CN111318244B - Phosphonate ester hydrolysis device and method - Google Patents
Phosphonate ester hydrolysis device and method Download PDFInfo
- Publication number
- CN111318244B CN111318244B CN202010122249.5A CN202010122249A CN111318244B CN 111318244 B CN111318244 B CN 111318244B CN 202010122249 A CN202010122249 A CN 202010122249A CN 111318244 B CN111318244 B CN 111318244B
- Authority
- CN
- China
- Prior art keywords
- valve
- water
- hydrolysis
- steam
- kettle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
- B01D3/4211—Regulation; Control of columns
- B01D3/4216—Head stream
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
Abstract
A phosphonate ester hydrolysis device and a method belong to the technical field of organic phosphorus flame retardant synthesis. The invention solves the problem of difficult phosphonic acid source. The device comprises a hydrolysis kettle, an elevated tank, a packed tower, a condenser and a receiving tank, wherein water in the elevated tank is continuously dropped into the hydrolysis kettle, appropriate process parameters such as temperature, catalyst and the like are controlled in the hydrolysis kettle to hydrolyze phosphonate, mixed steam of hydrolysis by-products methanol and excessive water sequentially enters the packed tower and the condenser to undergo mass transfer separation and liquefaction, water returns to the hydrolysis kettle, and the methanol is distilled and collected in the receiving tank. The device is suitable for hydrolyzing various methyl phosphonates and performing semi-continuous operation, has simple and flexible operation method, thorough hydrolysis and high efficiency, can simultaneously obtain high-purity methanol and high-concentration phosphonic acid aqueous solution, and is suitable for industrial production and use.
Description
Technical Field
The invention relates to a phosphonate ester hydrolysis device and a phosphonate ester hydrolysis method, in particular to a methyl phosphonate ester hydrolysis device and a methyl phosphonate ester hydrolysis method, and belongs to the technical field of synthesis of organic phosphorus flame retardants.
Background
The phosphonic acid being phosphoric acid (HO)3Compounds in which one or both of the hydroxyl groups of the PO molecule are replaced by an alkyl or aryl group. According to the number of substituted alkyl groups, they can be classified into alkylphosphonic acids RP (O) (OH)2And dialkylphosphonic acids R2P (O) OH, in particular the former, the latter being dialkylphosphinic acids.
The phosphonic acid has a molecular structure containing carbon-phosphorus bonds, has very high thermal stability and can be broken only at very high temperature.
Phosphonic acid has the characteristics of dibasic acid, can perform neutralization reaction with alkaline compounds and esterification reaction with alcohol, and has wide application, especially in the flame retardant industry.
For example, phosphonic acid can be neutralized with melamine to form P, N-containing flame retardants; phosphonic acid can react with dibasic acid and dihydric alcohol to generate saturated or unsaturated polyester, and the molecular structure of the polyester contains phosphonate ester units and has intrinsic flame retardance.
The phosphonic acid downstream product is used as a flame retardant, has excellent compatibility with organic polymer materials, does not precipitate, does not absorb moisture, has high flame retardant efficiency due to the addition of phosphorus element, is environment-friendly, is favored by users, and is especially suitable for high-end users.
Phosphonic acid is generally prepared by using trialkyl phosphite as a starting material and by preparing dialkyl alkylphosphonate through Arbuzov rearrangement and hydrolyzing the dialkyl alkylphosphonate to obtain phosphonic acid. Among them, the rearrangement process is very mature, and the hydrolysis process is rarely studied.
With the development and progress of society, the market demands for high-end flame retardants more and more, and the research and development of phosphonic acid downstream flame retardants are called, but the difficulty in the source of phosphonic acid is always a bottleneck problem restricting the development of phosphonic acid downstream flame retardants.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the problem that the phosphonic acid source which restricts the development of the phosphonic acid downstream flame retardant is difficult, a phosphonate ester hydrolysis device is researched and designed, and a scientific and reasonable use method is determined.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a phosphonate ester hydrolysis device comprises a hydrolysis kettle 1, an overhead tank 2, a packed tower 3, a condenser 4 and a receiving tank 5; a process water inlet at the top of the hydrolysis kettle 1 is connected with a process water outlet at the bottom of the elevated tank 2 through a sight glass 16 and a drip valve 21 in sequence, a balance port at the top of the elevated tank 2 is connected with a balance port at the top of the hydrolysis kettle 1 through a balance valve 18, an ascending gas port at the top of the hydrolysis kettle 1 is connected with a steam inlet at the side lower part of the packed tower 3, a liquid outlet at the bottom of the packed tower 3 is connected with a reflux port at the top of the hydrolysis kettle 1, a steam outlet at the top of the packed tower 3 is connected with a steam inlet of the condenser 4 through a top temperature thermometer 24, a condensate outlet of the condenser 4 is connected with a reflux port at the side upper part of the packed tower 3 through a sight glass 27 and a reflux valve 28 in sequence, and a fraction inlet valve 29 connected with a fraction inlet at the top of the receiving tank 5 is arranged at the downstream of the sight glass 27; the hydrolysis kettle 1 is an open type stirring container with a thermometer sleeve and a stirrer arranged inside and a jacket arranged outside, a discharge port at the bottom is connected with a discharge pipe through a discharge valve 10, a feed inlet at the top is connected with a feed pipe through a feed valve 15, a thermometer sleeve port at the top is inserted into a kettle thermometer 17, a stirring port at the center of the top is inserted into a stirring shaft connected with a stirring motor (19), a pressure measuring port at the top is connected with a kettle pressure gauge 20, an inlet and an outlet at the lower part of the jacket are divided into three parts, one part is connected with a circulating water upper water pipe through a circulating water inlet valve 6, the other part is connected with a steam water drain pipe through a drain valve 7, the other part is connected with a condensate pipe through a front drain valve 8 and a drain valve 9 sequentially, water inlets and outlets at the upper part of the jacket are also divided into three parts, one part is connected with a circulating water return pipe through a circulating water outlet valve 13, the other part is connected with a steam pipe through a steam valve 12, and the other part is connected with a steam pipe sequentially through a steam pressure gauge 11 and a steam pressure gauge 11, The emptying valve 14 is connected with an emptying pipe; the elevated tank 2 is a vertical elliptic seal head storage tank, a glass tube liquid level meter is arranged on the outer side of the elevated tank, a process water inlet at the top is connected with a water feeding pipe through a water feeding valve 22, and an emptying port is connected with an emptying pipe through an emptying valve 23; the packed tower 3 is an elliptical end enclosure container and is filled with random packing; the condenser 4 is a tubular heat exchanger, a material passes through a tube pass, cooling water passes through a shell pass, a cooling water inlet at the lower part is connected with a circulating water upper water pipe through a circulating water inlet valve 26, and a cooling water outlet at the upper part is connected with a circulating water return pipe through a circulating water outlet valve 25; the receiving tank 5 is a vertical elliptic seal head storage tank, a glass tube liquid level meter is arranged on the outer side of the receiving tank, a vent pipe is connected with a vent hole at the top, and a discharge hole at the bottom is connected with a fraction conveying pipe through a fraction outlet valve 30.
The use method of the device is as follows:
(1) preparing: checking to confirm that a stirring motor 19, a steam pressure gauge 11, a kettle pressure gauge 20, a kettle temperature thermometer 17 and a top temperature thermometer 24 are in a good state, opening an emptying valve 23 and a fraction inlet valve 29, checking to confirm that other valves are in a closed state, opening a feeding valve 15 to add phosphonate and catalyst into a hydrolysis kettle 1, wherein the mass of the catalyst is 0.5-40% of that of the phosphonate, so that the charging coefficient is 0.6-0.8, closing the feeding valve 15, opening a water adding valve 22 to supplement and add process water into an elevated tank 2 until the charging coefficient is 0.85-0.95, closing the water adding valve 22, checking to confirm that the steam and circulating water are normally supplied;
(2) hydrolysis: opening a circulating water inlet valve 26 and a circulating water outlet valve 25 of a condenser 4, introducing circulating water to the shell pass of the condenser 4, closing an emptying valve 23 of a head tank 2, starting a stirring motor 19, opening a hydrophobic front valve 8 and a steam valve 12, introducing steam to a jacket of a hydrolysis kettle 1 for heating, opening a balance valve 18 and a dropping valve 21 when a kettle temperature thermometer 17 displays the temperature of 140 ℃, dropping process water into the hydrolysis kettle 1 to start hydrolysis reaction, opening a reflux valve 28, controlling the opening degree of the steam valve 12 and the dropping valve 21 to ensure that the material temperature in the hydrolysis kettle is 140-150 ℃ in the dropping hydrolysis reaction process, controlling the opening degree of the reflux valve 28 to ensure that the top temperature of a filler is 63-66 ℃, controlling the molar ratio of raw materials to be water phosphonate = 2-20: 1, and periodically dropping for 20-100 hours, opening a discharging valve 10 at the bottom of the hydrolysis kettle 1 during the period to sample and detect the acid value, and when the acid value tends to be stable and unchanged, after the hydrolysis reaction is finished, closing the balance valve 18 and the water dropping valve 21 to stop water dropping, continuing the reaction for 1-2 hours, and closing the steam valve 12 to stop heating;
(3) discharging: opening a purge valve 7, discharging steam in a jacket of the hydrolysis kettle 1, closing the purge valve 7 and a water drainage front valve 8, opening a circulating water inlet valve 6 and a circulating water outlet valve 13 of the jacket of the hydrolysis kettle 1, introducing circulating water into the jacket for cooling, closing the circulating water inlet valve 6 and the circulating water outlet valve 13 when a kettle temperature thermometer 17 shows that the temperature is reduced to be below 40 ℃, fully opening a reflux valve 28, opening a discharge valve 10, discharging a hydrolysis product, closing the reflux valve 28 and the discharge valve 10 after discharging, opening a fraction outlet valve 30, discharging fractions, closing the fraction outlet valve 30, opening a purge valve 14 and a purge valve 7 of the jacket of the hydrolysis kettle 1, purging water in the jacket of the hydrolysis kettle 1, and closing the purge valve 14 and the purge valve 7 to prepare for next batch production.
The process water is deionized water, including distilled water, steam condensate or reverse osmosis water.
The steam is low-pressure saturated steam of 0.5-0.6 MPa.
The circulating water is circulating cooling water at normal temperature.
The phosphonate is one of dimethyl methylphosphonate, dimethyl ethylphosphonate, dimethyl propylphosphonate, dimethyl phenylphosphonate and dimethyl benzylphosphonate.
The catalyst is one of sulfuric acid, phosphoric acid, polyphosphoric acid, benzenesulfonic acid, methyl phosphoric acid, ethyl phosphonic acid, propyl phosphonic acid, phenyl phosphonic acid and benzyl phosphonic acid.
The acid number is the acid number of the hydrolysis mixture minus water.
The invention has the beneficial effects that: (1) continuously dripping water, continuously evaporating and removing a byproduct methanol, and integrally and semi-continuously operating, so that a reaction mixture can be maintained at a higher reaction temperature, the reaction rate is high, and the production efficiency is improved; (2) reaction-rectification coupling, namely rectifying the methanol during the reaction, wherein the methanol content is high, and the methanol can be directly applied to producing trimethyl phosphite, so that energy is saved and consumption is reduced; (3) the hydrolysis kettle jacket is designed to switch between steam and circulating water, has heating and cooling functions, realizes multiple functions of one kettle, and reduces equipment investment; (4) the top temperature of the rectification tower can be conveniently controlled by reflux of the top of the rectification tower through a reflux valve, a flowmeter is omitted, and the operation is convenient and simple.
The present invention will be described in further detail with reference to the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic structural view of a phosphonate ester hydrolyzing apparatus of the present invention
In the figure: 1. the system comprises a hydrolysis kettle, 2, an elevated tank, 3, a packed tower, 4, a condenser, 5, a receiving tank, 6, a circulating water inlet valve, 7, a purge valve, 8, a hydrophobic front valve, 9, a drain valve, 10, a discharge valve, 11, a steam pressure gauge, 12, a steam valve, 13, a circulating water outlet valve, 14, a vent valve, 15, a feeding valve, 16, a sight glass, 17, a kettle temperature thermometer, 18, a balance valve, 19, a stirring motor, 20, a kettle pressure gauge, 21, a drip valve, 22, a water adding valve, 23, a vent valve, 24, a top temperature thermometer, 25, a circulating water outlet valve, 26, a circulating water inlet valve, 27, a sight glass, 28, a reflux valve, 29, a fraction inlet valve, 30 and a fraction outlet valve.
Detailed Description
As shown in figure 1, the phosphonate ester hydrolysis device comprises a hydrolysis kettle 1, an overhead tank 2, a packed tower 3, a condenser 4 and a receiving tank 5.
The process water inlet at the top of the hydrolysis kettle 1 is connected with the process water outlet at the bottom of the elevated tank 2 through a sight glass 16 and a drip valve 21 in sequence, the balance port at the top of the elevated tank 2 is connected with the balance port at the top of the hydrolysis kettle 1 through a balance valve 18, the ascending gas port at the top of the hydrolysis kettle 1 is connected with the steam inlet at the lower part of the side of the packed tower 3, the liquid outlet at the bottom of the packed tower 3 is connected with the reflux port at the top of the hydrolysis kettle 1, the steam outlet at the top of the packed tower 3 is connected with the steam inlet of the condenser 4 through a bimetal type top temperature thermometer 24, the condensate outlet of the condenser 4 is connected with the reflux port at the upper part of the side of the packed tower 3 through a sight glass 27 and a reflux valve 28, and a.
The hydrolysis kettle 1 is a 500L glass-lined open type stirring container with a thermometer sleeve and a stirrer arranged inside and a jacket arranged outside, a discharge port at the bottom is connected with a discharge pipe through a discharge valve 10, a feed inlet at the top is connected with a feed pipe through a feed valve 15, a bimetallic thermometer 17 is inserted into a thermometer sleeve port at the top, a stirring port at the center of the top is inserted into a stirring shaft connected with a stirring motor 19, a pressure measuring port at the top is connected with a diaphragm type pressure gauge 20, an inlet and an outlet at the lower part of the jacket are divided into three parts, one part is connected with a circulating water upper water pipe through a circulating water inlet valve 6, the other part is connected with a steam water discharge pipe through a discharge valve 7, the other part is connected with a condensate pipe through a front drain valve 8 and a drain valve 9 sequentially, water inlets at the upper part of the jacket are also divided into three parts, one part is connected with a circulating water return pipe through a circulating water outlet valve 13, the other part is connected with a steam pipe through a steam valve 12, the other part is connected with a steam pipe sequentially connected with the diaphragm type pressure gauge 11, The blow valve 14 is connected with a blow pipe.
Elevated tank 2 is the vertical oval head basin of 300L of warding off glass material, and the outside is equipped with the glass pipe level gauge, and the process water entry at top is connected the filler pipe through water valve 22, and the drain passes through atmospheric valve 23 and connects the blow-down pipe.
The packed tower 3 is an elliptic end enclosure container which is made of glass lining materials and has the diameter of 200mm and the height of 3m, and ceramic phi 25 pall ring random packing is filled in the container.
The condenser 4 is 3m made of 316L stainless steel2The shell pass is walked to the material to shell pass, and the cooling water inlet of lower part passes through circulating water inlet valve 26 and connects the circulating water inlet pipe, and the cooling water outlet of upper portion passes through circulating water outlet valve 25 and connects the circulating water wet return.
The receiving tank 5 is a 300L vertical elliptical head storage tank made of 304 stainless steel, a glass tube liquid level meter is arranged on the outer side of the receiving tank, a vent pipe is connected with a vent hole at the top, and a discharge hole at the bottom is connected with a fraction conveying pipe through a fraction outlet valve 30.
The process water is deionized water obtained by a distillation method, namely distilled water.
The steam is low-pressure saturated steam of 0.5-0.6 MPa.
The circulating water is circulating cooling water with the temperature of 5-40 ℃.
The phosphonate is dimethyl methylphosphonate or dimethyl propylphosphonate.
The catalyst is a phosphonate ester hydrolysate, i.e., methylphosphonic acid or propylphosphonic acid.
The acid number is the acid number of the hydrolysis mixture determined by subtracting the water content from the sample.
The method of use of the device is described in examples 1-2 below.
Example 1
(1) Preparing: checking to confirm that a stirring motor 19, a steam pressure gauge 11, a kettle pressure gauge 20, a kettle temperature thermometer 17 and a top temperature thermometer 24 are in a good state, opening an emptying valve 23 and a fraction inlet valve 29, checking to confirm that other valves are in a closed state, opening a feeding valve 15, adding 300kg of dimethyl methyl phosphonate and 75kg of methyl phosphonate catalyst (the charging coefficient is 0.75 and the catalyst quantity is 20% of phosphonate) into a hydrolysis kettle 1, closing the feeding valve 15, opening a water adding valve 22, supplementing and adding 270L of process water (the charging coefficient is 0.9) into an elevated tank 2, closing the water adding valve 22, checking to confirm that the steam and circulating water are normally supplied;
(2) hydrolysis: opening a circulating water inlet valve 26 and a circulating water outlet valve 25 of a condenser 4, introducing circulating water to the shell pass of the condenser 4, closing an emptying valve 23 of a head tank 2, starting a stirring motor 19, opening a hydrophobic front valve 8 and a steam valve 12, introducing steam to a jacket of a hydrolysis kettle 1 for heating, opening a balance valve 18 and a dropping valve 21 when a kettle temperature thermometer 17 displays the temperature of 140 ℃, dropping process water into the hydrolysis kettle 1 to start hydrolysis reaction, opening a reflux valve 28, controlling the opening degree of the steam valve 12 and the dropping valve 21 to ensure that the material temperature in the hydrolysis kettle is 140-145 ℃ in the dropping hydrolysis reaction process, controlling the opening degree of the reflux valve 28 to ensure that the top temperature of a filler is 63-65 ℃, periodically opening a discharging valve 10 at the bottom of the hydrolysis kettle 1 during the dropping hydrolysis reaction process to sample and detect the acid value, and when 240kg of process water (mole ratio of raw materials: phosphonate =5.37: 1) is dropped for 86 hours, the acid value tends to be stabilized at 1160mgKOH/g, the hydrolysis reaction is finished, the balance valve 18 and the water dropping valve 21 are closed to stop dropping water, the reaction is continued for 2 hours, the steam valve 12 is closed to stop heating;
(3) discharging: opening a purge valve 7, discharging steam in a jacket of the hydrolysis kettle 1, closing the purge valve 7 and a water-repellent front valve 8, opening a circulating water inlet valve 6 and a circulating water outlet valve 13 of the jacket of the hydrolysis kettle 1, introducing circulating water into the jacket for cooling, closing the circulating water inlet valve 6 and the circulating water outlet valve 13 when a kettle temperature thermometer 17 shows that the temperature is reduced to be below 40 ℃, fully opening a return valve 28, opening a discharge valve 10, discharging hydrolysis products to obtain 460kg of methylphosphonic acid with the concentration of 66.5%, closing the return valve 28 and the discharge valve 10, opening a fraction outlet valve 30 to discharge fractions to obtain 156.5kg of recovered methanol with the content of 99%, closing a fraction outlet valve 30, opening a purge valve 14 and a purge valve 7 of the jacket of the hydrolysis kettle 1, purging the water in the jacket of the hydrolysis kettle 1, and closing the purge valve 14 and the purge valve 7 for preparing for the next batch of production.
Example 2
(1) Preparing: checking to confirm that a stirring motor 19, a steam pressure gauge 11, a kettle pressure gauge 20, a kettle temperature thermometer 17 and a top temperature thermometer 24 are in a good state, opening an emptying valve 23 and a fraction inlet valve 29, checking to confirm that other valves are in a closed state, opening a feeding valve 15, adding 280kg of dimethyl propyl phosphonate and 70kg of propyl phosphonic acid catalyst (the charging coefficient is 0.70, and the quantity of the catalyst is 25 percent of phosphonate mass) into a hydrolysis kettle 1, closing the feeding valve 15, opening a water adding valve 22, supplementing and adding process water to 270L (the charging coefficient is 0.9) into an overhead tank 2, closing the water adding valve 22, checking to confirm that the steam and circulating water are normally supplied;
(2) hydrolysis: opening a circulating water inlet valve 26 and a circulating water outlet valve 25 of a condenser 4, introducing circulating water to the shell pass of the condenser 4, closing an emptying valve 23 of an elevated tank 2, starting a stirring motor 19, opening a hydrophobic front valve 8 and a steam valve 12, introducing steam to a jacket of a hydrolysis kettle 1 for heating, opening a balance valve 18 and a dropping valve 21 when a kettle temperature thermometer 17 displays the temperature of 145 ℃, dropping process water into the hydrolysis kettle 1 to start hydrolysis reaction, opening a reflux valve 28, controlling the opening degrees of the steam valve 12 and the dropping valve 21 to ensure that the material temperature in the hydrolysis kettle is 145-150 ℃ in the dropping hydrolysis reaction process, controlling the opening degree of the reflux valve 28 to ensure that the top temperature of a filler is 63-65 ℃, periodically opening a discharging valve 10 at the bottom of the hydrolysis kettle 1 during the dropping hydrolysis reaction to sample and detect the acid value, and when dropping 220kg of process water (mole ratio of the raw materials: phosphonate =6.63: 1) for 84 hours, the acid value tends to be stabilized at 900mgKOH/g, the hydrolysis reaction is finished, the balance valve 18 and the water dropping valve 21 are closed to stop dropping water, the reaction is continued for 1.5h, and the steam valve 12 is closed to stop heating;
(3) discharging: opening a purge valve 7, discharging steam in a jacket of a hydrolysis kettle 1, closing the purge valve 7 and a drain front valve 8, opening a circulating water inlet valve 6 and a circulating water outlet valve 13 of the jacket of the hydrolysis kettle 1, introducing circulating water into the jacket for cooling, closing the circulating water inlet valve 6 and the circulating water outlet valve 13 when a kettle temperature thermometer 17 shows that the temperature is reduced to be below 40 ℃, fully opening a reflux valve 28, opening a discharge valve 10, discharging hydrolysate to obtain 452kg of propyl phosphonic acid with the concentration of 66%, closing the reflux valve 28 and the discharge valve 10, opening a fraction outlet valve 30 to discharge fraction to obtain 119kg of recovered methanol with the content of 99%, closing the fraction outlet valve 30, opening a purge valve 14 and a purge valve 7 of the jacket of the hydrolysis kettle 1, purging the water in the jacket of the hydrolysis kettle 1, and closing the purge valve 14 and the purge valve 7 to prepare for the next production batch.
Claims (6)
1. The phosphonate ester hydrolysis process is characterized in that phosphonate ester is one of dimethyl methylphosphonate, dimethyl ethylphosphonate, dimethyl propylphosphonate, dimethyl phenylphosphonate and dimethyl benzylphosphonate; the adopted hydrolysis device comprises a hydrolysis kettle (1), an elevated tank (2), a packed tower (3), a condenser (4) and a receiving tank (5); a process water inlet at the top of the hydrolysis kettle (1) is connected with a process water outlet at the bottom of the elevated tank (2) through a sight glass (16) and a water dropping valve (21) in sequence, a balance port at the top of the elevated tank (2) is connected with a balance port at the top of the hydrolysis kettle (1) through a balance valve (18), an ascending gas port at the top of the hydrolysis kettle (1) is connected with a steam inlet at the side lower part of the packed tower (3), a liquid outlet at the bottom of the packed tower (3) is connected with a reflux port at the top of the hydrolysis kettle (1), a steam outlet at the top of the packed tower (3) is connected with a steam inlet of the condenser (4) through a top temperature thermometer (24), a condensate outlet of the condenser (4) is connected with a reflux port at the side upper part of the packed tower (3) through a sight glass (27) and a reflux valve (28) in sequence, and a fraction inlet connected to the top of the receiving tank (5) via a fraction inlet valve (29) is branched off downstream of the sight glass (27); the hydrolysis kettle (1) is an open type stirring container with a thermometer sleeve and a stirrer arranged inside, a jacket is arranged outside the open type stirring container, a discharge hole at the bottom is connected with a discharge pipe through a discharge valve (10), a feed inlet at the top is connected with a feed pipe through a feed valve (15), a thermometer sleeve opening at the top is inserted into a kettle thermometer (17), a stirring opening at the center of the top is inserted into a stirring shaft connected with a stirring motor (19), a pressure measuring opening at the top is connected with a kettle pressure gauge (20), an inlet and an outlet at the lower part of the jacket are divided into three parts, one part is connected with a circulating water upper water pipe through a circulating water inlet valve (6), one part is connected with a steam water discharge pipe through a discharge valve (7), the other part is connected with a condensate water pipe through a drainage front valve (8) and a drain valve (9) in sequence, a water inlet and a water outlet at the upper part are also divided into three parts, and the other part is connected with a circulating water pipe through a circulating water outlet valve (13), one branch is connected with a steam pipe through a steam valve (12), and the other branch is connected with an emptying pipe through a steam pressure gauge (11) and an emptying valve (14) in sequence; the elevated tank (2) is a vertical elliptic seal head storage tank, a glass tube liquid level meter is arranged on the outer side of the elevated tank, a process water inlet at the top is connected with a water feeding pipe through a water feeding valve (22), and an emptying port is connected with an emptying pipe through an emptying valve (23); the packed tower (3) is an oval end enclosure container and is filled with random packing; the condenser (4) is a shell-and-tube heat exchanger, the material passes through a tube pass, the cooling water passes through a shell pass, a cooling water inlet at the lower part is connected with a circulating water upper water pipe through a circulating water inlet valve (26), and a cooling water outlet at the upper part is connected with a circulating water return pipe through a circulating water outlet valve (25); the receiving tank (5) is a vertical elliptic seal head storage tank, a glass tube liquid level meter is arranged on the outer side of the receiving tank, a vent hole at the top is connected with a vent pipe, and a discharge hole at the bottom is connected with a fraction conveying pipe through a fraction outlet valve (30);
the hydrolysis process comprises the following steps:
1) preparing: checking and confirming that a stirring motor (19), a steam pressure gauge (11), a kettle pressure gauge (20), a kettle temperature thermometer (17) and a top temperature thermometer (24) are in a good state, opening an emptying valve (23) and a fraction inlet valve (29), checking and confirming that other valves are in a closed state, opening a feeding valve (15) to add phosphonate and a catalyst into a hydrolysis kettle (1), wherein the mass of the catalyst is 0.5-40% of that of the phosphonate, so that the charging coefficient is 0.6-0.8, closing the feeding valve (15), opening a water adding valve (22) to supplement and add process water into an elevated tank (2) until the charging coefficient is 0.85-0.95, closing the water adding valve (22), checking and confirming that the steam and circulating water are normally supplied;
2) hydrolysis: opening a circulating water inlet valve (26) and a circulating water outlet valve (25) of a condenser (4), introducing circulating water into the shell pass of the condenser (4), closing an emptying valve (23) of a head tank (2), starting a stirring motor (19), opening a hydrophobic front valve (8) and a steam valve (12), introducing steam into a jacket of a hydrolysis kettle (1) for heating, opening a balance valve (18) and a dropping valve (21) when a kettle temperature thermometer (17) displays that the temperature is 140 ℃, dropping process water into the hydrolysis kettle (1) to start hydrolysis reaction, opening a reflux valve (28), controlling the opening degrees of the steam valve (12) and the dropping valve (21) to enable the material temperature in the hydrolysis kettle to be 140-150 ℃ in the dropping hydrolysis reaction process, controlling the opening degree of the reflux valve (28) to enable the top temperature of a filler to be 63-66 ℃, and controlling the molar ratio of raw materials to be water phosphonate = 2-20: 1, wherein the dropping time is 20-100 hours, opening a discharge valve (10) at the bottom of the hydrolysis kettle (1) periodically during the period, sampling and detecting the acid value, closing a balance valve (18) and a water dropping valve (21) to stop dropping water when the acid value tends to be stable and unchanged, continuing to react for 1-2 h, and closing a steam valve (12) to stop heating;
3) discharging: opening a purge valve (7), discharging steam in a jacket of the hydrolysis kettle (1), closing the purge valve (7) and a drain front valve (8), opening a circulating water inlet valve (6) and a circulating water outlet valve (13) of the jacket of the hydrolysis kettle (1), introducing circulating water into the jacket for cooling, when the kettle thermometer (17) displays that the temperature is reduced to below 40 ℃, a circulating water inlet valve (6) and a circulating water outlet valve (13) are closed, a return valve (28) is fully opened, a discharge valve (10) is opened, a hydrolysate is discharged, after the discharge is finished, the return valve (28) and the discharge valve (10) are closed, a fraction outlet valve (30) is opened, a fraction outlet valve (30) is closed, a jacket vent valve (14) and a drain valve (7) of the hydrolysis kettle (1) are opened, water in the jacket of the hydrolysis kettle (1) is drained, and the drain valve (14) and the drain valve (7) are closed for preparing for the next production batch.
2. The hydrolysis process of claim 1, wherein the process water is deionized water, including distilled water, steam condensate, or reverse osmosis water.
3. The hydrolysis process of claim 1, wherein the steam is low pressure saturated steam of 0.5 to 0.6 MPa.
4. The hydrolysis process according to claim 1, wherein the circulating water is normal-temperature circulating cooling water.
5. The hydrolysis process of claim 1, wherein said catalyst is one of sulfuric acid, phosphoric acid, polyphosphoric acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid.
6. The hydrolysis process of claim 1, wherein the acid number is the acid number of the hydrolysis mixture minus water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010122249.5A CN111318244B (en) | 2020-02-26 | 2020-02-26 | Phosphonate ester hydrolysis device and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010122249.5A CN111318244B (en) | 2020-02-26 | 2020-02-26 | Phosphonate ester hydrolysis device and method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111318244A CN111318244A (en) | 2020-06-23 |
| CN111318244B true CN111318244B (en) | 2021-09-24 |
Family
ID=71165372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010122249.5A Active CN111318244B (en) | 2020-02-26 | 2020-02-26 | Phosphonate ester hydrolysis device and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111318244B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443459C (en) * | 2006-10-28 | 2008-12-17 | 周烜 | Preparation method and device of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction |
| US8524046B2 (en) * | 2010-03-30 | 2013-09-03 | Uop Llc | Distillation column pressure control |
| CN201949861U (en) * | 2010-12-08 | 2011-08-31 | 江苏兄弟维生素有限公司 | Dripping device for producing vitamin B1 intermediate aminopropionitrile |
| CN202173925U (en) * | 2011-07-28 | 2012-03-28 | 上虞帝瑞云涛化工有限公司 | Device for quantitatively throwing raw materials |
| CN205586970U (en) * | 2016-01-21 | 2016-09-21 | 山东蜀中药业有限公司 | Hydrolysis reaction cauldron |
-
2020
- 2020-02-26 CN CN202010122249.5A patent/CN111318244B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111318244A (en) | 2020-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102459091B (en) | Recovery of phosphorus values and salt impurities from aqueous waste streams | |
| SU952110A3 (en) | Process for producing poly(oxyorganophosphate)phosphonate | |
| AU2009239897B2 (en) | Method for the manufacture of aminoalkylene phosphonic acid | |
| CN1134703A (en) | Process for producing N-amino-1-hydroxy-alkyl-idene-1,1-Bisphosphonic acids | |
| CN101108864A (en) | 9, 10- dihydro-9- oxa -10- phosphine hetero- phenanthrene -10- oxide compound and its derivant and method of preparing the same | |
| IE60219B1 (en) | 1-hydroxy-3-(n-methyl-n-propylamino)-1,1-diphosphonic acid, process for the preparation thereof and pharmaceutical compositions containing it | |
| CN111318244B (en) | Phosphonate ester hydrolysis device and method | |
| CN101514253A (en) | Environment-friendly flame-retarded unsaturated polyester resin and preparation method thereof | |
| IE66755B1 (en) | Polymerisation reactor and polymerisation process | |
| JP3270619B2 (en) | Method for producing poly (hydrocarbylene aryl phosphate) composition | |
| CN111793086A (en) | Synthesis method of methylphosphinic acid ester | |
| CN100436460C (en) | Synthetic method for N-phosphonyl methyl imino diacetic acid | |
| KR20000053014A (en) | Use of monosodium iminodiacetic acid solutions in the preparation of n-phosphonomethyliminodiacetic acid | |
| Blackburn et al. | The dealkylation of phosphate and phosphonate esters by lodotrimethylsilane: a mild and selective procedure | |
| Pienaar et al. | Synthesis of alkyl hydrogen alkylphosphonates | |
| CN205419779U (en) | Novel production of high -purity phosphorous oxychloride device | |
| WO2010136573A1 (en) | Method for the manufacture of aminopolyalkylene phosphonic acids | |
| CN106188549A (en) | A kind of poly phosphate oligomer fire retardant and preparation method thereof | |
| US3956431A (en) | Process for forming phosphonate polymers | |
| US4529559A (en) | Process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid | |
| CN1132838C (en) | Process for preparing N,N-diacetate aminomethylene phosphoric acid (diglycerophosphine) | |
| SU481159A3 (en) | The method of producing phosphonic dichlorides | |
| CN111909199B (en) | Resource utilization method for rectification high-boiling residues of diethyl methylphosphonite | |
| SU724528A1 (en) | Method of producing cation-exchange resins | |
| RU2011150947A (en) | METHOD FOR PRODUCING DIALKYL PHOSPHYFES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |