CN114213572B - Production method of polyacrylic acid super absorbent resin - Google Patents

Production method of polyacrylic acid super absorbent resin Download PDF

Info

Publication number
CN114213572B
CN114213572B CN202210042715.8A CN202210042715A CN114213572B CN 114213572 B CN114213572 B CN 114213572B CN 202210042715 A CN202210042715 A CN 202210042715A CN 114213572 B CN114213572 B CN 114213572B
Authority
CN
China
Prior art keywords
primary
horizontal reactor
tank
mixing tank
flash
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
Application number
CN202210042715.8A
Other languages
Chinese (zh)
Other versions
CN114213572A (en
Inventor
张西标
路文学
尹洪清
赵梅梅
刘峰
王振华
李涛
刘莹
杨澜
乔波
王红星
杨国辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yankuang Coal Water Slurry Gasification And Coal Chemical Industry National Engineering Research Center Co ltd
Original Assignee
Yankuang Coal Water Slurry Gasification And Coal Chemical Industry National Engineering Research Center Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yankuang Coal Water Slurry Gasification And Coal Chemical Industry National Engineering Research Center Co ltd filed Critical Yankuang Coal Water Slurry Gasification And Coal Chemical Industry National Engineering Research Center Co ltd
Priority to CN202210042715.8A priority Critical patent/CN114213572B/en
Publication of CN114213572A publication Critical patent/CN114213572A/en
Application granted granted Critical
Publication of CN114213572B publication Critical patent/CN114213572B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/01Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/14Organic medium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a production method of polyacrylic acid super absorbent resin, which is controlled from two aspects of production equipment and production process, adjusts the type and structure of a polymerization reaction kettle for the production equipment, and simultaneously converts the production process of synthesizing the super absorbent resin by an inverse suspension method into a continuous production process by taking a flash tank, a crawler-type vacuum filter and the like as auxiliary equipment, thereby greatly improving the production efficiency and ensuring the uniformity of products; in the secondary polymerization unit, a steam outlet of the flash tank is connected with the secondary horizontal reactor, and steam flashed out from the flash tank is used as a heat source of the secondary horizontal reactor, so that the consumption of heating steam in polymerization reaction is reduced, and the consumption of condensed water in a subsequent condensation process is also reduced. The production process is divided into two times of polymerization, the temperature distribution gradient of different positions in the reaction kettle, the temperature of a plurality of mixing grooves and the like are respectively controlled, and the high-quality polyacrylic water-absorbent resin is obtained by combining the control in the aspect of the production equipment.

Description

Production method of polyacrylic acid super absorbent resin
Technical Field
The invention relates to the field of water-absorbing materials, in particular to a production method of polyacrylic acid super absorbent resin.
Background
The super absorbent resin is mainly applied to diapers, adult incontinence products, female hygiene and the like as an absorbent of water and aqueous solutions. The main preparation methods of the super absorbent resin include an aqueous solution method, an inverse suspension method, a radiation polymerization method, an inverse emulsion polymerization method and the like. Wherein, the reversed phase suspension method is the most advanced synthesis process for synthesizing the super absorbent resin.
At present, the reversed phase suspension method for synthesizing the super absorbent resin is mainly produced by a batch method, and the method is the most advanced technology for synthesizing the super absorbent resin at present. However, the batch production process has a series of disadvantages, such as small production scale, high labor intensity of workers, high labor cost and the like; meanwhile, the intermittent method has more human factors, so that the water absorption performance of the produced polyacrylic acid super absorbent resin has certain difference. Theoretically speaking, the continuous production process can well avoid a series of defects caused by the intermittent production process, and meanwhile, the labor intensity of workers can be reduced, the labor cost is reduced, and the profit margin of enterprises is improved. However, in actual production, how to ensure the smooth operation of the continuous method and ensure the product quality still faces certain technical difficulties.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for producing a polyacrylic acid super absorbent resin, which can realize mass production, reduce production cost, ensure product quality, and reduce energy consumption.
The invention provides a production method of polyacrylic acid super absorbent resin, which utilizes continuous production equipment to produce;
the continuous production apparatus comprises: a primary polymerization unit and a secondary polymerization unit;
the primary polymerization unit includes:
a primary mixing tank; the primary mixing tank comprises a continuous phase mixing tank V101 and a disperse phase mixing tank V102;
a primary horizontal reactor R101 with a feeding hole communicated with a discharging hole of the primary mixing tank;
a primary flash tank V103 with a feeding port communicated with a discharging port of the primary horizontal reactor R101;
a primary condenser E101 with an air inlet communicated with a vapor outlet of the primary flash tank V103;
the primary demixer S101 is communicated with a liquid outlet of the primary condenser E101 through a liquid inlet;
a filter S102 with a feed inlet communicated with a discharge outlet of the primary flash tank V103;
the secondary polymerization unit includes:
a secondary mixing groove V201; the secondary mixing tank V201 is respectively communicated with a solid discharge port of the filter S102 and a discharge port of the dispersed phase mixing tank V102;
a secondary horizontal reactor R201 with a feeding hole communicated with a discharging hole of the secondary mixing groove V201;
a secondary flash tank V202 with a feeding hole communicated with a discharging hole of the secondary horizontal reactor R201;
the feed inlet of the cross-linking unit R202 is communicated with the discharge outlet of the secondary flash tank V202;
a secondary condenser E201 connected to the secondary horizontal reactor R201;
the liquid inlet of the secondary delayer S201 is communicated with the liquid outlet of the secondary condenser E201;
the production process comprises the following steps:
s1, conveying a solvent, a surfactant and a dispersing agent to a continuous phase mixing tank V101 for mixing to obtain a continuous phase; sending the mixed solution of the initiator and the cross-linking agent and the acrylic acid solution to a dispersed phase mixing tank V102 for mixing to obtain a dispersed phase; sending the continuous phase and the dispersed phase to a primary horizontal reactor R101 for primary polymerization reaction to obtain primary reaction liquid;
s2, sending the primary reaction liquid to a primary flash tank V103 for flash separation, wherein the flashed steam and the flashed material run in two paths: the steam which is flashed out enters a primary condenser E101 for cooling, the obtained condensate is sent to a primary delayer S101 for layering and is divided into an organic phase and a water phase, the organic phase is extracted from the top of the primary delayer S101, and the water phase is discharged from the bottom of the primary delayer S101; the flash-evaporated material is sent to a filter S102 for filtering to respectively obtain solid and filtrate;
s3, conveying the solid to a secondary mixing tank V201, conveying the dispersed phase to the secondary mixing tank V201, conveying a solvent into the secondary mixing tank V201, and mixing the three materials in the secondary mixing tank V201 to obtain a mixed solution;
s4, sending the mixed solution to a secondary horizontal reactor R201 for secondary polymerization reaction to obtain a secondary reaction solution;
s5, conveying the secondary reaction liquid to a secondary flash tank V202 for flash separation, and operating the flashed steam and the flashed material in two ways: the steam flashed out is discharged from the top of the secondary flash tank V202; and (3) sending the flash-evaporated material to a crosslinking unit R202, and adding a crosslinking agent solution into the crosslinking unit R202 to perform surface crosslinking treatment on the flash-evaporated material to obtain the polyacrylic acid super absorbent resin.
Preferably, in the continuous production apparatus:
the length-diameter ratio of the primary horizontal reactor R101 is more than 2;
a heating sleeve is arranged on the periphery of the primary horizontal reactor R101;
the temperature of a feed port of the primary horizontal reactor R101 is maintained to be less than or equal to 60 ℃, and the temperature of a discharge port is maintained to be 70-75 ℃;
the discharge hole of the primary horizontal reactor R101 is arranged below the central axis of the primary horizontal reactor R101;
the length-diameter ratio of the secondary horizontal reactor R201 is more than 2;
a heating sleeve is arranged on the periphery of the secondary horizontal reactor R201;
the temperature of the feed port of the secondary horizontal reactor R201 is maintained to be less than or equal to 60 ℃, and the temperature of the discharge port is maintained to be 70-75 ℃;
and a discharge hole of the secondary horizontal reactor R201 is arranged below the central axis of the secondary horizontal reactor R201.
Preferably, in the continuous production apparatus:
a stirring paddle is arranged in the primary horizontal reactor R101;
the stirring rake is multilayer stirring rake, includes: the stirring shaft is connected with a plurality of layers of blades; the stirring shaft is superposed with the central axis of the primary horizontal reactor R101;
the inclination angle of the paddle is 45 degrees; the inclination angle is the angle of the paddle deviating from the cross section of the stirring shaft;
a stirring paddle is arranged in the secondary horizontal reactor R201;
the stirring rake is multilayer stirring rake, includes: the stirring shaft and a plurality of layers of blades connected to the stirring shaft; the stirring shaft is superposed with the central axis of the secondary horizontal reactor R201;
the inclination angle of the paddle is 45 degrees; the inclination angle is the angle of the blade deviating from the cross section of the stirring shaft.
Preferably, in the continuous production apparatus:
the crosslinking unit R202 comprises three crosslinking reaction kettles connected in parallel: a first crosslinking reaction kettle R202-1, a second crosslinking reaction kettle R202-2 and a third crosslinking reaction kettle R202-3;
a discharge hole of the secondary flash tank V202 is respectively communicated with a feed hole of the first crosslinking reaction kettle R202-1, a feed hole of the second crosslinking reaction kettle R202-2 and a feed hole of the third crosslinking reaction kettle R202-3;
in the production process, in the step S5, the flashed material is sequentially sent to the first crosslinking reactor R202-1, the second crosslinking reactor R202-2 and the third crosslinking reactor R202-3, and meanwhile, a crosslinking agent solution is respectively sent to the first crosslinking reactor R202-1, the second crosslinking reactor R202-2 and the third crosslinking reactor R202-3, and the flashed material is subjected to surface crosslinking treatment to obtain the polyacrylic acid super absorbent resin.
Preferably, in the continuous production apparatus:
a steam outlet of the secondary flash tank V202 is communicated with a peripheral heating sleeve of the secondary horizontal reactor R201;
in the production process, in the step S5, after being discharged from the top of the secondary flash tank V202, the flashed vapor is sent to a peripheral heating jacket of the secondary horizontal reactor R201, a part of the vapor stays in the heating jacket to serve as a heat source for heating the secondary horizontal reactor R201, a part of the vapor enters a secondary condenser E201 through the heating jacket for condensation, the obtained condensate is sent to the secondary demixer S201 for demixing, and is divided into two layers, i.e., an organic phase and a water phase, the organic phase is extracted from the top of the secondary demixer S201, and the water phase is discharged from the bottom of the secondary demixer S201.
Preferably, in the continuous production apparatus:
in the primary polymerization unit, the filter S102 is a vacuum filter;
the primary polymerization unit further includes: a settling tank V104 communicated with the filtrate outlet of the filter S102; a solvent recovery device H101 communicated with the supernatant outlet of the settling tank V104;
in the production process, in the step S2, the filtrate is sent to a settling tank V104 for treatment, the obtained supernatant is sent to a solvent recovery device H101, and the obtained sediment is discharged from the settling tank V104.
Preferably, in step S1:
the solvent is selected from one or more of n-heptane, cyclohexane, n-octane, cyclopentane, benzene, toluene and xylene;
the surfactant is one or more selected from sucrose fatty acid ester, sorbitan monolaurate, sorbitan monostearate, acetic acid monolaurate, citric acid monostearate, lactic acid monostearate and polyglycerol fatty acid ester;
the dispersing agent is selected from one or more of maleic anhydride modified ethylene-propylene copolymer, maleic anhydride modified polypropylene, maleic anhydride modified ethylene-propylene copolymer, maleic anhydride modified EPDM (ethylene-propylene-diene-terpolymer), butadiene-maleic anhydride copolymer, oxidized polyethylene, ethylene-acrylic acid copolymer, ethyl cellulose and ethyl hydroxyethyl cellulose;
the mass ratio of the surfactant to the dispersant is 1: 0.5-5;
the mass ratio of the solvent to the surfactant to the total amount of the dispersant is preferably 1: 0.002-0.008;
the temperature of the solvent, the surfactant and the dispersant mixed in the continuous phase mixing tank (V101) is 50-80 ℃.
Preferably, in step S1:
the acrylic acid solution is prepared by the following method: dissolving acrylic acid in water, mixing with a NaOH solution, and carrying out incomplete neutralization reaction to obtain an incompletely neutralized acrylic acid solution;
the neutralization degree of the acrylic acid solution is 50-80%;
the mixed solution of the initiator and the cross-linking agent is an aqueous solution of the initiator and the cross-linking agent;
the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, azobisisobutyronitrile formamide, hydrogen peroxide, lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, di-tert-butyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-alkane hydroperoxide and bis (2-phenoxyethyl) peroxydicarbonate;
the cross-linking agent is selected from one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, polyglycerol diglycidyl ether and N, N' -methylenebis (meth) acrylamide;
the mass concentration of the mixed solution of the initiator and the cross-linking agent is 0.15-0.4%;
the mass ratio of the initiator to the cross-linking agent is 1: 0.05-0.09;
sending the mixed solution of the initiator and the cross-linking agent and the acrylic acid solution to a disperse phase mixing tank V102 for mixing to obtain a disperse phase, and keeping the temperature at 10-25 ℃.
Preferably, in the step S3, the temperature in the secondary mixing bowl V201 is maintained at 20 to 50 ℃.
Preferably, in the continuous production apparatus:
in the primary polymerization unit, an organic phase outlet of a primary delayer S101 is also communicated with a continuous phase mixing tank V101;
in the secondary polymerization unit, an organic phase outlet of a secondary delayer S201 is also communicated with a secondary mixing tank V201;
in the production process, in the step S2, the organic phase is extracted from the top of the primary delayer S101 and then returned to the continuous phase mixing tank V101 for recycling;
in the step S5, the organic phase is extracted from the top of the secondary delayer S201 and then returned to the secondary mixing tank V201 for recycling;
in the step S5, after the surface cross-linking treatment, the method further includes drying the obtained cross-linked product, so as to obtain the polyacrylic acid super absorbent resin.
The production method provided by the invention is controlled from two aspects of production equipment and production process, the type and structure of the polymerization reaction kettle are adjusted for the production equipment, and meanwhile, a production process for synthesizing the super absorbent resin by the reversed phase suspension method is converted into a continuous production process by taking a flash tank, a crawler-type vacuum filter and the like as auxiliary equipment, so that the production efficiency can be greatly improved, the defects of batch production are overcome, and the uniformity of the product is ensured; in the secondary polymerization unit, a steam outlet of the flash tank is connected with the secondary horizontal reactor, and steam flashed from the flash tank is used as a heat source of the secondary horizontal reactor to heat the secondary polymerization reactor, so that the consumption of heating steam in polymerization reaction is reduced, and the consumption of condensed water in a subsequent condensation process is also reduced. The production process is divided into two times of polymerization, the temperature distribution gradients of different positions in the reaction kettle, the temperatures of a plurality of mixing tanks and the like are respectively controlled, and the particle size of the obtained polyacrylic spherical resin particles is uniform by combining the control on the production equipment, so that the good water absorption performance and the good water retention performance are ensured.
The test result shows that the resin particles prepared by the invention are spherical and have no foreign shape, the resin particles are formed by agglomerating a plurality of small spherical resin particles, the absorption capacity to 0.9 percent saline reaches more than 60.5g/g, and the centrifugal water retention capacity reaches more than 30.7 g/g.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic view showing the structure of a continuous production apparatus used in the production process provided by the present invention;
FIG. 2 is an SEM photograph of spherical resin particles obtained in example 1;
FIG. 3 is a graph showing a particle size distribution of spherical resin particles obtained in example 1;
FIG. 4 is an SEM photograph of spherical resin particles obtained in example 2;
FIG. 5 is a graph showing the particle size distribution of the spherical resin particles obtained in example 2.
Detailed Description
The invention provides a production method of polyacrylic acid super absorbent resin, which utilizes continuous production equipment to produce;
the continuous production apparatus comprises: a primary polymerization unit and a secondary polymerization unit;
the primary polymerization unit includes:
a primary mixing tank; the primary mixing tank comprises a continuous phase mixing tank V101 and a disperse phase mixing tank V102;
a primary horizontal reactor R101 with a feeding hole communicated with a discharging hole of the primary mixing groove;
a primary flash tank V103 with a feeding hole communicated with a discharging hole of the primary horizontal reactor R101;
a primary condenser E101 with an air inlet communicated with a vapor outlet of the primary flash tank V103;
a primary delayer S101, the liquid inlet of which is communicated with the liquid outlet of the primary condenser E101;
a filter S102 with a feed inlet communicated with a discharge outlet of the primary flash tank V103;
the secondary polymerization unit includes:
a secondary mixing groove V201; the secondary mixing tank V201 is respectively communicated with a solid discharge port of the filter S102 and a discharge port of the dispersed phase mixing tank V102;
a secondary horizontal reactor R201 with a feeding hole communicated with a discharging hole of the secondary mixing groove V201;
a secondary flash tank V202 with a feeding hole communicated with a discharging hole of the secondary horizontal reactor R201;
the feed inlet of the cross-linking unit R202 is communicated with the discharge outlet of the secondary flash tank V202;
a secondary condenser E201 connected to the secondary horizontal reactor R201;
the liquid inlet of the secondary delayer S201 is communicated with the liquid outlet of the secondary condenser E201;
the production process comprises the following steps:
s1, conveying a solvent, a surfactant and a dispersing agent to a continuous phase mixing tank V101 for mixing to obtain a continuous phase; sending the mixed solution of the initiator and the cross-linking agent and the acrylic acid solution to a dispersed phase mixing tank V102 for mixing to obtain a dispersed phase; sending the continuous phase and the dispersed phase to a primary horizontal reactor R101 for primary polymerization reaction to obtain primary reaction liquid;
s2, sending the primary reaction liquid to a primary flash tank V103 for flash separation, wherein the flashed steam and the flashed material run in two paths: the steam which is flashed out enters a primary condenser E101 for cooling, the obtained condensate is sent to a primary delayer S101 for layering and is divided into an organic phase and a water phase, the organic phase is extracted from the top of the primary delayer S101, and the water phase is discharged from the bottom of the primary delayer S101; the flash-evaporated material is sent to a filter S102 for filtering to respectively obtain solid and filtrate;
s3, conveying the solid to a secondary mixing tank V201, conveying the dispersed phase to the secondary mixing tank V201, conveying a solvent to the secondary mixing tank V201, and mixing the three materials in the secondary mixing tank V201 to obtain a mixed solution;
s4, conveying the mixed solution to a secondary horizontal reactor R201 for secondary polymerization reaction to obtain secondary reaction liquid;
s5, conveying the secondary reaction liquid to a secondary flash tank V202 for flash separation, and operating the flashed steam and the flashed material in two ways: the steam flashed out is discharged from the top of the secondary flash tank V202; and (3) sending the flash-evaporated material to a crosslinking unit R202, and adding a crosslinking agent solution into the crosslinking unit R202 to perform surface crosslinking treatment on the flash-evaporated material to obtain the polyacrylic acid super absorbent resin.
Referring to fig. 1, fig. 1 is a schematic structural view of a continuous production apparatus used in the production method provided by the present invention; wherein, L101 is a first solvent storage tank, P101 is a first solvent delivery pump, L102 is an additive storage tank, P102 is an additive delivery pump, V101 is a continuous phase mixing tank, and P103 is a continuous phase delivery pump; l103 is an acrylic acid solution storage tank, P104 is an acrylic acid solution delivery pump, L104 is an additive mixed solution storage tank, P105 is an additive mixed solution delivery pump, V102 is a disperse phase mixing tank, and P106 is a disperse phase delivery pump; r101 is a primary horizontal reactor, V103 is a primary flash tank, E101 is a primary condenser, S101 is a primary delayer, S102 is a filter, and V104 is a settling tank; l201 is a second solvent storage tank, P201 is a second solvent delivery pump, P202 is a dispersed phase secondary delivery pump, V201 is a secondary mixing tank, R201 is a secondary horizontal reactor, V202 is a secondary flash tank, E201 is a secondary condenser, S201 is a secondary delayer, L202 is a cross-linking agent solution storage tank, P203 is a cross-linking agent solution delivery pump, R202 is a cross-linking unit, R202-1 is a first cross-linking reaction kettle, R202-2 is a second cross-linking reaction kettle, and R202-3 is a third cross-linking reaction kettle; g201 is a drying device.
In the present invention, the continuous production apparatus comprises: a primary polymerization unit and a secondary polymerization unit.
With respect to the primary polymerization unit
According to the present invention, the primary polymerization unit includes a primary mixing tank; the first mixing groove comprises: a continuous phase mixing tank V101 and a dispersed phase mixing tank V102.
In the present invention, the continuous phase mixing tank V101 is used to obtain a continuous phase; the production process comprises the following specific steps: the solvent, the surfactant and the dispersant were sent to a continuous phase mixing tank V101 to be mixed, to obtain a continuous phase.
In the invention, preferably, a stirring paddle is arranged in the continuous phase mixing tank V101; the stirring rake is multilayer stirring rake, includes: the stirring shaft and a plurality of layers of blades connected to the stirring shaft. The materials in the continuous phase mixing tank V101 are uniformly mixed by the stirring action of the stirring paddle.
In the present invention, preferably, the primary polymerization unit further includes: a first solvent storage tank L101 with a discharge port communicated with a feed port of the continuous phase mixing tank V101; and the discharge port of the additive storage tank L102 is communicated with the feed port of the continuous phase mixing tank V101. The solvent is fed into the continuous phase mixing tank V101 through the solvent tank L101, and the mixture of the surfactant and the dispersant is fed into the continuous phase mixing tank V101 through the additive tank L102.
In the present invention, preferably, the primary polymerization unit further includes: a first solvent delivery pump P101 communicating between the solvent tank L101 and the continuous phase mixing tank V101, and an additive delivery pump P102 communicating between the additive tank L102 and the continuous phase mixing tank V101. Materials are respectively conveyed into the continuous phase mixing tank V101 through the first solvent conveying pump P101 and the additive conveying pump P102. In the present invention, preferably, the first solvent delivery pump P101 is a peristaltic pump; the additive delivery pump P102 is a nitrogen pneumatic delivery pump.
In the present invention, the dispersed phase mixing tank V102 is used to obtain a dispersed phase; the production process comprises the following specific steps: sending the mixed solution of the initiator and the cross-linking agent and the acrylic acid solution to a dispersed phase mixing tank V102 for mixing to obtain a dispersed phase.
In the invention, preferably, a stirring paddle is arranged in the disperse phase mixing tank V102; the stirring rake is multilayer stirring rake, includes: the stirring shaft and a plurality of layers of blades connected to the stirring shaft. The materials in the dispersed phase mixing tank V102 are mixed evenly by the stirring action of the stirring paddle.
In the present invention, preferably, the primary polymerization unit further includes: an acrylic acid solution storage tank L103 with a discharge port communicated with the feed port of the dispersed phase mixing tank V102; and the discharge port is communicated with the feed port of the dispersed phase mixing tank V102 to form an additive mixed solution storage tank L104. The acrylic acid solution is fed into the dispersed phase mixing tank V102 through the acrylic acid solution storage tank L103, and the mixed solution of the initiator and the crosslinking agent is fed into the dispersed phase mixing tank V102 through the additive mixed solution storage tank L104.
In the present invention, preferably, the primary polymerization unit further includes: an acrylic acid solution transfer pump P104 communicating between the acrylic acid solution tank L103 and the disperse phase mixing tank V102, and an additive mixed solution transfer pump P105 communicating between the additive mixed solution tank L104 and the disperse phase mixing tank V102. The invention respectively conveys materials into a disperse phase mixing tank V102 through the acrylic acid solution conveying pump P104 and the additive mixed solution conveying pump P105.
According to the present invention, the primary polymerization unit includes: and the feed inlet of the primary horizontal reactor R101 is communicated with the discharge outlet of the primary mixing groove. Specifically, the feed inlet of the primary horizontal reactor R101 is respectively communicated with the discharge outlet of the continuous phase mixing tank V101 and the discharge outlet of the dispersed phase mixing tank V102, that is, the continuous phase mixing tank V101 and the dispersed phase mixing tank V102 are not communicated with each other, and the discharge outlets of the two are both communicated with the feed inlet of the primary horizontal reactor R101.
In the present invention, preferably, the primary polymerization unit further includes: a continuous phase transfer pump P103 communicating between the continuous phase mixing tank V101 and the primary horizontal reactor R101, and a dispersed phase transfer pump P106 communicating between the dispersed phase mixing tank V102 and the primary horizontal reactor R101. The continuous phase in a continuous phase mixing tank V101 is conveyed to a primary horizontal reactor R101 by a continuous phase conveying pump P103, and the dispersed phase in a dispersed phase mixing tank V102 is conveyed to the primary horizontal reactor R101 by a dispersed phase conveying pump P106. In the invention, the continuous phase delivery pump P103 is preferably a metering pump which can deliver the continuous phase quantitatively; the dispersed phase delivery pump P106 is preferably a metering pump, which can deliver the dispersed phase quantitatively.
In the present invention, the primary horizontal reactor R101 is a horizontal reactor, and is fed from one end, and after the primary polymerization reaction is completed in the horizontal reactor, it flows horizontally, and is discharged from the other end. In the invention, the primary horizontal reactor R101 is a horizontal polymerization reactor.
In the present invention, the aspect ratio of the primary horizontal reactor R101 is preferably > 2, and more preferably 2.3 to 2.8.
In the present invention, it is preferable that the discharge port of the primary horizontal reactor R101 is disposed below the central axis of the primary horizontal reactor R101 and near the inner wall of the bottom of the reaction vessel. In the invention, the central axis refers to the central direction from the feeding end to the discharging end.
In the present invention, it is preferable that a heating jacket is disposed at the periphery of the primary horizontal reactor R101, for controlling the temperature of the primary horizontal reactor R101. In the invention, the heating sleeve is provided with a steam inlet, and the primary horizontal reactor R101 can be heated by taking external steam (see Z101 in figure 1) as a heat source. A steam heat source enters a heating sleeve to heat the primary horizontal reactor R101, heat exchange is carried out between steam and the primary horizontal reactor R101, the steam is cooled to form condensate, the condensate is discharged from the heating sleeve, and the discharged condensate refers to N101 in the figure 1. In the present invention, preferably, the heating jacket is provided with a condensate outlet, and condensate formed after heat exchange of the vapor is discharged from the condensate outlet. In the invention, preferably, the steam inlet of the heating jacket is arranged at one end of the heating jacket close to the discharge end of the primary horizontal reactor R101, and the condensate outlet is arranged at the other end of the heating jacket, namely, at one end close to the feed end of the primary horizontal reactor R101; according to the invention, the steam inlet is arranged at the discharge end close to the primary horizontal reactor R101, so that steam enters the heating jacket from the position close to the discharge end, and the steam runs to the feed end along the discharge end at the periphery of the primary horizontal reactor R101, so that the temperature of the discharge end of the primary horizontal reactor R101 is higher, and the temperature of the feed end is lower. In the invention, the temperature of the feeding port of the primary horizontal reactor R101 is preferably controlled to be less than or equal to 60 ℃, more preferably 50-60 ℃, and the temperature of the discharging port is preferably controlled to be 70-75 ℃.
In the invention, preferably, a stirring paddle is arranged in the primary horizontal reactor R101; the stirring rake is multilayer stirring rake, includes: the stirring shaft is connected with a plurality of layers of blades; the stirring shaft is superposed with the central axis of the primary horizontal reactor R101; the inclination angle of the paddle is 45 degrees; the inclination angle is the angle of the blade deviating from the cross section of the stirring shaft, namely the included angle between the blade and the direction perpendicular to the stirring shaft. In a conventional stirring paddle, the paddle is generally perpendicular to the stirring shaft, i.e., the inclination angle is 0 (no inclination). The invention controls the inclination angle of the paddle to be specific 45 degrees, which is beneficial to enabling materials to be uniformly and fully reacted and obtaining products with higher quality and uniform and stable quality, if the inclination angle of the paddle is too small (for example, the paddle is vertical to the stirring shaft, namely the inclination angle is 0), the reaction liquid can be well dispersed, but vortex is formed in the reaction, so that the flow of the reaction liquid in the horizontal direction is not uniform, meanwhile, the flow in the horizontal direction loses power, thereby not only affecting the smooth production but also affecting the quality of the products; if the inclination of paddle is too big, the contained angle of paddle and reaction liquid flow direction is too big, loses stirring effect easily, also can prevent the ascending flow of the horizontal direction of reaction liquid simultaneously, influences production and product quality. In the invention, the paddles of each layer are preferably four-blade paddles.
According to the present invention, the primary polymerization unit includes: and a feeding hole of the primary flash tank V103 is communicated with a discharging hole of the primary horizontal reactor R101. In the present invention, preferably, the primary flash tank V103 is a vacuum flash tank. The production process specifically comprises the following steps: the primary reaction liquid formed after the reaction in the primary horizontal reactor R101 enters a primary flash tank V103 for flash separation, the flash steam ascends and is discharged from a steam outlet, and the flash solid material (incomplete solid and certain liquid) descends and is discharged from a material outlet.
According to the present invention, the primary polymerization unit includes: a primary condenser E101, an air inlet of the primary condenser E101 being in communication with a vapor outlet of the primary flash tank V103. The production process comprises the following specific steps: the vapor flashed in the primary flash tank V103 is discharged and then cooled in the primary condenser E101 to form a condensate.
According to the present invention, the primary polymerization unit includes: and a liquid inlet of the primary delaminating device S101 is communicated with a liquid outlet of the primary condenser E101. The production process specifically comprises the following steps: the condensate formed in the primary condenser E101 enters the primary delayer S101 for delamination and is divided into two layers, namely an organic phase and a water phase, wherein the organic phase is extracted from the top of the primary delayer S101, and the water phase is discharged from the bottom of the primary delayer S101.
In the present invention, it is preferable that the organic phase outlet of the primary delayer S101 is further communicated with the continuous phase mixing tank V101. The production process specifically comprises the following steps: and the organic phase is extracted from the top of the primary delayer S101 and then returned to the continuous phase mixing tank V101 for recycling. The invention is beneficial to reducing the production cost by recycling the organic phase.
In the present invention, it is preferable that the aqueous phase in the primary stratifier S101 is discharged from the bottom of the primary stratifier S101 and sent to a sewage treatment plant (see W101 in fig. 1) for treatment.
According to the present invention, the primary polymerization unit includes: and a feed inlet of the filter S102 is communicated with a discharge outlet of the primary flash tank V103. The production process specifically comprises the following steps: and the material subjected to flash separation by the primary flash tank V103 enters a filter for filtration, the obtained filtrate is discharged from a filtrate outlet, and the obtained solid is discharged from a solid outlet and is sent to a secondary polymerization unit as a raw material in the secondary polymerization unit. In the present invention, it is preferable that the filter S102 is a vacuum filter. In the invention, more preferably, the vacuum filter is a crawler-type vacuum filter; more particularly to a crawler-type vacuum filter with a sealing device.
In the present invention, preferably, the primary polymerization unit further comprises: a settling tank V104 communicated with the filtrate outlet of the filter S102; and the solvent recovery device H101 is communicated with the supernatant outlet of the settling tank V104. The production process specifically comprises the following steps: after being filtered by the filter S102, the obtained filtrate is sent to a settling tank V104 for settling treatment, the formed supernatant is sent to a solvent recovery device H101 for recovery treatment, and the formed sediment is sent to the settling tank V104 for discharge, and can be sent to a sludge treatment plant (see W102 in figure 1) for treatment.
With respect to the secondary polymerization unit
According to the present invention, the secondary polymerization unit includes: and the secondary mixing tank V201 is communicated with a solid discharge port of the filter S102 and a discharge port of the dispersed phase mixing tank V102 respectively. The production process specifically comprises the following steps: the solid material obtained after filtration in the primary polymerization unit by the filter S102 is sent to the secondary mixing tank V201 as the raw material for the secondary polymerization reaction, and simultaneously, the dispersed phase mixing tank V102 in the primary polymerization unit sends the dispersed phase to the secondary mixing tank V201.
In the invention, preferably, a stirring paddle is arranged in the secondary mixing tank V201; the stirring rake is multilayer stirring rake, includes: the stirring shaft and a plurality of layers of blades connected to the stirring shaft. The materials in the secondary mixing groove V201 are uniformly mixed under the stirring action of the stirring paddle.
In the present invention, preferably, the secondary polymerization unit further comprises: and a dispersed phase secondary delivery pump P202 communicating between the dispersed phase mixing tank V102 and the secondary mixing tank V201. The dispersed phase in the dispersed phase mixing tank V102 is sent to the secondary mixing tank V201 by the dispersed phase secondary feed pump P202.
In the present invention, preferably, the secondary polymerization unit further comprises: and the discharge hole is communicated with the feed inlet of the secondary mixing groove V201, and the second solvent storage tank L201 is communicated with the discharge hole. During the production process, the solvent is supplied into the secondary mixing tank V201 through the second solvent storage tank L201. In the present invention, the second solvent tank L201 may be a single solvent tank independent of the primary polymerization unit, or may be the first solvent tank L101 in the primary polymerization unit, that is, a single solvent tank common to the primary polymerization unit.
In the present invention, preferably, the secondary polymerization unit further includes: and a second solvent delivery pump P201 communicating between the second solvent tank L201 and the secondary mixing tank V201. The solvent in the second solvent storage tank L201 is sent to the second mixing tank V201 by the second solvent feed pump P201.
In the production process, the solid material, the dispersion phase and the solvent are sent into a secondary mixing tank V201 to be mixed, and mixed liquid is obtained.
According to the present invention, the secondary polymerization unit includes: and the feed inlet of the secondary horizontal reactor R201 is communicated with the discharge outlet of the secondary mixing groove V201. The production process specifically comprises the following steps: and (3) sending the mixed liquid formed in the secondary mixing tank V201 to a secondary horizontal reactor R201 for secondary polymerization reaction to obtain a reaction liquid.
In the invention, the secondary horizontal reactor R201 is a horizontal reactor, and is fed from one end, and after the secondary polymerization reaction is completed in the horizontal reactor, the secondary horizontal reactor flows horizontally, and is discharged from the other end. In the invention, the secondary horizontal reactor R201 is a horizontal polymerization reactor.
In the present invention, the aspect ratio of the secondary horizontal reactor R201 is preferably > 2, and more preferably 2.3 to 2.8.
In the present invention, preferably, the discharge port of the secondary horizontal reactor R201 is disposed below the central axis of the secondary horizontal reactor R201 and near the inner wall of the bottom of the reaction vessel. In the invention, the central axis refers to the central direction from the feeding end to the discharging end.
In the present invention, preferably, a heating jacket is disposed on the periphery of the secondary horizontal reactor R201 for controlling the temperature of the secondary horizontal reactor R201. In the invention, the heating sleeve is provided with a steam inlet, and steam can be used as a heat source to heat the secondary horizontal reactor R201. And a steam heat source enters a heating sleeve to heat the secondary horizontal reactor R201, heat exchange is carried out between steam and the secondary horizontal reactor R201, and the steam is condensed to form condensate. In the present invention, preferably, the heating jacket is provided with a condensate outlet, and condensate formed after heat exchange of the vapor is discharged from the condensate outlet. In the invention, preferably, the steam inlet of the heating jacket is arranged at one end of the heating jacket close to the discharge end of the secondary horizontal reactor R201, and the condensate outlet is arranged at the other end of the heating jacket, namely, one end close to the feed end of the secondary horizontal reactor R201; according to the invention, the steam inlet is arranged at the discharge end close to the secondary horizontal reactor R201, so that steam enters the heating jacket from the position close to the discharge end, and the steam runs to the feed end along the discharge end at the periphery of the secondary horizontal reactor R201, thereby ensuring that the temperature of the discharge end of the secondary horizontal reactor R201 is higher and the temperature of the feed end is lower. In the invention, the temperature of the feed inlet of the secondary horizontal reactor R201 is preferably controlled to be less than or equal to 60 ℃, more preferably 50-60 ℃, and the temperature of the discharge outlet is preferably controlled to be 70-75 ℃.
In the invention, preferably, a stirring paddle is arranged in the secondary horizontal reactor R201; the stirring rake is multilayer stirring rake, includes: the stirring shaft and a plurality of layers of blades connected to the stirring shaft; the stirring shaft is superposed with the central axis of the secondary horizontal reactor R201; the inclination angle of the paddle is 45 degrees; the inclination angle is the angle of the blade deviating from the cross section of the stirring shaft, namely the included angle between the blade and the direction perpendicular to the stirring shaft. The invention controls the inclination angle of the paddle to be 45 degrees, which is beneficial to the uniform and sufficient reaction of materials and the obtaining of products with higher quality and uniform and stable quality, and if the inclination angle of the paddle is too small or too large, the smooth production and the quality of the products are affected. In the invention, the paddles of each layer are preferably four-blade paddles.
According to the present invention, the secondary polymerization unit includes: and a feed inlet of the secondary flash tank V202 is communicated with a discharge outlet of the secondary horizontal reactor R201. In the present invention, preferably, the secondary flash tank V202 is a vacuum flash tank. The production process comprises the following specific steps: and the secondary reaction liquid formed after the reaction in the secondary horizontal reactor R201 enters a secondary flash tank V202 for flash separation, the flash steam ascends and is discharged from a steam outlet, and the flash solid material descends and is discharged from a material outlet.
In the present invention, preferably, a vapor outlet of the secondary flash tank V202 is communicated with a heating jacket around the secondary horizontal reactor R201, specifically, communicated with a vapor inlet of the heating jacket. The production process specifically comprises the following steps: and (3) carrying out flash separation in the secondary flash tank V202, discharging the flash steam upwards, and sending the flash steam to a heating jacket at the periphery of the secondary horizontal reactor R201 to be used as a heat source.
According to the present invention, the secondary polymerization unit includes: and a secondary condenser E201 connected with the secondary horizontal reactor R201. In the present invention, more specifically, the connection mode of the secondary condenser E201 and the secondary horizontal reactor R201 is: the secondary condenser E201 is communicated with a heating jacket at the periphery of the secondary horizontal reactor R201. The production process comprises the following specific steps: and (2) carrying out flash separation in a secondary flash tank V202, discharging the flashed steam (which is the mixed steam of the organic solvent and water) upwards, sending the flashed steam to a heating jacket on the periphery of a secondary horizontal reactor R201, stopping a part of steam in the heating jacket to serve as a heat source to heat the secondary horizontal reactor R201, and condensing a part of steam in a secondary condenser E201 through the heating jacket to form condensate. The invention takes the steam flashed out from the flash tank as the heat source of the secondary horizontal reactor R201 to heat the secondary polymerization reactor, thereby not only reducing the consumption of heating steam in polymerization reaction, but also reducing the consumption of condensed water in the subsequent condensation process, and further greatly reducing the production cost.
According to the present invention, the secondary polymerization unit includes: and the liquid inlet of the secondary demixer S201 is communicated with the liquid outlet of the secondary condenser E201. The production process specifically comprises the following steps: the condensate formed in the secondary condenser E201 is sent to the secondary delayer S201 for delamination and is divided into two layers, namely an organic phase and a water phase, the organic phase is extracted from the top of the secondary delayer S201, and the water phase is discharged from the bottom of the secondary delayer S201.
In the present invention, it is preferable that the organic phase outlet of the secondary delaminator S201 is also communicated with the secondary mixing groove V201. The production process comprises the following specific steps: and after being extracted from the top of the secondary delaminator S201, the organic phase is returned to the secondary mixing tank V201 for recycling.
In the present invention, it is preferable that the aqueous phase in the secondary stratifier S201 is discharged from the bottom of the secondary stratifier S201 and then sent to a sewage treatment plant (see W201 in fig. 1) for treatment.
According to the present invention, the secondary polymerization unit includes: a cross-linking unit R202 (see the dotted enclosed part in the figure 1), wherein the feed port of the cross-linking unit R202 is communicated with the discharge port of the secondary flash tank V202. The production process specifically comprises the following steps: and the material subjected to flash separation by the secondary flash tank V202 is sent to a crosslinking unit R202 for surface crosslinking treatment.
In the present invention, preferably, the crosslinking unit R202 includes three crosslinking reaction kettles connected in parallel: a first crosslinking reaction kettle R202-1, a second crosslinking reaction kettle R202-2 and a third crosslinking reaction kettle R202-3; and a discharge hole of the secondary flash tank V202 is respectively communicated with a feed hole of the first crosslinking reaction kettle R202-1, a feed hole of the second crosslinking reaction kettle R202-2 and a feed hole of the third crosslinking reaction kettle R202-3. The production process specifically comprises the following steps: the materials subjected to flash separation by the secondary flash tank V202 are sequentially sent to a first crosslinking reaction kettle R202-1, a second crosslinking reaction kettle R202-2 and a third crosslinking reaction kettle R202-3 for reaction.
In the invention, preferably, a stirring paddle is arranged in the first crosslinking reaction kettle R202-1; the stirring rake is multilayer stirring rake, includes: the stirring shaft and a plurality of layers of blades connected to the stirring shaft. The materials in the first crosslinking reaction kettle R202-1 are uniformly mixed through the stirring action of the stirring paddle.
In the invention, preferably, a stirring paddle is arranged in the second crosslinking reaction kettle R202-2; the stirring rake is multilayer stirring rake, includes: the stirring shaft and a plurality of layers of blades connected to the stirring shaft. The materials in the second crosslinking reaction kettle R202-2 are uniformly mixed through the stirring action of the stirring paddle.
In the invention, preferably, a stirring paddle is arranged in the third crosslinking reaction kettle R202-3; the stirring rake is multilayer stirring rake, includes: the stirring shaft and a plurality of layers of blades connected to the stirring shaft. The materials in the third crosslinking reaction kettle R202-3 are uniformly mixed by the stirring action of the stirring paddle.
In the present invention, preferably, the secondary polymerization unit further includes: and a cross-linking agent solution storage tank L202 communicated with the cross-linking unit R202. During production, a crosslinker solution is fed into the crosslinking unit R202 via the crosslinker solution reservoir L202. In the invention, preferably, the discharge port of the cross-linking agent solution storage tank L202 is communicated with the liquid inlet of the first cross-linking reaction kettle R202-1, the liquid inlet of the second cross-linking reaction kettle R202-2 and the liquid inlet of the third cross-linking reaction kettle R202-3 respectively.
In the present invention, preferably, the secondary polymerization unit further comprises: a crosslinking agent solution delivery pump P203 communicated between the crosslinking agent solution storage tank L202 and the crosslinking unit R202; the crosslinking agent solution in the crosslinking agent solution reservoir L202 is sent to the crosslinking unit R202 by the crosslinking agent solution delivery pump P203. The production process specifically comprises the following steps: the material after flash separation of the secondary flash tank V202 is sequentially sent to a first crosslinking reaction kettle R202-1, a second crosslinking reaction kettle R202-2 and a third crosslinking reaction kettle R202-3, meanwhile, a crosslinking agent solution is respectively added into the first crosslinking reaction kettle R202-1, the second crosslinking reaction kettle R202-2 and the third crosslinking reaction kettle R202-3 by a crosslinking agent solution delivery pump P203, and the material after flash separation is subjected to surface crosslinking treatment to form the polyacrylic acid super absorbent resin.
In the present invention, preferably, the secondary polymerization unit further includes: and the drying device G201 is communicated with the discharge port of the crosslinking unit R202. More specifically, the feed inlet of the drying device G201 is respectively communicated with the discharge outlet of the first crosslinking reactor R202-1, the discharge outlet of the second crosslinking reactor R202-2 and the discharge outlet of the third crosslinking reactor R202-3, and receives and dries the polyacrylic acid super absorbent resin generated by the above 3 crosslinking reactors, thereby obtaining the polyacrylic acid super absorbent resin product.
In the continuous production equipment, each connecting pipeline is provided with a valve for controlling the on-off of the material conveying of the corresponding pipeline.
The continuous production equipment provided by the invention adjusts the type and structure of the polymerization reaction kettle, simultaneously uses a flash tank, a crawler-type vacuum filter and the like as auxiliary equipment, converts the production process of synthesizing the super absorbent resin by using the reversed phase suspension method into a continuous production process, and ensures that the product has uniformity. In addition, in the secondary polymerization unit, a steam outlet of the flash tank is connected with the secondary horizontal reactor, and steam flashed by the flash tank is used as a heat source of the secondary horizontal reactor to heat the secondary polymerization reactor, so that not only is the consumption of heating steam in polymerization reaction reduced, but also the consumption of condensed water in a subsequent condensation process is reduced, and the production cost is greatly reduced. In addition, the invention also provides a primary delayer which is communicated with the continuous phase mixing tank, and a secondary delayer which is communicated with the secondary mixing tank, so that the utilized organic phase is separated out and sent back to the preorder unit for recycling, thereby reducing the production cost.
In the invention, the production process of the polyacrylic acid super absorbent resin by using the continuous production equipment comprises the following steps:
s1, conveying a solvent, a surfactant and a dispersing agent to a continuous phase mixing tank V101 for mixing to obtain a continuous phase; sending the mixed solution of the initiator and the cross-linking agent and the acrylic acid solution to a dispersed phase mixing tank V102 for mixing to obtain a dispersed phase; sending the continuous phase and the dispersed phase to a primary horizontal reactor R101 for primary polymerization reaction to obtain primary reaction liquid;
s2, sending the primary reaction liquid to a primary flash tank V103 for flash separation, wherein the flashed steam and the flashed material run in two paths: the steam which is flashed out enters a primary condenser E101 for cooling, the obtained condensate is sent to a primary delayer S101 for layering and is divided into an organic phase and a water phase, the organic phase is extracted from the top of the primary delayer S101, and the water phase is discharged from the bottom of the primary delayer S101; the flash-evaporated material is sent to a filter S102 for filtering to respectively obtain solid and filtrate;
s3, conveying the solid to a secondary mixing tank V201, conveying the dispersed phase to the secondary mixing tank V201, conveying a solvent to the secondary mixing tank V201, and mixing the three materials in the secondary mixing tank V201 to obtain a mixed solution;
s4, conveying the mixed solution to a secondary horizontal reactor R201 for secondary polymerization reaction to obtain secondary reaction liquid;
s5, conveying the secondary reaction liquid to a secondary flash tank V202 for flash separation, and operating the flashed steam and the flashed materials in two ways: the steam flashed out is discharged from the top of the secondary flash tank V202; and (3) sending the flash-evaporated material to a crosslinking unit R202, and meanwhile, conveying a crosslinking agent solution to the crosslinking unit R202 to carry out surface crosslinking treatment on the flash-evaporated material to obtain the polyacrylic acid super absorbent resin.
With respect to step S1
In the invention, the solvent is an organic solvent, preferably one or more of n-heptane, cyclohexane, n-octane, cyclopentane, benzene, toluene and xylene, and more preferably n-heptane. In the present invention, the surfactant is preferably one or more selected from sucrose fatty acid ester, sorbitan monolaurate, sorbitan monostearate, glycerol acetate monolaurate, glycerol citrate monostearate, glycerol lactate monostearate and polyglycerol fatty acid ester, and more preferably sucrose fatty acid ester. The dispersant is preferably one or more of maleic anhydride modified ethylene-propylene copolymer, maleic anhydride modified polypropylene, maleic anhydride modified ethylene-propylene copolymer, maleic anhydride modified EPDM (ethylene-propylene-diene-terpolymer), butadiene-maleic anhydride copolymer, oxidized polyethylene, ethylene-acrylic acid copolymer, ethyl cellulose and ethyl hydroxyethyl cellulose, and more preferably maleic anhydride modified ethylene-propylene copolymer. In the invention, the mass ratio of the surfactant to the dispersant is preferably 1: 0.5-5, and specifically may be 1: 0.5, 1: 1, 1: 2, 1: 3, 1: 4, or 1: 5. In the present invention, the mass ratio of the mixture of the solvent, the surfactant and the dispersant is preferably 1: (0.002 to 0.008). The mixing temperature of the solvent, the surfactant and the dispersant in the continuous phase mixing tank V101 is preferably 50-80 ℃, and specifically can be 50 ℃, 60 ℃, 70 ℃ and 80 ℃. In the present invention, preferably, the mixing process is specifically as follows: the solvent is first fed into the continuous phase mixing tank V101 by the solvent feed pump P101 and heated to a target temperature, and then the mixture of the surfactant and the dispersant is fed into the continuous phase mixing tank V101 by the additive feed pump P102 and sufficiently mixed in the continuous phase mixing tank V101 to obtain a continuous phase.
In the present invention, the acrylic acid solution is preferably prepared by the following method: dissolving acrylic acid in water, mixing with NaOH solution for incomplete neutralization reaction to obtain an incompletely neutralized acrylic acid solution. Wherein the NaOH solution is NaOH aqueous solution. The mass fraction of the NaOH solution is preferably 20-35%. In the present invention, the neutralization degree of the acrylic acid solution is preferably 50% to 80%, and specifically may be 50%, 60%, 70%, or 80%. The neutralization degree of the acrylic acid solution refers to the ratio of the molar amount of sodium acrylate generated by the neutralization reaction to the molar amount of acrylic acid before the neutralization reaction.
In the present invention, the initiator is preferably one or more of sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride (AIBA), azobisisobutyrimidazoline hydrochloride (AIBI), azobisisobutyronitrile formamide (V30), hydrogen peroxide, lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, di-tert-butyl peroxide, cumene hydroperoxide, dicumyl hydroperoxide, p-menthane hydroperoxide, and bis (2-phenoxyethyl) peroxydicarbonate. The cross-linking agent is preferably one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, polyglycerol diglycidyl ether and N, N' -methylenebis (meth) acrylamide. The mixed solution of the initiator and the crosslinking agent is a solution formed by dissolving the initiator and the crosslinking agent in water. In the present invention, the mass concentration of the mixed solution of the initiator and the crosslinking agent is preferably 0.15% to 0.4%. In the present invention, in the mixed solution of the initiator and the crosslinking agent, the mass ratio of the initiator to the crosslinking agent is preferably 1: (0.05 to 0.09). In the present invention, the mass ratio of the mixed solution of the initiator and the crosslinking agent to the acrylic acid solution is preferably (0.15 to 0.35) to 1.
In the present invention, the process for obtaining the dispersed phase is preferably as follows: the acrylic acid solution is sent to the disperse phase mixing tank V102 by an acrylic acid solution delivery pump P104, and the mixed solution of the initiator and the crosslinking agent is sent to the disperse phase mixing tank V102 by an additive mixed solution delivery pump P105, and is fully mixed in the disperse phase mixing tank V102, so that the disperse phase is obtained. In the present invention, the temperature of the dispersed phase in the dispersed phase mixing tank V102 is preferably controlled to 10 to 25 ℃, specifically 10 ℃, 15 ℃, 20 ℃, 25 ℃, and more preferably 15 ℃.
The present invention is not particularly limited to the above order for obtaining the continuous phase and the dispersed phase, and preferably, the continuous phase and the dispersed phase are simultaneously obtained, that is, the continuous phase mixing tank V101 and the dispersed phase mixing tank V102 in fig. 1 are operated simultaneously to obtain the continuous phase and the dispersed phase, respectively, and then are simultaneously transported to the next link. In the present invention, the mass ratio of the continuous phase to the dispersed phase is preferably (1.0 to 1.8): 1.
In the invention, after a continuous phase and a dispersed phase are obtained, the continuous phase and the dispersed phase are sent to a primary horizontal reactor R101 for primary polymerization reaction to obtain a primary reaction liquid. In the present invention, more specifically, the continuous phase in the continuous phase mixing tank V101 is transferred to the primary horizontal reactor R101 by the continuous phase transfer pump P103, and the dispersed phase in the dispersed phase mixing tank V102 is transferred to the primary horizontal reactor R101 by the dispersed phase transfer pump P106, and the continuous phase and the dispersed phase are mixed and reacted in the primary horizontal reactor R101 to form a primary reaction liquid. In the mixing reaction process, a stirring paddle with a specific structure in the primary horizontal reactor R101 is used for stirring, so that the reaction is fully and stably carried out, and the reaction liquid is smoothly pushed.
In the invention, the heating jacket is arranged on the periphery of the primary horizontal reactor R101, and the inlet position and the outlet position of a heat source of the heating jacket are controlled, the length-diameter ratio and the like of the primary horizontal reactor R101 are controlled, and then the inlet temperature and the outlet temperature of the primary horizontal reactor R101 are controlled. In the invention, preferably, the temperature of the feeding port of the primary horizontal reactor R101 is controlled to be less than or equal to 60 ℃, and the temperature of the discharging port is controlled to be 70-75 ℃. In the present invention, the feed port temperature is preferably 50 to 60 ℃ and specifically 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃. The temperature of the discharge port can be 70 deg.C, 71 deg.C, 72 deg.C, 73 deg.C, 74 deg.C, and 75 deg.C.
In the invention, in the process of the primary polymerization reaction, the initiator is heated and decomposed to form primary free radicals, the formed free radicals react with the acrylic acid/sodium acrylate monomer to form monomer free radicals, the monomer free radicals continue to react with the acrylic acid/sodium acrylate to form free radicals with 2 structural units, the free radicals with 2 structural units continue to react with the acrylic acid/sodium acrylate to form free radicals with 3 structural units, and the like, and the reaction is stopped when the acrylic acid/sodium acrylate in the reaction system is completely consumed. Meanwhile, because the cross-linking agent exists in the reaction system, the generated polymer can be agglomerated into small balls under the stirring action, so that the reaction liquid containing the polymer spherical particles is obtained.
With respect to step S2
In the invention, the material which finishes the reaction in the primary horizontal reactor R101 is sent to a primary flash tank V103 for flash separation. In the present invention, the operating condition parameters of the flash tank are preferably: the temperature is 85-98 ℃, and the pressure is-0.03 MPa to-0.05 MPa. The temperature may be 85 deg.C, 86 deg.C, 87 deg.C, 88 deg.C, 89 deg.C, 90 deg.C, 91 deg.C, 92 deg.C, 93 deg.C, 94 deg.C, 95 deg.C, 96 deg.C, 97 deg.C, 98 deg.C. The pressure can be specifically-0.03 MPa, -0.04MPa or-0.05 MPa.
In the invention, flash separation is carried out by a flash tank, and the steam obtained by flash evaporation and the material after flash evaporation are operated in two ways: the steam (mainly organic solvent and water) which is flashed out enters a primary condenser E101 for cooling, the obtained condensate is sent to a primary delayer S101 for layering and is divided into an organic phase layer and a water phase layer, the organic phase is extracted from the top of the primary delayer S101, and the water phase is discharged from the bottom of the primary delayer S101; and (4) sending the flash-evaporated material into a filter S102 for filtering to respectively obtain solid and filtrate.
In the invention, preferably, the organic phase is extracted from the top of the primary delayer S101 and then returned to the continuous phase mixing tank V101 for recycling, which is favorable for reducing the cost. In the present invention, the aqueous phase is discharged from the bottom of the primary demixer S101 and then sent to a sewage treatment plant for treatment.
In the present invention, preferably, the material after flash evaporation is sent to the filter S102 for filtration, and after the solid and the filtrate are obtained respectively, the solid and the filtrate go to: the filtrate is sent to a settling tank V104 for treatment, the obtained supernatant is sent to a solvent recovery device H101, and the obtained sediment is discharged from the settling tank V104. The solid is used as a reaction raw material of a secondary polymerization process and is sent to a secondary polymerization unit.
With respect to step S3
In the invention, three materials are added into a secondary mixing tank V201, specifically: the solid matter separated by filtration in the filter S102 in the preceding step is sent to the secondary mixing tank V201, and at the same time, the dispersed phase is sent to the secondary mixing tank V201, and the solvent is transported into the secondary mixing tank V201.
The dispersed phase refers to the dispersed phase formed in the dispersed phase mixing tank V102 in the primary polymerization unit. In the present invention, when the dispersed phase is fed into the secondary mixing tank V201, the mass ratio of the dispersed phase to the charged solid matter is controlled to 0.8 to 1.5: 1.
Wherein the solvent is an organic solvent, preferably one or more of n-heptane, n-hexane, cyclohexane, n-octane, cyclopentane, benzene, toluene and xylene. In the present invention, the mass ratio of the solvent to the charged solid matter is (5-10): 1.
In the invention, the three materials are fully mixed in the secondary mixing tank V201 to obtain mixed liquid. In the present invention, the temperature in the secondary mixing tank V201 is maintained at 20 to 50 ℃, specifically 20 ℃, 25 ℃,30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, and preferably 30 ℃.
With respect to step S4
In the present invention, after the mixed liquid is obtained in step S3, the mixed liquid is sent to the secondary horizontal reactor R201 to perform a secondary polymerization reaction, thereby obtaining a secondary reaction liquid. In the invention, in the process of mixing reaction, the stirring paddle with a specific structure in the secondary horizontal reactor R201 is used for stirring, so that the reaction is fully and stably carried out and the reaction liquid is smoothly pushed.
In the invention, a heating jacket is arranged on the periphery of the secondary horizontal reactor R201, and the inlet position and the outlet position of a heat source of the heating jacket are controlled, the length-diameter ratio and the like of the secondary horizontal reactor R201 are controlled, and then the inlet temperature and the outlet temperature of the secondary horizontal reactor R201 are controlled. In the invention, preferably, the temperature of the feed inlet of the secondary horizontal reactor R201 is controlled to be less than or equal to 60 ℃, and the temperature of the discharge outlet is controlled to be 70-75 ℃. In the present invention, the feed port temperature is preferably 50 to 60 ℃ and specifically 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃. The temperature of the discharge port can be 70 deg.C, 71 deg.C, 72 deg.C, 73 deg.C, 74 deg.C, and 75 deg.C.
In the present invention, in the secondary polymerization process, the polymer particles produced in the primary polymerization reaction are further subjected to a polymerization reaction to form a polyacrylic acid-based polymer, thereby obtaining a secondary reaction liquid containing polyacrylic acid-based polymer particles.
With respect to step S5
In the invention, the secondary reaction liquid is sent to a secondary flash tank V202 for flash separation. In the present invention, the operating conditions of the secondary flash tank V202 are preferably: the temperature is 82 ℃ to 95 ℃, and the pressure is-0.01 MPa to-0.03 MPa. The temperature can be 82 deg.C, 83 deg.C, 84 deg.C, 85 deg.C, 86 deg.C, 87 deg.C, 88 deg.C, 89 deg.C, 90 deg.C, 91 deg.C, 92 deg.C, 93 deg.C, 94 deg.C, 95 deg.C. The pressure can be-0.01 MPa, -0.02MPa or-0.03 MPa.
In the invention, flash separation is carried out by a flash tank, and the steam obtained by flash separation and the material obtained by flash separation are operated in two ways:
and (2) discharging the flashed steam (mainly organic solvent and water) from the top of the secondary flash tank V202, and then sending the flashed steam to a peripheral heating jacket of a secondary horizontal reactor R201, wherein a part of the steam stays in the heating jacket to be used as a heat source to heat the secondary horizontal reactor R201, a part of the steam enters a secondary condenser E201 through the heating jacket to be condensed, the obtained condensate is sent to a secondary demixer S201 to be demixed and is divided into an organic phase layer and a water phase layer, the organic phase is extracted from the top of the secondary demixer S201, and the water phase is discharged from the bottom of the secondary demixer S201. In the invention, preferably, the organic phase is extracted from the top of the secondary delayer S201 and then returned to the secondary mixing tank V201 for recycling, which is beneficial to reducing the production cost. The water phase is discharged from the bottom of the secondary demixer S201 and then can be sent to a sewage treatment plant for treatment.
And (3) sending the flash-evaporated material to a crosslinking unit R202, and adding a crosslinking agent solution into the crosslinking unit R202 to perform surface crosslinking treatment on the flash-evaporated material, thereby obtaining the polyacrylic acid super absorbent resin. In the present invention, the mass concentration of the crosslinking agent solution is preferably 0.5% to 5%. The cross-linking agent is preferably one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, polyglycerol diglycidyl ether and N, N-methylene bisacrylamide. In the present invention, the ratio of the amount of the crosslinking agent solution to the amount of the material after flash evaporation is preferably 1: 40 to 60. In the crosslinking unit R202, under the action of a crosslinking agent, the flash-evaporated material is added to form a network polymer with more structural units, so that the polyacrylic resin is obtained. In the present invention, the working temperature of the crosslinking unit R202 is preferably 70 to 80 ℃, and specifically 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ and 80 ℃.
In the present invention, the crosslinking unit R202 preferably comprises three crosslinking reaction kettles connected in parallel: the method comprises the following steps of firstly, conveying flash-evaporated materials to a first crosslinking reaction kettle R202-1, a second crosslinking reaction kettle R202-2 and a third crosslinking reaction kettle R202-3 in sequence, conveying a crosslinking agent solution to the first crosslinking reaction kettle R202-1, the second crosslinking reaction kettle R202-2 and the third crosslinking reaction kettle R202-3 respectively, and carrying out surface crosslinking treatment on the flash-evaporated materials to obtain the polyacrylic acid super absorbent resin. The three cross-linking reaction kettles connected in parallel operate simultaneously, the treatment capacity can be increased, the production efficiency is improved, and the phenomenon that the resin particles after flash evaporation form large gel due to long-time storage and aggregation to cause production stop can be avoided.
In the present invention, it is preferable to further perform a drying treatment after the polyacrylic resin is obtained by the surface crosslinking treatment. Specifically, the material produced from the crosslinking unit R202 was sent to the drying apparatus G201 and dried, thereby obtaining a polyacrylic acid resin. In the present invention, the drying temperature is preferably 50 to 80 ℃.
The production method provided by the invention is controlled from two aspects of production equipment and production process, the type and structure of the polymerization reaction kettle are adjusted for the production equipment, meanwhile, a flash tank, a crawler-type vacuum filter and the like are used as auxiliary equipment, the production process for synthesizing the super absorbent resin by the reversed phase suspension method is converted into a continuous production process, the production efficiency can be greatly improved, the defects of batch production are overcome, and the uniformity of the product is ensured. In the secondary polymerization unit, a steam outlet of the flash tank is connected with the secondary horizontal reactor, and steam flashed from the flash tank is used as a heat source of the secondary horizontal reactor to heat the secondary polymerization reactor, so that the consumption of heating steam in polymerization reaction is reduced, and the consumption of condensed water in a subsequent condensation process is also reduced. In addition, the invention also arranges a primary delayer which is communicated with the continuous phase mixing tank and a secondary delayer which is communicated with the secondary mixing tank to separate out the utilized organic phase and send the organic phase back to the preorder unit for recycling, thereby reducing the production cost. The production process is divided into two times of polymerization, the temperature distribution gradients of different positions in the reaction kettle, the temperatures of a plurality of mixing tanks and the like are respectively controlled, and the control in the aspect of production equipment is combined, so that the particle size of the obtained polyacrylic acid series spherical resin particles is uniform, and the good water absorption performance and water retention performance are ensured.
The test result shows that the resin particles prepared by the invention are spherical and have no abnormal shape, the resin particles are formed by agglomerating a plurality of small spherical resin particles, the absorption capacity to 0.9 percent saline reaches more than 60.5g/g, and the centrifugal water retention capacity reaches more than 30.7 g/g.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
1. Preparation of super absorbent resin
The production was carried out by using a continuous production apparatus shown in FIG. 1.
S1, conveying n-heptane into a mixing tank V101 through a pump P101, heating to 60 ℃, conveying a mixture of a surfactant sucrose fatty acid ester (S-370) and a dispersant maleic anhydride modified ethylene-propylene copolymer (H1105A) (wherein the mass ratio of S-370: H1105A is = 1: 1) into the mixing tank V101 through a nitrogen pneumatic conveying pump P102, and fully mixing the materials to obtain a continuous phase. Wherein the mass ratio of the mixture of the n-heptane, the surfactant and the dispersant is = 1: 0.056.
An acrylic acid solution (neutralization degree of 70%) is fed into the mixing tank V102 by a pump P104, and simultaneously, an aqueous solution of an initiator and a crosslinking agent (the mass concentration of the solution is 0.42%, wherein the mass ratio of the initiator to the crosslinking agent is = 1: 0.075; the initiator is potassium persulfate, and the crosslinking agent is ethylene glycol diglycidyl ether) is fed into the mixing tank V102 by a pump P105, and the materials are fully mixed to obtain a dispersed phase, and the dispersed phase is maintained at 15 ℃. Wherein the mass ratio of the acrylic acid solution to the aqueous solution of the initiator to the cross-linking agent is = 1: 0.083.
The continuous phase and the dispersed phase were fed into a single horizontal reactor R101 having a heating jacket (length-to-diameter ratio of 2.3, stirring paddle with stirring paddle in multiple stages, paddle inclination angle of 45 °) by a metering pump P103 and a metering pump P106, respectively, to perform a polymerization reaction, and the inlet temperature and the outlet temperature of the single horizontal reactor R101 were maintained at 50 ℃ and 70 ℃.
S2, discharging reaction liquid which finishes reaction in the primary horizontal reactor R101 from a discharge hole close to the bottom of the primary horizontal reactor R101, entering a vacuum flash tank V103 (the temperature is 85 ℃, and the pressure is-0.03 MPa) for flash separation, and operating the flashed steam and the flashed materials in two ways: and the flashed steam enters a primary condenser E101 for cooling, the obtained condensate is sent to a primary delayer S101 for layering and is divided into an organic phase layer and a water phase layer, the organic phase is extracted from the top of the primary delayer S101 and is sent to a mixing tank V101 for recycling, and the water phase is discharged from the bottom of the primary delayer S101 and is sent to a sewage treatment plant for treatment. The flash-evaporated material is sent to a belt vacuum filter S102 with a sealing device for filtering, and solid and filtrate are respectively obtained; wherein, the filtrate is sent to a settling tank V104 for treatment, the supernatant in the settling tank V104 is sent to a solvent recovery device H101 for recovery treatment, and the sediment is sent to a sludge treatment plant for treatment; the solid matter after filtration was collected and sent to a mixing tank V201 as a reaction raw material in the secondary polymerization process.
S3, feeding the solid obtained in the step S2 into a mixing tank V201, simultaneously feeding n-heptane into the mixing tank V201 through a pump P201, feeding the dispersed phase into the mixing tank V201 through a pump P202, and fully and uniformly mixing the three materials in the mixing tank V201 to obtain a mixed solution, wherein the temperature in the mixing tank V201 is kept at 30 ℃. Wherein the mass ratio of the solid, the n-heptane and the dispersed phase is = 1: 3.68: 0.56.
And S4, conveying the mixed solution into a secondary horizontal reactor R201 with a heating jacket (the length-diameter ratio is 2.5, the mixing paddle is arranged, the mixing paddle is a multilayer mixing paddle, the inclination angle of the paddle is 45 degrees), and performing secondary polymerization, wherein the inlet temperature and the outlet temperature of the secondary horizontal reactor R201 are respectively maintained at 50 ℃ and 70 ℃.
S5, discharging the reaction liquid which finishes the reaction in the secondary horizontal reactor R201 from a discharge hole close to the bottom of the secondary horizontal reactor R201, then entering a vacuum flash tank V202 (with the temperature of 82 ℃ and the pressure of-0.01 MPa) for flash separation, and carrying out two-way operation on the flash steam and the flash material:
and after being discharged from the top of the vacuum flash tank V202, the flashed steam is sent to a peripheral heating jacket of a secondary horizontal reactor R201, part of the steam stays in the heating jacket to be used as a heat source to heat the secondary horizontal reactor R201, part of the steam enters a secondary condenser E201 through the heating jacket to be condensed, the obtained condensate is sent to a secondary delayer S201 to be layered and divided into two layers of an organic phase and a water phase, the organic phase is extracted from the top of the secondary delayer S201 and sent back to the mixing tank V201 to be recycled, and the water phase is discharged from the bottom of the secondary delayer S201 and sent to a sewage treatment plant to be treated.
And (3) sequentially conveying the flash-evaporated material to a first crosslinking reaction kettle R202-1, a second crosslinking reaction kettle R202-2 and a third crosslinking reaction kettle R202-3, simultaneously conveying a crosslinking agent solution to the first crosslinking reaction kettle R202-1, the second crosslinking reaction kettle R202-2 and the third crosslinking reaction kettle R202-3 respectively, and carrying out surface crosslinking treatment on the flash-evaporated material to obtain the polyacrylic acid series super absorbent resin. Wherein the cross-linking agent is ethylene glycol diglycidyl ether, the mass concentration of the cross-linking agent solution is 2 percent, and the mass ratio of the cross-linking agent solution to the flash-evaporated material is 0.05: 1.
2. Product characterization and testing
(1) SEM characterization
The resin particles obtained were observed by a scanning electron microscope, and as a result, see fig. 2, and fig. 2 is an SEM image of the spherical resin particles obtained in example 1. It can be seen that the resulting resin particles were spherical and free from foreign shapes, and the resin particles were formed by agglomeration of a plurality of small spherical resin particles.
(2) Particle size analysis
The obtained spherical resin particles were subjected to size analysis by sieving, and the results are shown in FIG. 3, which is a graph showing the size distribution of the sieved spherical resin particles obtained in example 1. It was found that the obtained spherical resin particles contained 0% of particles having a particle diameter of 150 μm or less, 0.34% of particles having a particle diameter of 150 to 300 μm, and 99.66% of particles having a particle diameter of 300 μm or more.
Example 2
1. Preparation of super absorbent resin
The production was carried out using a continuous production apparatus shown in FIG. 1.
S1, conveying n-heptane into a mixing tank V101 through a pump P101, heating to 70 ℃, conveying a mixture of a surfactant sucrose fatty acid ester and a dispersant maleic anhydride modified polyethylene (wherein the mass ratio of the surfactant to the dispersant = 1: 0.5) into the mixing tank V101 through a nitrogen pneumatic conveying pump P102, and fully mixing the materials to obtain a continuous phase. Wherein the mass ratio of the mixture of the n-heptane, the surfactant and the dispersant is = 1: 0.039.
An acrylic acid solution (neutralization degree of 80%) is fed into the mixing tank V102 by a pump P104, and simultaneously, an aqueous solution of an initiator and a crosslinking agent (the mass concentration of the solution is 0.42%, wherein the mass ratio of the initiator to the crosslinking agent is = 1: 0.075; the initiator is potassium persulfate, and the crosslinking agent is ethylene glycol diglycidyl ether) is fed into the mixing tank V102 by a pump P105, and the materials are fully mixed to obtain a dispersed phase, and the dispersed phase is maintained at 10 ℃. Wherein the mass ratio of the acrylic acid solution to the aqueous solution of the initiator to the cross-linking agent is = 1: 0.083.
The continuous phase and the dispersed phase were fed into a single horizontal reactor R101 having a heating jacket (length-to-diameter ratio of 2.3, stirring paddle with stirring paddle in multiple stages, paddle inclination angle of 45 °) by a metering pump P103 and a metering pump P106, respectively, to perform a polymerization reaction, and the inlet temperature and the outlet temperature of the single horizontal reactor R101 were maintained at 55 ℃ and 73 ℃.
S2, discharging reaction liquid which finishes reaction in the primary horizontal reactor R101 from a discharge hole close to the bottom of the primary horizontal reactor R101, entering a vacuum flash tank V103 (the temperature is 90 ℃, and the pressure is-0.04 MPa) for flash separation, and operating the flashed steam and the flashed materials in two ways: and the flashed steam enters a primary condenser E101 for cooling, the obtained condensate is sent to a primary delayer S101 for layering and is divided into two layers, namely an organic phase and a water phase, the organic phase is extracted from the top of the primary delayer S101 and sent to a mixing tank V101 for recycling, and the water phase is discharged from the bottom of the primary delayer S101 and sent to a sewage treatment plant for treatment. The flash-evaporated material is sent to a belt vacuum filter S102 with a sealing device for filtering, and solid and filtrate are respectively obtained; wherein, the filtrate is sent to a settling tank V104 for treatment, the supernatant in the settling tank V104 is sent to a solvent recovery device H101 for recovery treatment, and the sediment is sent to a sludge treatment plant for treatment; the solid matter after filtration was collected and sent to a mixing tank V201 as a reaction raw material in the secondary polymerization process.
S3, feeding the solid obtained in the step S2 into a mixing tank V201, simultaneously feeding n-heptane into the mixing tank V201 through a pump P201, feeding the dispersed phase into the mixing tank V201 through a pump P202, and fully and uniformly mixing the three materials in the mixing tank V201 to obtain a mixed solution, wherein the temperature in the mixing tank V201 is kept at 30 ℃. Wherein the mass ratio of the solid, the solvent and the dispersed phase is = 1: 3.68: 0.8.
And S4, conveying the mixed solution into a secondary horizontal reactor R201 with a heating jacket (the length-diameter ratio is 2.3, the mixing paddle is arranged, the mixing paddle is a multilayer mixing paddle, the inclination angle of the paddle is 45 degrees), and performing secondary polymerization, wherein the inlet temperature and the outlet temperature of the secondary horizontal reactor R201 are respectively maintained at 55 ℃ and 73 ℃.
S5, discharging the reaction liquid which finishes the reaction in the secondary horizontal reactor R201 from a discharge hole close to the bottom of the secondary horizontal reactor R201, then entering a vacuum flash tank V202 (the temperature is 90 ℃, and the pressure is-0.02 MPa) for flash separation, and carrying out two-way operation on the flash steam and the flash material:
and after being discharged from the top of the vacuum flash tank V202, the flashed steam is sent to a peripheral heating jacket of a secondary horizontal reactor R201, part of the steam stays in the heating jacket to be used as a heat source to heat the secondary horizontal reactor R201, part of the steam enters a secondary condenser E201 through the heating jacket to be condensed, the obtained condensate is sent to a secondary delayer S201 to be layered and divided into two layers of an organic phase and a water phase, the organic phase is extracted from the top of the secondary delayer S201 and sent back to the mixing tank V201 to be recycled, and the water phase is discharged from the bottom of the secondary delayer S201 and sent to a sewage treatment plant to be treated.
And (3) sequentially conveying the flash-evaporated material to a first crosslinking reaction kettle R202-1, a second crosslinking reaction kettle R202-2 and a third crosslinking reaction kettle R202-3, simultaneously conveying a crosslinking agent solution to the first crosslinking reaction kettle R202-1, the second crosslinking reaction kettle R202-2 and the third crosslinking reaction kettle R202-3 respectively, and carrying out surface crosslinking treatment on the flash-evaporated material to obtain the polyacrylic acid series super absorbent resin. Wherein the cross-linking agent is ethylene glycol diglycidyl ether, the mass concentration of the cross-linking agent solution is 2 percent, and the mass ratio of the cross-linking agent solution to the flash-evaporated material is 0.05: 1.
2. Product characterization and testing
(1) SEM characterization
The obtained resin particles were observed by a scanning electron microscope, and as a result, see fig. 4, and fig. 4 is an SEM image of the spherical resin particles obtained in example 2. It can be seen that the resulting resin particles were spherical, free from foreign shapes, and the resin particles were formed by agglomeration of a plurality of small spherical resin particles.
(2) Particle size analysis
The obtained spherical resin particles were subjected to particle size analysis by sieving, and the results are shown in FIG. 5, which is a graph showing the particle size distribution data of the spherical resin particles obtained in example 2. It was found that the spherical resin particles obtained had a particle size of 150 μm or less of 1.39%, particles of 150 to 300 μm of 0.5%, and particles of 300 μm or more of 98.11%.
Example 3
1. Preparation of super absorbent resin
The production was carried out by using a continuous production apparatus shown in FIG. 1.
S1, conveying n-heptane into a mixing tank V101 through a pump P101, heating to 80 ℃, conveying a mixture of surfactant polyglycerol fatty acid ester and dispersant maleic anhydride modified polyethylene (wherein the mass ratio of the surfactant to the dispersant = 1: 1) into the mixing tank V101 through a nitrogen pneumatic conveying pump P102, and fully mixing the materials to obtain a continuous phase. Wherein the mass ratio of the mixture of the n-heptane, the surfactant and the dispersant is = 1: 0.0056.
An acrylic acid solution (neutralization degree of 75%) is fed into the mixing tank V102 by a pump P104, and simultaneously, an aqueous solution of an initiator and a crosslinking agent (the mass concentration of the solution is 0.42%, wherein the mass ratio of the initiator to the crosslinking agent is = 1: 0.075; the initiator is potassium persulfate, and the crosslinking agent is ethylene glycol diglycidyl ether) is fed into the mixing tank V102 by a pump P105, and the materials are fully mixed to obtain a dispersed phase, and the dispersed phase is maintained at 25 ℃. Wherein the mass ratio of the acrylic acid solution to the aqueous solution of the initiator to the cross-linking agent is = 1: 0.083.
The continuous phase and the dispersed phase are respectively conveyed into a primary horizontal reactor R101 with a heating jacket (the length-diameter ratio is 2.5, the stirring paddle is arranged, the stirring paddle is a multilayer stirring paddle, the inclination angle of the paddle is 45 degrees) through a metering pump P103 and a metering pump P106 to carry out primary polymerization reaction, the inlet temperature of the primary horizontal reactor R101 is maintained at 60 ℃, and the outlet temperature is maintained at 75 ℃.
S2, discharging reaction liquid which finishes reaction in the primary horizontal reactor R101 from a discharge hole close to the bottom of the primary horizontal reactor R101, entering a vacuum flash tank V103 (with the temperature of 98 ℃ and the pressure of-0.05 MPa) for flash separation, and operating the flashed steam and the flashed materials in two ways: and the flashed steam enters a primary condenser E101 for cooling, the obtained condensate is sent to a primary delayer S101 for layering and is divided into two layers, namely an organic phase and a water phase, the organic phase is extracted from the top of the primary delayer S101 and sent to a mixing tank V101 for recycling, and the water phase is discharged from the bottom of the primary delayer S101 and sent to a sewage treatment plant for treatment. The flash-evaporated material is sent to a belt vacuum filter S102 with a sealing device for filtering, and solid and filtrate are respectively obtained; wherein, the filtrate is sent to a settling tank V104 for treatment, the supernatant in the settling tank V104 is sent to a solvent recovery device H101 for recovery treatment, and the sediment is sent to a sludge treatment plant for treatment; the solid matter after filtration was collected and sent to the mixing tank V201 as a reaction material in the secondary polymerization process.
S3, feeding the solid obtained in the step S2 into a mixing tank V201, simultaneously feeding n-heptane into the mixing tank V201 through a pump P201, feeding the dispersed phase into the mixing tank V201 through a pump P202, and fully and uniformly mixing the three materials in the mixing tank V201 to obtain a mixed solution, wherein the temperature in the mixing tank V201 is kept at 30 ℃. Wherein the mass ratio of the solid, the solvent and the dispersed phase is = 1: 3.68: 1.
And S4, conveying the mixed solution into a secondary horizontal reactor R201 with a heating jacket (the length-diameter ratio is 2.5, the mixing paddle is arranged, the mixing paddle is a multilayer mixing paddle, the inclination angle of the paddle is 45 degrees), performing secondary polymerization, and maintaining the inlet temperature and the outlet temperature of the secondary horizontal reactor R201 at 60 ℃ and 75 ℃.
S5, discharging the reaction liquid which finishes the reaction in the secondary horizontal reactor R201 from a discharge hole close to the bottom of the secondary horizontal reactor R201, then, carrying out flash separation in a vacuum flash tank V202 (the temperature is 95 ℃ and the pressure is-0.03 MPa), and carrying out flash separation on the flashed steam and the flashed materials in two ways:
and after being discharged from the top of the vacuum flash tank V202, the flashed steam is sent to a peripheral heating jacket of a secondary horizontal reactor R201, part of the steam stays in the heating jacket to be used as a heat source to heat the secondary horizontal reactor R201, part of the steam enters a secondary condenser E201 through the heating jacket to be condensed, the obtained condensate is sent to a secondary delayer S201 to be layered and divided into two layers of an organic phase and a water phase, the organic phase is extracted from the top of the secondary delayer S201 and sent back to the mixing tank V201 to be recycled, and the water phase is discharged from the bottom of the secondary delayer S201 and sent to a sewage treatment plant to be treated.
And (3) sequentially conveying the flash-evaporated material to a first crosslinking reaction kettle R202-1, a second crosslinking reaction kettle R202-2 and a third crosslinking reaction kettle R202-3, simultaneously conveying a crosslinking agent solution to the first crosslinking reaction kettle R202-1, the second crosslinking reaction kettle R202-2 and the third crosslinking reaction kettle R202-3 respectively, and carrying out surface crosslinking treatment on the flash-evaporated material to obtain the polyacrylic acid series super absorbent resin. Wherein the cross-linking agent is ethylene glycol diglycidyl ether, the mass concentration of the cross-linking agent solution is 2 percent, and the mass ratio of the cross-linking agent solution to the flash-evaporated material is 0.1: 1.
2. Product characterization and testing
The obtained resin particles were tested according to the characterization and test method of example 1, and it was revealed that the obtained resin particles were spherical and free from foreign bodies, and the resin particles were formed by agglomeration of a plurality of small spherical resin particles. Particle size sieving data shows that the spherical resin particles account for 7.52% below 150 μm, 3.13% between 150-300 μm, and 89.35% above 300 μm.
Further, the resin particles obtained in examples 1 to 3 were tested for water absorption retention property, wherein the water absorption property was as follows: weighing m 0 Putting the resin particles of =0.200g into physiological saline, soaking for 0.5h at room temperature, taking out and standing for 10min, and weighing the mass m of the resin after water absorption 1 The water absorption of the resin was calculated using the following formula:
Figure BDA0003470930020000261
the water retention was tested as follows: the resin particles after standing for 10min were dehydrated for 3min under a centrifugal force of 250 g. After the centrifugation, the mass m of the resin particles was weighed 2 The water retention of the resin was calculated using the following formula:
Figure BDA0003470930020000262
see table 1 for results.
TABLE 1 Water absorbing and retaining Properties of resin particles obtained in examples 1 to 3
Water absorption capacity, g/g Water retention, g/g
Example 1 69.17 56.17
Example 2 61.87 30.70
Example 3 60.59 32.50
As can be seen from the test results of examples 1 to 3, the resin particles obtained in the present invention were spherical and free from foreign bodies, and the resin particles were formed by agglomeration of a plurality of small spherical resin particles. The water absorption capacity of the resin particles reaches more than 60.5g/g, and the water retention capacity reaches more than 30.7 g/g.
The foregoing examples are included merely to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. The production method of the polyacrylic acid high water absorption resin is characterized in that continuous production equipment is utilized for production;
the continuous production apparatus comprises: a primary polymerization unit and a secondary polymerization unit;
the primary polymerization unit includes:
a primary mixing tank; the primary mixing tank comprises a continuous phase mixing tank (V101) and a disperse phase mixing tank (V102);
a primary horizontal reactor (R101) with a feed inlet communicated with a discharge outlet of the primary mixing groove;
a primary flash tank (V103) with a feed inlet communicated with a discharge outlet of the primary horizontal reactor (R101);
a primary condenser (E101) having an air inlet in communication with the vapor outlet of the primary flash tank (V103);
a primary delayer (S101) with a liquid inlet communicated with a liquid outlet of the primary condenser (E101);
a filter (S102) with a feed inlet communicated with a discharge outlet of the primary flash tank (V103);
the secondary polymerization unit includes:
a secondary mixing groove (V201); the secondary mixing tank (V201) is respectively communicated with a solid discharge port of the filter (S102) and a discharge port of the dispersed phase mixing tank (V102);
a secondary horizontal reactor (R201) with a feeding hole communicated with a discharging hole of the secondary mixing groove (V201);
a secondary flash tank (V202) with a feed inlet communicated with a discharge outlet of the secondary horizontal reactor (R201);
a cross-linking unit (R202) with a feed inlet communicated with a discharge outlet of the secondary flash tank (V202);
a secondary condenser (E201) connected to the secondary horizontal reactor (R201);
a secondary delayer (S201) with a liquid inlet communicated with a liquid outlet of the secondary condenser (E201);
the production process comprises the following steps:
s1, conveying a solvent, a surfactant and a dispersant to a continuous phase mixing tank (V101) for mixing to obtain a continuous phase; sending the mixed solution of the initiator and the cross-linking agent and the acrylic acid solution to a dispersed phase mixing tank (V102) for mixing to obtain a dispersed phase; sending the continuous phase and the dispersed phase to a primary horizontal reactor (R101) for primary polymerization reaction to obtain primary reaction liquid;
s2, sending the primary reaction liquid to a primary flash tank (V103) for flash separation, wherein the flashed steam and the flashed materials are operated in two ways: the flashed vapor enters a primary condenser (E101) for cooling, the obtained condensate is sent to a primary demixer (S101) for demixing and is divided into an organic phase layer and a water phase layer, the organic phase is extracted from the top of the primary demixer (S101), and the water phase is discharged from the bottom of the primary demixer (S101); the flash-evaporated material is sent into a filter (S102) for filtering to respectively obtain solid and filtrate;
s3, conveying the solid to a secondary mixing tank (V201), conveying the dispersed phase to the secondary mixing tank (V201), conveying a solvent to the secondary mixing tank (V201), and mixing the three materials in the secondary mixing tank (V201) to obtain a mixed solution;
s4, sending the mixed solution to a secondary horizontal reactor (R201) for secondary polymerization reaction to obtain secondary reaction liquid;
s5, conveying the secondary reaction liquid to a secondary flash tank (V202) for flash separation, and operating the flashed steam and the flashed materials in two ways: the steam flashed out is discharged from the top of a secondary flash tank (V202); and (3) conveying the flash-evaporated material to a crosslinking unit (R202), and adding a crosslinking agent solution into the crosslinking unit (R202) to perform surface crosslinking treatment on the flash-evaporated material to obtain the polyacrylic acid super absorbent resin.
2. The production method according to claim 1, wherein in the continuous production apparatus:
the length-diameter ratio of the primary horizontal reactor (R101) is more than 2;
a heating sleeve is arranged at the periphery of the primary horizontal reactor (R101);
the temperature of a feed port of the primary horizontal reactor (R101) is maintained to be less than or equal to 60 ℃, and the temperature of a discharge port is maintained to be 70-75 ℃;
the discharge hole of the primary horizontal reactor (R101) is arranged below the central axis of the primary horizontal reactor (R101);
the length-diameter ratio of the secondary horizontal reactor (R201) is more than 2;
a heating sleeve is arranged at the periphery of the secondary horizontal reactor (R201);
the temperature of a feed port of the secondary horizontal reactor (R201) is maintained to be less than or equal to 60 ℃, and the temperature of a discharge port is maintained to be 70-75 ℃;
the discharge hole of the secondary horizontal reactor (R201) is arranged below the central axis of the secondary horizontal reactor (R201).
3. The production method according to claim 1, wherein in the continuous production apparatus:
a stirring paddle is arranged in the primary horizontal reactor (R101);
the stirring rake is multilayer stirring rake, includes: the stirring shaft is connected with a plurality of layers of blades; the stirring shaft coincides with the central axis of the primary horizontal reactor (R101);
the inclination angle of the paddle is 45 degrees; the inclination angle is the angle of the paddle deviating from the cross section of the stirring shaft;
a stirring paddle is arranged in the secondary horizontal reactor (R201);
the stirring rake is multilayer stirring rake, includes: the stirring shaft and a plurality of layers of blades connected to the stirring shaft; the stirring shaft is superposed with the central axis of the secondary horizontal reactor (R201);
the inclination angle of the paddle is 45 degrees; the inclination angle is the angle of the blade deviating from the cross section of the stirring shaft.
4. The production method according to claim 1, wherein in the continuous production apparatus:
the crosslinking unit (R202) comprises three crosslinking reaction kettles connected in parallel: a first crosslinking reaction kettle (R202-1), a second crosslinking reaction kettle (R202-2) and a third crosslinking reaction kettle (R202-3);
a discharge hole of the secondary flash tank (V202) is respectively communicated with a feed hole of the first crosslinking reaction kettle (R202-1), a feed hole of the second crosslinking reaction kettle (R202-2) and a feed hole of the third crosslinking reaction kettle (R202-3);
in the production process, in the step S5, the flash-evaporated material is sequentially sent to a first crosslinking reaction kettle (R202-1), a second crosslinking reaction kettle (R202-2) and a third crosslinking reaction kettle (R202-3), and meanwhile, a crosslinking agent solution is respectively sent to the first crosslinking reaction kettle (R202-1), the second crosslinking reaction kettle (R202-2) and the third crosslinking reaction kettle (R202-3), and the flash-evaporated material is subjected to surface crosslinking treatment, so as to obtain the polyacrylic acid super absorbent resin.
5. The production method according to claim 2, wherein in the continuous production apparatus:
the steam outlet of the secondary flash tank (V202) is communicated with a peripheral heating jacket of the secondary horizontal reactor (R201);
in the production process, in the step S5, after being discharged from the top of the secondary flash tank (V202), the flashed steam is sent to a peripheral heating jacket of the secondary horizontal reactor (R201), a part of steam stays in the heating jacket to be used as a heat source to heat the secondary horizontal reactor (R201), a part of steam enters a secondary condenser (E201) through the heating jacket to be condensed, the obtained condensate is sent to the secondary demixer (S201) to be demixed and is divided into two layers, namely an organic phase and a water phase, the organic phase is collected from the top of the secondary demixer (S201), and the water phase is discharged from the bottom of the secondary demixer (S201).
6. The production method according to claim 1, wherein in the continuous production apparatus:
in the primary polymerization unit, the filter (S102) is a vacuum filter;
the primary polymerization unit further includes: a settling tank (V104) communicated with the filtrate outlet of the filter (S102); a solvent recovery unit (H101) in communication with the supernatant outlet of the settling tank (V104);
in the production process, in the step S2, the filtrate is sent to a settling tank (V104) for treatment, the obtained supernatant is sent to a solvent recovery device (H101), and the obtained sediment is discharged from the settling tank (V104).
7. The production method according to claim 1, wherein in the step S1:
the solvent is selected from one or more of n-heptane, cyclohexane, n-octane, cyclopentane, benzene, toluene and xylene;
the surfactant is one or more selected from sucrose fatty acid ester, sorbitan monolaurate, sorbitan monostearate, acetic acid monolaurate, citric acid monostearate, lactic acid monostearate and polyglycerol fatty acid ester;
the dispersing agent is selected from one or more of maleic anhydride modified polypropylene, maleic anhydride modified ethylene-propylene copolymer, maleic anhydride modified EPDM (ethylene-propylene-diene-terpolymer), butadiene-maleic anhydride copolymer, oxidized polyethylene, ethylene-acrylic acid copolymer, ethyl cellulose and ethyl hydroxyethyl cellulose;
the mass ratio of the surfactant to the dispersant is 1: 0.5 to 5;
the mass ratio of the solvent to the surfactant to the total amount of the dispersant is 1: 0.002 to 0.008;
the temperature for mixing the solvent, the surfactant and the dispersant in the continuous phase mixing tank (V101) is 50 to 80 ℃.
8. The production method according to claim 1, characterized in that in step S1:
the acrylic acid solution is prepared by the following method: dissolving acrylic acid in water, mixing with a NaOH solution, and carrying out incomplete neutralization reaction to obtain an incompletely neutralized acrylic acid solution;
the neutralization degree of the acrylic acid solution is 50% -80%;
the mixed solution of the initiator and the cross-linking agent is an aqueous solution of the initiator and the cross-linking agent;
the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, azobisisobutyronitrile formamide, hydrogen peroxide, lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, di-tert-butyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide and bis (2-phenoxyethyl) peroxydicarbonate;
the cross-linking agent is selected from one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, polyglycerol diglycidyl ether and N, N' -methylenebis (meth) acrylamide;
the mass concentration of the mixed solution of the initiator and the cross-linking agent is 0.15-0.4%;
the mass ratio of the initiator to the cross-linking agent is 1: 0.05 to 0.09;
sending the mixed solution of the initiator and the cross-linking agent and the acrylic acid solution to a dispersed phase mixing tank (V102) for mixing to obtain a dispersed phase, and keeping the temperature at 10-25 ℃.
9. The production method according to claim 1, wherein in the step S3, the temperature in the secondary mixing tank (V201) is kept at 20 to 50 ℃.
10. The production method according to claim 5, wherein in the continuous production apparatus:
in the primary polymerization unit, an organic phase outlet of the primary delayer (S101) is also communicated with a continuous phase mixing tank (V101);
in the secondary polymerization unit, an organic phase outlet of a secondary delayer (S201) is also communicated with a secondary mixing tank (V201);
in the production process, in the step S2, the organic phase is extracted from the top of the primary delayer (S101) and then returned to the continuous phase mixing tank (V101) for recycling;
in the step S5, the organic phase is extracted from the top of the secondary delayer (S201) and then returned to the secondary mixing tank (V201) for recycling;
and in the step S5, after the surface crosslinking treatment, drying the obtained crosslinked product to obtain the polyacrylic acid super absorbent resin.
CN202210042715.8A 2022-01-14 2022-01-14 Production method of polyacrylic acid super absorbent resin Active CN114213572B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210042715.8A CN114213572B (en) 2022-01-14 2022-01-14 Production method of polyacrylic acid super absorbent resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210042715.8A CN114213572B (en) 2022-01-14 2022-01-14 Production method of polyacrylic acid super absorbent resin

Publications (2)

Publication Number Publication Date
CN114213572A CN114213572A (en) 2022-03-22
CN114213572B true CN114213572B (en) 2022-12-09

Family

ID=80708273

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210042715.8A Active CN114213572B (en) 2022-01-14 2022-01-14 Production method of polyacrylic acid super absorbent resin

Country Status (1)

Country Link
CN (1) CN114213572B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012144595A1 (en) * 2011-04-20 2012-10-26 株式会社日本触媒 Process and apparatus for producing water-absorbable resin of polyacrylic acid (salt) type
CN103554331A (en) * 2013-11-05 2014-02-05 中海油能源发展股份有限公司惠州石化分公司 Method for preparing polyacrylic acid high-water-absorptivity resin microspheres by reversed phase suspension polymerization
CN111978436A (en) * 2020-08-27 2020-11-24 万华化学集团股份有限公司 High-efficiency and low-consumption reverse suspension polymerization preparation process of water-absorbing compound
CN112574360A (en) * 2020-11-23 2021-03-30 万华化学集团股份有限公司 High water absorption resin prepared continuously by reversed phase suspension polymerization
CN113912779A (en) * 2021-11-01 2022-01-11 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 Super absorbent resin and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100909182B1 (en) * 2001-09-12 2009-07-23 에보닉 스톡하우젠 게엠베하 Continuous polymerization process to prepare superabsorbent polymer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012144595A1 (en) * 2011-04-20 2012-10-26 株式会社日本触媒 Process and apparatus for producing water-absorbable resin of polyacrylic acid (salt) type
CN103554331A (en) * 2013-11-05 2014-02-05 中海油能源发展股份有限公司惠州石化分公司 Method for preparing polyacrylic acid high-water-absorptivity resin microspheres by reversed phase suspension polymerization
CN111978436A (en) * 2020-08-27 2020-11-24 万华化学集团股份有限公司 High-efficiency and low-consumption reverse suspension polymerization preparation process of water-absorbing compound
CN112574360A (en) * 2020-11-23 2021-03-30 万华化学集团股份有限公司 High water absorption resin prepared continuously by reversed phase suspension polymerization
CN113912779A (en) * 2021-11-01 2022-01-11 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 Super absorbent resin and preparation method thereof

Also Published As

Publication number Publication date
CN114213572A (en) 2022-03-22

Similar Documents

Publication Publication Date Title
CN102176926B (en) Continuous process for production of superabsorbent polymer
EP2980128B1 (en) Water-absorbent resin composition production method
CA1258338A (en) Continuous solution polymerisation to water-containing cross-linked gel polymer
US8063121B2 (en) Process for the production of a superabsorbent polymer
US6150477A (en) Process for the preparation of hydrophilic hydrogels of high swelling capacity
CN103449699B (en) Device and method for realizing continuous pyrohydrolysis treatment of organic material
CN102869689A (en) A process for the production of a superabsorbent polymer
KR102635153B1 (en) Method for producing water absorbent resin and water absorbent resin
CN102177182B (en) A process for the production of a superabsorbent polymer
CN104053705A (en) Heat-treatment of water-absorbing polymeric particles in fluidized bed at fast heat-up rate
CN114213572B (en) Production method of polyacrylic acid super absorbent resin
CN102176925B (en) Process for production of superabsorbent polymer
CN216879344U (en) Continuous production equipment for polyacrylic acid super absorbent resin
CN104066774A (en) Heat-treatment of water-absorbing polymeric particles in a fluidized bed
CN214636371U (en) Device for producing polyvinyl chloride by multi-kettle continuous polymerization
CN107572723A (en) A kind of hydroquinones Waste Water Treatment
CN110142017B (en) Chlorinated high polymer integrated production platform
CN113087363A (en) Deep dehydration method for biogas residues
CN114133471B (en) Production method of super absorbent resin
CN112812206B (en) Device and method for producing polyvinyl chloride by multi-kettle continuous polymerization
CN114874378B (en) Preparation method of high-absorptivity resin
CN221701261U (en) Sludge Fenton conditioning reaction hedging cyclone reactor
CN214982427U (en) ASA resin production device for PVC outdoor products
CN110862479B (en) Method for preparing spherical super absorbent resin system by using reversed phase suspension method
CN210163362U (en) Device for producing uniform-particle functional high-molecular polymer microspheres

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