，步骤(2)中所述的反应釜容量为釜底到溢出口的釜内体积容量。Wherein, the reactor capacity described in step (2) is the internal volume capacity of the reactor from the bottom of the reactor to the overflow port.
其中，步骤(2)中所述的物料填充满反应釜的时间为70±5min。Wherein, the time for filling the reactor with the materials described in step (2) is 70±5 min.
其中，步骤(2)中所述的一定流量由反应釜容量和填充物料时间及各物料配比决定，由于时间，物料配比已经固定，流量根据反应釜容量大小调整。Wherein, the certain flow rate described in step (2) is determined by the capacity of the reactor, the filling material time and the ratio of each material. Due to the time, the material ratio has been fixed, and the flow rate is adjusted according to the capacity of the reactor.
其中，步骤(2)中所述的反应釜在一定温度下持续搅拌的温度为95～125℃，优选为110～120℃。Wherein, the reaction kettle described in step (2) is continuously stirred at a certain temperature at a temperature of 95-125°C, preferably 110-120°C.
其中，步骤(3)中所述的保温釜保温时间优选为60±5min。Wherein, the heat preservation time of the heat preservation kettle described in step (3) is preferably 60±5 min.
其中，步骤(3)中所述的保温釜在一定温度下保温的温度范围是105～120℃，优选为110～120℃。Wherein, the temperature range of the heat preservation kettle described in step (3) at a certain temperature is 105-120°C, preferably 110-120°C.
其中，步骤(3)中所述的冲蒸至一定浓度为70～85％，优选为75～80％。Wherein, in step (3), it is steamed to a certain concentration of 70-85%, preferably 75-80%.
本发明提供了一种高效的连续化生产方法。此方法实现连续化投料，连续化出料，设备和资源利用率高，生产周期短，副产少，质量稳定。此方法设备需求简单，反应流程简单，设备利用率高。The invention provides an efficient continuous production method. This method realizes continuous feeding and discharging, high utilization rate of equipment and resources, short production cycle, few by-products, and stable quality. This method has simple equipment requirements, simple reaction process, and high equipment utilization.
此方法原料的一次转化率高，无需从出料中分离产品和原料，节约工时和成本，节能降耗。此方法所用盐酸可视为催化剂，通过处理后能重复使用，无三废产生，绿色环保。综上所述，本发明可有效推动氨基三甲叉膦酸的工业化规模发展。The method has a high primary conversion rate of raw materials, and does not need to separate products and raw materials from the discharged materials, saves working hours and costs, and saves energy and reduces consumption. The hydrochloric acid used in this method can be regarded as a catalyst, can be reused after treatment, no three wastes are generated, and it is green and environmentally friendly. In summary, the present invention can effectively promote the industrial scale development of amino trimethylene phosphonic acid.
本发明有益效果：The beneficial effects of the present invention:
[根据细则91更正 18.09.2020]　
此法通过连续化投放液体原料，连续化出料的简单操作方式，实现连续化生产，大大缩短了生产周期。此法通过控制反应条件，实现ATMP一次转化率≥98％，无需再分离原料，节约工时和成本。此法所用盐酸为催化剂，经处理后可重复使用，无三废产生，绿色环保。
附图说明
图1为本发明方法流程图。
[Correct 18.09.2020 according to Rule 91]
This method realizes continuous production through the simple operation mode of continuous feeding of liquid raw materials and continuous discharging, which greatly shortens the production cycle. By controlling the reaction conditions, this method realizes the conversion rate of ATMP ≥98%, no need to separate the raw materials, saving labor time and cost. The hydrochloric acid used in this method is a catalyst, which can be reused after treatment, no three wastes are generated, and it is green and environmentally friendly.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart of the method of the present invention.
具体实施方式Detailed ways
下面结合具体实施方式和附图1说明对本发明进行进一步说明。The present invention will be further described below in conjunction with the specific embodiments and the description of FIG. 1.
实施例1Example 1
向一到三级反应釜分别加入200kg的ATMP底料，开启搅拌，温度升至100℃后，向一级反应釜按氨水517L/h、盐酸1041L/h、亚磷酸2673L/h的流量匀速打入氨水、盐酸和亚磷酸，三级反应釜按甲醛1768L/h的流量匀速打入甲醛，氨水、盐酸、亚磷酸、甲醛物质的量比n 氨 水:n 盐酸:n 亚磷酸:n 甲醛为1：1.2：3.0：3.1。反应釜内物料从开始加入到开始溢流时间为70min。打料20min后反应釜内温度控制在118±2℃，氨水、盐酸、亚磷酸、甲醛的质量分数分别为25％、32％、70％、40％。 Add 200kg of ATMP bottom material to the first to third-stage reactors, turn on the stirring, and after the temperature rises to 100°C, the first-stage reactor is fed to the first-stage reactor at a constant rate at a flow rate of 517L/h of ammonia, 1041L/h of hydrochloric acid, and 2673L/h of phosphorous acid. aqueous ammonia, hydrochloric acid and phosphorous acid, formaldehyde press three reactor 1768L / h of flow rate ratio into the uniform n formaldehyde, ammonia, hydrochloric acid, phosphorous acid, formaldehyde, ammonia water substance: n hydrochloric acid: phosphorous acid n: n formaldehyde 1:1.2:3.0:3.1. The time from the beginning of the addition of the materials in the reactor to the beginning of overflow is 70 minutes. The temperature in the reactor is controlled at 118±2°C after 20 minutes of feeding, and the mass fractions of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde are 25%, 32%, 70%, and 40%, respectively.
反应釜开始溢流后，继续按上述流量匀速打入各原料，反应釜内物料从一级反应釜逐级溢流至保温釜①，保温釜①接收反应物料20min后，控温118±2℃，在接收物料60min后，通过阀门控制将物料转入保温釜②，保温釜①继续在118±2℃温度下保温60min，然后转入 冲蒸釜①。保温釜②接收反应物料20min后，同样控温118±2℃，在接收物料60min后，通过阀门控制将物料转入保温釜①，保温釜②继续在118±2℃温度下保温60min，然后转入冲蒸釜②，如此循环操作。After the reactor starts to overflow, continue to feed the raw materials at the above flow rate at a constant speed. The materials in the reactor overflow gradually from the first-level reactor to the insulation kettle①. After the insulation kettle① receives the reaction materials for 20 minutes, the temperature is controlled to 118±2℃ , After receiving the material for 60 minutes, the material is transferred to the insulation kettle ② through the valve control, and the insulation kettle ① continues to be kept at a temperature of 118 ± 2 ℃ for 60 minutes, and then transferred to the steaming kettle ①. Insulation kettle ② After receiving the reaction materials for 20 minutes, the temperature is also controlled at 118±2°C. After receiving the materials for 60 minutes, the materials are transferred to the holding kettle ①, the holding kettle ② continues to be kept at 118±2°C for 60 minutes, then transfer Enter the steaming kettle ②, and operate in this way.
冲蒸釜①和②分别水蒸汽冲蒸浓缩物料至76％左右时，停止冲蒸，稀释成含量50％ATMP水溶液转至ATMP成品罐。盐酸酸吸收罐内吸收液入HEDP生产线的盐酸多级吸收装置，生成32％盐酸循环使用。When the steaming kettle ① and ② steam the concentrated material to about 76%, stop the steaming, and transfer to the ATMP finished product tank after being diluted to 50% ATMP aqueous solution. The absorption liquid in the hydrochloric acid absorption tank enters the hydrochloric acid multi-stage absorption device of the HEDP production line to generate 32% hydrochloric acid for recycling.
产品检测指标：Product testing indicators:
1盐酸吸收液：1 Hydrochloric acid absorption solution:
盐酸含量15.12％，甲醛含量0.80％The content of hydrochloric acid is 15.12%, and the content of formaldehyde is 0.80%
2ATMP收集罐：2ATMP collection tank:
ATMP活性含量50.20％，氯化物(以Cl -计)含量1.31％，铁(以Fe 2+计)含量6.90mg/L，色度(Hezen)28.0，ATMP收率(以原料亚磷酸计)97.84％。 ATMP active content 50.20%, chloride ( calculated as Cl - ) content 1.31%, iron ( calculated as Fe 2+ ) content 6.90mg/L, color (Hezen) 28.0, ATMP yield (calculated as raw material phosphorous acid) 97.84 %.
实施例2Example 2
向一到三级反应釜分别加入200kg的ATMP底料，开启搅拌，温度升至100℃后，向一级反应釜按氨水517L/h、盐酸1041L/h、亚磷酸2673L/h的流量匀速打入氨水、盐酸和亚磷酸，三级反应釜按甲醛1768L/h的流量匀速打入甲醛，氨水、盐酸、亚磷酸、甲醛物质的量比n 氨 水:n 盐酸:n 亚磷酸:n 甲醛为1：1.2：3.0：3.1。反应釜内物料从开始加入到开始溢流时间为70min左右。打料20min后反应釜内温度控制在112±2℃，氨水、盐酸、亚磷酸、甲醛的质量分数分别为25％、32％、70％、40％。 Add 200kg of ATMP bottom material to the first to third-stage reactors, turn on the stirring, and after the temperature rises to 100°C, the first-stage reactor is fed to the first-stage reactor at a constant rate at a flow rate of 517L/h of ammonia, 1041L/h of hydrochloric acid, and 2673L/h of phosphorous acid. aqueous ammonia, hydrochloric acid and phosphorous acid, formaldehyde press three reactor 1768L / h of flow rate ratio into the uniform n formaldehyde, ammonia, hydrochloric acid, phosphorous acid, formaldehyde, ammonia water substance: n hydrochloric acid: phosphorous acid n: n formaldehyde 1:1.2:3.0:3.1. The time from the beginning of the addition of the materials in the reactor to the beginning of overflow is about 70 minutes. The temperature in the reactor is controlled at 112±2°C after 20 minutes of feeding, and the mass fractions of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde are 25%, 32%, 70%, and 40%, respectively.
反应釜开始溢流后，继续按上述流量匀速打入各原料，反应釜内物料从一级反应釜逐级溢流至保温釜①，保温釜①接收反应物料20min后，控温112±2℃，在接收物料60min后，通过阀门控制将物料转入保温釜②，保温釜①继续在112±2℃温度下保温60min，然后转入冲蒸釜①。保温釜②接收反应物料20min后，同样控温112±2℃，在接收物料60min后，通 过阀门控制将物料转入保温釜①，保温釜②继续在112±2℃温度下保温60min，然后转入冲蒸釜②，如此循环操作。After the reactor begins to overflow, continue to feed the raw materials at the above flow rate at a constant speed. The materials in the reactor gradually overflow from the first-stage reactor to the insulation kettle①. After the insulation pot① receives the reaction materials for 20 minutes, the temperature is controlled at 112±2℃. , After receiving the material for 60 minutes, the material is transferred to the heat preservation kettle ② through the valve control, and the heat preservation kettle ① continues to be kept at a temperature of 112 ± 2 ℃ for 60 minutes, and then transferred to the steaming kettle ①. Insulation kettle ② After receiving the reaction materials for 20 minutes, the temperature is also controlled at 112±2°C. After receiving the materials for 60 minutes, the materials are transferred to the holding kettle ①, the holding kettle ② continues to be kept at 112±2°C for 60 minutes, then transfer Enter the steaming kettle ②, and operate in this way.
冲蒸釜①和②分别水蒸汽冲蒸浓缩物料至79％左右时，停止冲蒸，稀释成含量50％的ATMP水溶液转至ATMP成品罐。盐酸酸吸收罐内吸收液入HEDP生产线的盐酸多级吸收装置，生成32％盐酸循环使用。When the steaming kettle ① and ② steam the concentrated material to about 79%, the steaming is stopped, and the ATMP water solution diluted to 50% is transferred to the ATMP finished product tank. The absorption liquid in the hydrochloric acid absorption tank enters the hydrochloric acid multi-stage absorption device of the HEDP production line to generate 32% hydrochloric acid for recycling.
产品检测指标：Product testing indicators:
1盐酸吸收液：1 Hydrochloric acid absorption solution:
盐酸含量14.92％，甲醛含量0.85％The content of hydrochloric acid is 14.92%, and the content of formaldehyde is 0.85%
2ATMP收集罐：2ATMP collection tank:
ATMP活性含量50.25％，氯化物(以Cl -计)含量1.27％，铁(以Fe 2+计)含量6.65mg/L，色度(Hezen)29.4，ATMP收率(以原料亚磷酸计)96.81％。 The active content of ATMP is 50.5%, the content of chloride (calculated as Cl - ) is 1.27%, the content of iron ( calculated as Fe 2+ ) is 6.65 mg/L, the color (Hezen) is 29.4, and the ATMP yield (calculated as the raw material phosphorous acid) is 96.81 %.
实施例3Example 3
向一到三级反应釜分别加入200kg的ATMP底料，开启搅拌，温度升至100℃后，向一级反应釜按氨水724L/h、盐酸1457L/h、亚磷酸3742L/h的流量匀速打入氨水、盐酸和亚磷酸，三级反应釜按甲醛2475L/h的流量匀速打入甲醛，氨水、盐酸、亚磷酸、甲醛物质的量比n 氨 水:n 盐酸:n 亚磷酸:n 甲醛为1：1.2：3.0：3.1。反应釜内物料从开始加入到开始溢流时间为50min左右。打料20min后反应釜内温度控制在118±2℃，氨水、盐酸、亚磷酸、甲醛的质量分数分别为25％、32％、70％、40％。 Add 200kg of ATMP bottom material to the first to third-stage reactors, turn on the stirring, and after the temperature rises to 100°C, the first-stage reactor is fed to the first-stage reactor at a constant rate at a flow rate of 724L/h of ammonia, 1457L/h of hydrochloric acid and 3742L/h of phosphorous aqueous ammonia, hydrochloric acid and phosphorous acid, formaldehyde according to the flow reactor three 2475L / h into a constant speed ratio n formaldehyde, ammonia, hydrochloric acid, phosphorous acid, formaldehyde, ammonia water substance: n hydrochloric acid: phosphorous acid n: n formaldehyde 1:1.2:3.0:3.1. The time from the beginning of adding the materials in the reactor to the beginning of overflow is about 50 minutes. The temperature in the reactor is controlled at 118±2°C after 20 minutes of feeding, and the mass fractions of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde are 25%, 32%, 70%, and 40%, respectively.
反应釜开始溢流后，继续按上述流量匀速打入各原料，反应釜内物料从一级反应釜逐级溢流至保温釜①，保温釜①接收反应物料20min后，控温118±2℃，在接收物料40min后，通过阀门控制将物料转入保温釜②，保温釜①继续在118±2℃温度下保温40min，然后转入冲蒸釜①。保温釜②接收反应物料20min后，同样控温118±2℃，在接收物料40min后，通过阀门控制将物料转入保温釜①，保温釜②继续在118±2℃温度下保温40min，然后转入冲 蒸釜②，如此循环操作。After the reactor starts to overflow, continue to feed the raw materials at the above flow rate at a constant speed. The materials in the reactor overflow gradually from the first-level reactor to the insulation kettle①. After the insulation kettle① receives the reaction materials for 20 minutes, the temperature is controlled to 118±2℃ , After receiving the material for 40 minutes, the material is transferred to the insulation kettle ② through the valve control, the insulation kettle ① continues to be kept at a temperature of 118 ± 2 ℃ for 40 minutes, and then transferred to the steaming kettle ①. Insulation kettle ② After receiving the reaction materials for 20 minutes, the temperature is also controlled at 118±2°C. After receiving the materials for 40 minutes, the materials are transferred to the holding kettle ①, the holding kettle ② continues to be kept at 118±2°C for 40 minutes, then transfer Enter the steaming kettle ②, and operate in this way.
冲蒸釜①和②分别水蒸汽冲蒸浓缩物料至77％左右时，停止冲蒸，稀释成含量50％的ATMP水溶液转至ATMP成品罐。盐酸酸吸收罐内吸收液入HEDP生产线的盐酸多级吸收装置，生成32％盐酸循环使用。When the steaming kettle ① and ② steam the concentrated material to about 77%, the steaming is stopped, and the ATMP water solution diluted to 50% is transferred to the ATMP finished product tank. The absorption liquid in the hydrochloric acid absorption tank enters the hydrochloric acid multi-stage absorption device of the HEDP production line to generate 32% hydrochloric acid for recycling.
产品检测指标：Product testing indicators:
1盐酸吸收液：1 Hydrochloric acid absorption solution:
盐酸含量15.10％，甲醛含量0.79％The content of hydrochloric acid is 15.10%, and the content of formaldehyde is 0.79%
2ATMP收集罐：2ATMP collection tank:
ATMP活性含量50.20％，氯化物(以Cl -计)含量1.31％，铁(以Fe 2+计)含量6.90mg/L，色度(Hezen)28.0，ATMP收率(以原料亚磷酸计)93.37％。 The active content of ATMP is 50.20%, the content of chloride ( calculated as Cl - ) is 1.31%, the content of iron ( calculated as Fe 2+ ) is 6.90mg/L, the color (Hezen) is 28.0, and the ATMP yield (calculated as the raw material phosphorous acid) is 93.37 %.
实施例4Example 4
向一到三级反应釜分别加入200kg的ATMP底料，开启搅拌，温度升至100℃后，向一级反应釜按氨水402L/h、盐酸810L/h、亚磷酸2079L/h的流量匀速打入氨水、盐酸和亚磷酸，三级反应釜按甲醛1375L/h的流量匀速打入甲醛，氨水、盐酸、亚磷酸、甲醛物质的量比n 氨水:n 盐酸:n 亚磷酸:n 甲醛为1：1.2：3.0：3.1。反应釜内物料从开始加入到开始溢流时间为90min。打料20min后反应釜内温度控制在118±2℃，氨水、盐酸、亚磷酸、甲醛的质量分数分别为25％、32％、70％、40％。 Add 200kg of ATMP bottom material to the first to third-stage reactors respectively, turn on the stirring, and after the temperature rises to 100°C, the first-stage reactor is fed to the first-stage reactor at a constant rate at a flow rate of 402L/h of ammonia water, 810L/h of hydrochloric acid, and 2079L/h of phosphorous acid. Enter ammonia, hydrochloric acid and phosphorous acid. The three-stage reactor is fed with formaldehyde at a constant rate of 1375L/h. The ratio of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde is n ammonia : n hydrochloric acid : n phosphorous acid : n formaldehyde is 1. : 1.2:3.0:3.1. The time from the beginning of the addition of the materials in the reactor to the beginning of overflow is 90 minutes. The temperature in the reactor is controlled at 118±2°C after 20 minutes of feeding, and the mass fractions of ammonia, hydrochloric acid, phosphorous acid, and formaldehyde are 25%, 32%, 70%, and 40%, respectively.
反应釜开始溢流后，继续按上述流量匀速打入各原料，反应釜内物料从一级反应釜逐级溢流至保温釜①，保温釜①接收反应物料20min后，控温118±2℃，在接收物料80min后，通过阀门控制将物料转入保温釜②，保温釜①继续在118±2℃温度下保温80min，然后转入冲蒸釜①。保温釜②接收反应物料20min后，同样控温118±2℃，在接收物料80min后，通过阀门控制将物料转入保温釜①，保温釜②继续在118±2℃温度下保温80min，然后转入冲蒸釜②，如此循环操作。After the reactor starts to overflow, continue to feed the raw materials at the above flow rate at a constant speed. The materials in the reactor overflow gradually from the first-level reactor to the insulation kettle①. After the insulation kettle① receives the reaction materials for 20 minutes, the temperature is controlled to 118±2℃ , After receiving the material for 80 minutes, the material is transferred to the insulation kettle ② through the valve control, the insulation kettle ① continues to be kept at a temperature of 118 ± 2 ℃ for 80 minutes, and then transferred to the steaming kettle ①. Insulation kettle ② After receiving the reaction materials for 20 minutes, the temperature is also controlled at 118±2°C. After receiving the materials for 80 minutes, the materials are transferred to the holding kettle ①, the holding kettle ② continues to be kept at 118±2°C for 80 minutes, then transfer Enter the steaming kettle ②, and operate in this way.
冲蒸釜①和②分别水蒸汽冲蒸浓缩物料至76％左右时，停止冲蒸，稀释成含量50％ATMP水溶液转至ATMP成品罐。盐酸酸吸收罐内吸收液入HEDP生产线的盐酸多级吸收装置，生成32％盐酸循环使用。When the steaming kettle ① and ② steam the concentrated material to about 76%, stop the steaming, and transfer to the ATMP finished product tank after being diluted to 50% ATMP aqueous solution. The absorption liquid in the hydrochloric acid absorption tank enters the hydrochloric acid multi-stage absorption device of the HEDP production line to generate 32% hydrochloric acid for recycling.
产品检测指标：Product testing indicators:
1盐酸吸收液：1 Hydrochloric acid absorption solution:
盐酸含量15.08％，甲醛含量0.81％The content of hydrochloric acid is 15.08%, and the content of formaldehyde is 0.81%
2ATMP收集罐：2ATMP collection tank:
ATMP活性含量50.18％，氯化物(以Cl -计)含量1.32％，铁(以Fe 2+计)含量6.95mg/L，色度(Hezen)29.2，ATMP收率(以原料亚磷酸计)97.93％。 The active content of ATMP is 50.18%, the content of chloride ( calculated as Cl - ) is 1.32%, the content of iron ( calculated as Fe 2+ ) is 6.95mg/L, the color (Hezen) is 29.2, and the yield of ATMP (calculated as the raw material phosphorous acid) is 97.93 %.
对比例Comparison
将摩尔比1：2.0：2.8氯化铵、亚磷酸、甲醛加入混料釜，加入80％质量的反渗透水，30～35℃混合均匀。将混合好的物料以800L/h的流量泵入管式反应器，管式反应器为直径60cm、长度50cm的石墨U型管式反应器，115℃油浴反应。Add ammonium chloride, phosphorous acid, and formaldehyde in a molar ratio of 1:2.0:2.8 into the mixing kettle, add 80% by mass of reverse osmosis water, and mix well at 30-35°C. The mixed materials are pumped into the tubular reactor at a flow rate of 800L/h. The tubular reactor is a graphite U-shaped tubular reactor with a diameter of 60cm and a length of 50cm. The reaction is performed in an oil bath at 115°C.
反应所得混合液进入喷淋吸收塔，从塔顶喷淋与以流量1000L/h、温度160℃的上升蒸汽接触，氨基三亚甲基膦酸水溶液进入塔底储料釜，没反应完的原料氯化铵、甲醛以及生成的氯化氢从塔顶进入精馏装置精馏分离。The mixed liquid obtained from the reaction enters the spray absorption tower, and is sprayed from the top of the tower to contact with rising steam at a flow rate of 1000L/h and a temperature of 160℃. The aqueous solution of amino trimethylene phosphonic acid enters the bottom storage tank, and the raw material chlorine that has not been reacted The ammonium chloride, formaldehyde and the generated hydrogen chloride enter the rectification device from the top of the tower for rectification and separation.
产品检测指标：Product testing indicators:
ATMP活性含量50.21％，氯化物(以Cl -计)含量1.42％，铁(以Fe 2+计)含量6.91mg/L，色度(Hezen)29.0，ATMP收率(以原料亚磷酸计)87.65％。 The active content of ATMP is 50.21%, the content of chloride ( calculated as Cl - ) is 1.42%, the content of iron ( calculated as Fe 2+ ) is 6.91mg/L, the color (Hezen) is 29.0, and the ATMP yield (calculated as the raw material phosphorous acid) is 87.65 %.
以上所述实施例仅表达了本发明专利的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明专利的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express the implementation mode of the patent of the present invention, and the description is relatively specific and detailed, but it should not be understood as a limitation to the scope of the patent of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all belong to the protection scope of the present invention patent. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

  1. 一种水处理剂氨基三甲叉膦酸的生产方法，其特征在于，A method for producing water treatment agent amino trimethylene phosphonic acid, which is characterized in that:
    生产设备具体为三级反应釜串联溢流，第3级反应釜与保温釜串联溢流，保温釜与外蒸釜串联；The production equipment is specifically the overflow of three-stage reactor in series, the overflow of the third-stage reactor and the insulation kettle in series, and the insulation and external steaming kettle in series;
    生产方法包括以下步骤：The production method includes the following steps:
    (1)第1-3级反应釜加入的ATMP底料，开启搅拌，温度升至90-120℃后，反应釜持续搅拌，第1级反应釜泵入氨水、盐酸和亚磷酸；第3级反应釜泵入甲醛，物料填充满反应釜后开始溢流，物料从第1反应釜开始逐级溢流至保温釜，甲醛气体从第3级反应釜以气体方式逐级鼓至第1级反应釜；(1) The bottom material of ATMP added to the reactor of stage 1-3, start stirring, after the temperature rises to 90-120℃, the reactor will continue to stir, and the reactor of stage 1 will be pumped into ammonia, hydrochloric acid and phosphorous acid; The reactor is pumped with formaldehyde, and the material overflows after filling the reactor. The material overflows from the first reactor to the holding tank step by step, and the formaldehyde gas is gradually drummed from the third reactor to the first reactor in a gaseous manner. kettle;
    (2)保温釜在接收物料60±5min后，换保温釜接收物料，接收完物料的保温釜进行保温反应，将物料转入冲蒸釜中用蒸气冲蒸稀释后，转料到ATMP收集罐。(2) After 60±5 minutes of receiving the material, the holding kettle is replaced with the holding kettle to receive the material. After receiving the material, the holding kettle performs the holding reaction, transfers the material to the steaming kettle and dilutes with steam, then transfers the material to the ATMP collection tank .
  2. 根据权利要求1所述的方法，其特征在于，所述生产设备中的串联溢流为梯度串联溢流，物料由釜的溢流口流向下一级釜，溢流口设有单向保护装置，防止倒吸。The method according to claim 1, characterized in that the series overflow in the production equipment is a gradient series overflow, the material flows from the overflow port of the kettle to the next stage of the kettle, and the overflow port is provided with a one-way protection device , To prevent back suction.
  3. 根据权利要求1所述的方法，其特征在于，所述步骤(1)中的投放物料氨水、盐酸、亚磷酸和甲醛的物质的量比为1：1～2：2～3：3～4。The method according to claim 1, characterized in that, in the step (1), the amount ratio of ammonia water, hydrochloric acid, phosphorous acid and formaldehyde is 1:1~2:2~3:3~4. .
  4. 根据权利要求1所述的方法，其特征在于，所述步骤(1)中的物料填充满反应釜的时间为70±5min。The method according to claim 1, wherein the time for filling the reactor with the materials in the step (1) is 70±5 min.
  5. 根据权利要求1所述的方法，其特征在于，所述步骤(1)反应温度为95～125℃。The method according to claim 1, wherein the reaction temperature in the step (1) is 95-125°C.
  6. 根据权利要求1所述的方法，其特征在于，所述步骤(2)中的保温釜保温反应时间为60±5min。The method according to claim 1, characterized in that, the reaction time of the heat preservation kettle in the step (2) is 60±5 min.
  7. 根据权利要求1所述的方法，其特征在于，所述步骤(2)中的保温釜保温的温度范围是105～120℃。The method according to claim 1, wherein the temperature range of the heat preservation kettle in the step (2) is 105-120°C.
  8. 根据权利要求1所述的方法，其特征在于，所述步骤(2)中的冲蒸稀释至浓度为70～85％。The method according to claim 1, wherein the steaming in the step (2) is diluted to a concentration of 70-85%.
  9. 根据权利要求1所述的方法，其特征在于，所述的生产设备中一级反应釜、保温釜和外蒸 釜的冷凝回流与盐酸吸收罐相连。The method according to claim 1, wherein the condensed reflux of the first-level reactor, the heat preservation kettle and the external steam kettle in the production equipment are connected to the hydrochloric acid absorption tank.
  10. 根据权利要求9所述的方法，其特征在于，所述的盐酸吸收液经HEDP生产线的盐酸多级吸收装置，生成32％盐酸循环使用。The method according to claim 9, wherein the hydrochloric acid absorption liquid is passed through the hydrochloric acid multi-stage absorption device of the HEDP production line to generate 32% hydrochloric acid for recycling.
PCT/CN2020/109683 2019-11-08 2020-08-18 Method for producing amino trimethylene phosphonic acid as water treatment agent WO2021088459A1 (en)

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