CN111704694B - Continuous production process and continuous production device of emulsion type polymer and application thereof - Google Patents

Continuous production process and continuous production device of emulsion type polymer and application thereof Download PDF

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CN111704694B
CN111704694B CN202010628248.8A CN202010628248A CN111704694B CN 111704694 B CN111704694 B CN 111704694B CN 202010628248 A CN202010628248 A CN 202010628248A CN 111704694 B CN111704694 B CN 111704694B
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emulsion
parts
emulsion polymer
reactor
pipeline
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CN111704694A (en
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郝世英
谢璇
任永宏
叶智
周宝
曾立详
李爱辉
李华
翟大治
李鹏
候新强
姜萍
张艳
胡鹏飞
王录勤
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XI'AN CHANGQING CHEMICAL GROUP CO Ltd
China National Petroleum Corp
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XI'AN CHANGQING CHEMICAL GROUP CO Ltd
China National Petroleum Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1812—Tubular reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/007—Feed or outlet devices as such, e.g. feeding tubes provided with moving parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure

Abstract

The invention provides a continuous production process and a continuous production device of emulsion type polymers and application thereof, wherein emulsion is prepared firstly, then the emulsion and an oxidant are mixed and conveyed to a tubular continuous reactor, and simultaneously the reductant is separately input, so that early polymerization can be prevented.

Description

Continuous production process and continuous production device of emulsion type polymer and application thereof
Technical Field
The invention belongs to the field of emulsion polymerization, and particularly relates to a continuous production process and a continuous production device of an emulsion polymer and application thereof.
Background
With the continuous advance of oil field exploitation, emulsion polymers developed for fractured reservoirs have the characteristics of blockage, injection, movement and the like, and at present, most of emulsion polymers adopt an old kettle type polymerization process, namely, an aqueous phase and an oil phase are emulsified firstly, and then an initiator is added to carry out single kettle polymerization under the stirring action, but the process has the following defects:
(1) the oxidant is added into the aqueous phase solution, so that self-polymerization easily occurs, and poor stability and safety are caused.
(2) The reducing agent is added at one time, the reaction speed is high, the temperature is difficult to control, and the product stability is poor.
Disclosure of Invention
The invention aims to provide a continuous production process and a continuous production device of emulsion type polymers and application thereof, so as to overcome the technical defects.
In order to solve the technical problem, the invention provides a continuous production process of an emulsion polymer, which comprises the following steps:
s1, preparing a water phase;
s2, preparing an oil phase;
s3, pumping the water phase and the oil phase into a static mixer to be mixed into emulsion, and enabling the emulsion to enter a manifold through a discharge port;
s4, weighing the composite oxidant, and continuously pumping the composite oxidant into a header through a metering pump;
s5, mixing the emulsion and the composite oxidant in a manifold, and then jointly feeding the mixture into a tubular continuous reactor;
s6, weighing a reducing agent, and continuously pumping the reducing agent to the tubular continuous reactor through a metering pump;
and S7, heating and polymerizing the emulsion, the composite oxidant and the reducing agent in the tubular continuous reactor to form an emulsion polymer, outputting the emulsion polymer from a discharge port of the tubular continuous reactor, and packaging the output to finish the production of the emulsion polymer.
Further, the preparation of the water phase by the S1 specifically comprises the steps of preparing raw materials and a preparation method, and specifically comprises the following steps:
preparing raw materials, which comprises the following components in parts by weight:
150-300 parts of deionized water;
90-150 parts of acrylamide;
10-30 parts of functional monomer;
50-80 parts of N, N-methylene bisacrylamide;
25-40 parts of acrylic acid;
40-64 parts of a pH regulator;
preparation method
Weighing deionized water, acrylamide, a functional monomer, N-methylene bisacrylamide, acrylic acid and a pH regulator according to the mass parts, adding all the raw materials into a container, and uniformly stirring to form a water phase.
Preferably, the functional monomer is one or more of glycidyl methacrylate, ethyl methacrylate and vinyl versatate.
Preferably, the pH regulator is NaOH, NaHCO3And citric acid or a mixture of more than one of them.
Further, S2 preparation of the oil phase specifically comprises preparation of raw materials and a preparation method, specifically:
preparing raw materials, which comprises the following components in parts by weight:
280-360 parts of 7# white oil;
40-80 parts of sorbitan monooleate polyoxyethylene ether;
60-120 parts of an oily emulsifier;
20-50 parts of trimeric monooleate;
preparation method
Weighing 7# white oil, sorbitan monooleate polyoxyethylene ether, oily emulsifier and trimeric monooleate according to the mass parts, adding all the raw materials into a container, and uniformly stirring to form an oil phase.
Preferably, the oily emulsifier is one or more of sorbitan monooleate SPan80, diethylene glycol monooleate and polyoxyethylene oleyl alcohol ether.
Preferably, the composite oxidant is one or more of ammonium persulfate, hydrogen peroxide and ferric chloride; the reducing agent is sodium bisulfite.
The invention also provides a continuous production device of the emulsion polymer, which comprises a tubular continuous reactor, wherein the tubular continuous reactor is provided with a bottom feeding hole and a top discharging hole, the outer wall of the tubular continuous reactor is sleeved with a jacket for circulating a heat transfer medium, the inner cavity of the tubular continuous reactor is provided with a plurality of temperature sensors for monitoring the temperature of reactants and a plurality of push type stirrers for pushing the reactants, and all the temperature sensors and all the push type stirrers are uniformly distributed at intervals along the flowing direction of the reactants;
the top discharge port of the tubular continuous reactor is connected with three parallel pipelines, wherein one pipeline is an emptying pipeline connected with an emptying valve in series, the other pipeline is a pressure measuring pipeline provided with a pressure detector, and the third pipeline is a discharge pipeline;
the bottom feed inlet of the tubular continuous reactor is connected with two pipelines connected in parallel, wherein one pipeline is provided with a first flowmeter and a first metering pump which are mutually linked, the other pipeline is a manifold, one end of the manifold is communicated with the bottom feed inlet of the tubular continuous reactor, the other end of the manifold is connected with two branch pipelines connected in parallel, one branch pipeline is sequentially provided with a second metering pump and a second flowmeter along the medium flowing direction, and the other branch pipeline is sequentially provided with a static mixer and a third flowmeter along the medium flowing direction;
the first flow meter, the first metering pump, the second flow meter, the third flow meter and all the temperature sensors are connected to the PLC.
Further, the propeller-type stirrer is divided into a push-up four-blade propeller-type stirrer and a push-down four-blade propeller-type stirrer, and the push-up four-blade propeller-type stirrer and the push-down four-blade propeller-type stirrer are distributed at intervals along the flowing direction of reactants.
The invention also provides an application of the continuous production device of the emulsion polymer, which comprises the continuous production device of the emulsion polymer, and the continuous production device of the emulsion polymer is used for a continuous production process of the emulsion polymer, and the specific application method comprises the following steps:
adding the water phase and the oil phase into a static mixer together, mixing the water phase and the oil phase into emulsion in the static mixer, and enabling the emulsion to enter a manifold through a third flowmeter;
the composite oxidant sequentially enters a header through a second metering pump and a second flowmeter;
the emulsion and the composite oxidant are converged in a manifold and then enter a tubular continuous reactor through a bottom feed inlet;
the reducing agent sequentially flows through the first metering pump and the first flowmeter and then enters the tubular continuous reactor through the bottom feed inlet;
and (2) heating and polymerizing the emulsion, the composite oxidant and the reducing agent in the tubular continuous reactor, stirring and shearing the mixture by a push type stirrer during reaction to form an emulsion type polymer product, outputting the emulsion type polymer product from a top discharge hole, and finally packaging to finish the preparation of the emulsion type polymer product.
Furthermore, temperature data collected by all temperature sensors are transmitted to the PLC, and the PLC adjusts the opening degree of a medium valve in the jacket according to the received temperature data.
The invention has the following beneficial effects:
(1) the continuous production process of emulsion type polymer includes mixing water phase and oil phase to form emulsion, mixing the emulsion and oxidant, inputting the mixture into the tubular continuous reactor, and pumping reductant to the tubular continuous reactor separately for continuous polymerization.
(2) The stirring paddle of the tubular continuous reactor consists of an upward-pushing four-blade paddle and a horizontal-pushing four-blade paddle, the four blades are arranged at intervals, the interval distance and the rotating speed are adjustable, and the characteristics of high stirring shear strength, no dead angle and strong thrust can be realized under the combined condition of the four blades, so that the first-in first-out of materials is ensured, and the continuous polymerization is realized.
(3) The initiator is controlled by adopting a high-precision metering pump and a flow meter, so that the proportion balance of the initiator and the emulsion is ensured; a plurality of groups of temperature measuring points are uniformly distributed in the reactor, and the opening degree of a cold/hot water valve in a jacket can be controlled by monitoring the temperature in the reactor in real time, so that the transfer of polymerization heat is controlled, and the continuous polymerization is ensured; the pressure detector arranged on the upper part of the reactor can monitor the internal pressure of the reactor in real time, control the pressure relief in the reactor and realize safe production.
In order to make the aforementioned and other objects of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is a flow diagram of a continuous process for producing an emulsion polymer.
FIG. 2 is a schematic view of a continuous production apparatus for an emulsion type polymer.
FIG. 3 is a schematic view of the structure of a tubular continuous reactor.
Description of reference numerals:
1. a tubular continuous reactor; 2. an emptying pipeline; 3. a pressure measuring pipeline; 4. a first flow meter; 5. a first metering pump; 6. collecting pipes; 7. a second metering pump; 8. a second flow meter; 9. a static mixer; 10. and a third flow meter.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
In the present invention, the upper, lower, left and right in the drawings are regarded as the upper, lower, left and right of the continuous production process of the emulsion polymer described in the present specification.
The exemplary embodiments of the present invention will now be described with reference to the accompanying drawings, however, the present invention may be embodied in many different forms and is not limited to the embodiments described herein, which are provided for complete and complete disclosure of the present invention and to fully convey the scope of the present invention to those skilled in the art. The terminology used in the exemplary embodiments illustrated in the accompanying drawings is not intended to be limiting of the invention. In the drawings, the same units/elements are denoted by the same reference numerals.
Unless otherwise defined, terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Further, it will be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense.
The first embodiment:
this embodiment relates to a process for the continuous production of emulsion polymers, see fig. 1, comprising the following steps:
s1, preparing a water phase;
s2, preparing an oil phase;
s3, pumping the water phase and the oil phase into a static mixer to be mixed into emulsion, and enabling the emulsion to enter a manifold through a discharge port;
s4, weighing the composite oxidant, and continuously pumping the composite oxidant into a header through a metering pump;
s5, mixing the emulsion and the composite oxidant in a manifold, and then jointly feeding the mixture into a tubular continuous reactor;
s6, weighing a reducing agent, and continuously pumping the reducing agent to the tubular continuous reactor through a metering pump;
and S7, heating and polymerizing the emulsion, the composite oxidant and the reducing agent in the tubular continuous reactor to form an emulsion polymer, outputting the emulsion polymer from a discharge port of the tubular continuous reactor, and packaging the output to finish the production of the emulsion polymer.
The existing oxidant is generally added into an aqueous phase solution, is easy to self-polymerize and has poor stability and safety.
In order to solve the above problems, the present embodiment first prepares an emulsion and then mixes the emulsion and an oxidizing agent in a pipeline, that is, mixes both at the downstream of the emulsion, so that it is possible to prevent premature polymerization and avoid formation of polymer lumps, while the oxidizing agent is continuously supplied in a fixed amount by a metering pump to achieve continuous polymerization.
In addition, most of the existing reducing agents are put in at one time, the reaction speed is high and difficult to control, the temperature is difficult to control, and the product stability is poor.
Second embodiment:
this embodiment relates to a process for the continuous production of emulsion polymers, see fig. 1, comprising the following steps:
s1, preparing a water phase, which specifically comprises the following steps of preparing raw materials and a preparation method:
(1) preparing raw materials, which comprises the following components in parts by weight:
150-300 parts of deionized water;
90-150 parts of acrylamide;
10-30 parts of functional monomer;
50-80 parts of N, N-methylene bisacrylamide;
25-40 parts of acrylic acid;
40-64 parts of a pH regulator;
wherein the mass ratio of the N, N-methylene bisacrylamide to the acrylic acid is 2; the mass ratio of the acrylic acid to the pH regulator is 0.625;
wherein the functional monomer is one or a mixture of glycidyl methacrylate, ethyl methacrylate and vinyl versatate; the pH regulator is NaOH or NaHCO3And citric acid or a mixture of more than one of them.
(2) Preparation method
Weighing deionized water, acrylamide, a functional monomer, N-methylene bisacrylamide, acrylic acid and a pH regulator according to the mass parts, adding all the raw materials into a container, and uniformly stirring to form a water phase. (ii) a
S2, preparing an oil phase, which specifically comprises the following steps of preparing raw materials and a preparation method:
(1) preparing raw materials, which comprises the following components in parts by weight:
280-360 parts of 7# white oil;
40-80 parts of sorbitan monooleate SPan80 polyoxyethylene ether;
60-120 parts of an oily emulsifier;
20-50 parts of trimeric monooleate;
preferably, the oily emulsifier is one or more of sorbitan monooleate SPan80, diethylene glycol monooleate and polyoxyethylene oleyl alcohol ether; the composite oxidant is one or more of ammonium persulfate, hydrogen peroxide and ferric chloride; the reducing agent is sodium bisulfite.
(2) Preparation method
Weighing 7# white oil, sorbitan monooleate polyoxyethylene ether, oily emulsifier and trimeric monooleate according to the mass parts, adding all the raw materials into a container, and uniformly stirring to form an oil phase.
S3, pumping the water phase and the oil phase into a static mixer to be mixed into emulsion, and enabling the emulsion to enter a manifold through a discharge port;
s4, weighing the composite oxidant, and continuously pumping the composite oxidant into a header through a metering pump;
s5, mixing the emulsion and the composite oxidant in a manifold, and then jointly feeding the mixture into a tubular continuous reactor;
s6, weighing a reducing agent, and continuously pumping the reducing agent to the tubular continuous reactor through a metering pump;
and S7, heating and polymerizing the emulsion, the composite oxidant and the reducing agent in the tubular continuous reactor to form an emulsion polymer, outputting the emulsion polymer from a discharge port of the tubular continuous reactor, and packaging the output to finish the production of the emulsion polymer.
This embodiment adds the oxidizing agent and the reducing agent separately to the emulsion to prevent premature polymerization.
The use and effect of the components in the water phase are as follows:
deionized water is used for dissolving materials such as acrylamide, functional monomers, N-methylene bisacrylamide and the like; acrylamide and acrylic acid as polymerization monomers; the functional monomer enables the polymerized product to have the functions of temperature resistance and salt resistance; n, N-methylene bisacrylamide is used as a cross-linking agent, so that the product is polymerized into a cross-linked polymer; the pH regulator is used for regulating the pH value of the water phase system and is used for controlling the polymerization speed of the system and the pH value of water-soluble water after the product is formed.
The use and effect of the components in the oil phase are as follows:
the 7# white oil is used as an organic solvent, so that the 7# white oil, the sorbitan monooleate polyoxyethylene ether, the oily emulsifier and the trimeric monooleate emulsifier can be fully and uniformly mixed, and the emulsifiers can be emulsified with a water phase to form a stable emulsion system after being mixed according to a certain proportion, so that the system has a certain HLB value.
HLB value: the surfactant is an amphiphilic molecule with a hydrophilic group and a lipophilic group, and the amount of the size and the force balance degree between the hydrophilic group and the lipophilic group in the surfactant molecule is defined as the hydrophilic-lipophilic balance value of the surfactant.
The reaction mechanism of the emulsion polymer of the present embodiment is as follows:
Figure BDA0002565571930000071
the third embodiment:
the continuous production process of the emulsion polymer is implemented according to the following steps:
(1) 150 parts of deionized water, 102 parts of acrylamide, 10 parts of functional monomer, 60 parts of N, N-methylene-bisacrylamide, 30 parts of acrylic acid and 48 parts of pH regulator are dissolved according to weight to form a water phase for later use.
(2) According to the weight, 360 parts of 7# white oil, 8080 parts of sorbitan monooleate polyoxyethylene ether Tween, 120 parts of oily emulsifier and 40 parts of trimeric monooleate are uniformly stirred to form an oil phase for later use.
(3) According to the mass ratio, 400 parts of prepared water phase and 600 parts of prepared oil phase are pumped into an online mixer by a metering pump in proportion for online emulsification to form stable emulsion. Wherein the water phase flow rate is 20L/min, the oil phase flow rate is 30L/min, and the total emulsion flow rate is 50L/min.
(4) At the rear end of the mixer, the composite oxidant was continuously added by a high precision metering pump at a flow rate of 50 mlL/min.
(5) And (3) the emulsion added with the oxidant enters from the bottom of the tubular reactor and is gradually conveyed to the top of the tubular reactor under the driving of a pump.
(6) The reducing agent is continuously pumped into the bottom of the reactor according to the proportion, and the flow rate is 175 mL/min.
(7) And gradually initiating the temperature rise polymerization of the emulsion added with the reducing agent in the reactor to 75 ℃ to form a required product, discharging the product from a discharge hole at the top of the reactor, and finally packaging to finish the preparation.
Fourth embodiment:
the continuous production process of the emulsion polymer is implemented according to the following steps:
(1) 175 parts of deionized water, 145 parts of acrylamide, 15 parts of functional monomer, 50 parts of N, N-methylene bisacrylamide, 25 parts of acrylic acid and 40 parts of pH regulator are dissolved according to weight to form a water phase for later use.
(2) 350 parts of 7# white oil, 8060 parts of sorbitan monooleate polyoxyethylene ether Tween, 90 parts of oily emulsifier and 50 parts of trimeric monooleate are uniformly stirred according to the weight to form an oil phase for later use.
(3) According to the mass ratio, 450 parts of prepared water phase and 550 parts of prepared oil phase are pumped into an online mixer by a metering pump in proportion for online emulsification to form stable emulsion. Wherein the water phase flow rate is 45L/min, the oil phase flow rate is 55L/min, and the total emulsion flow rate is 100L/min.
(4) At the rear end of the mixer, the composite oxidant was continuously added by a high precision metering pump at a flow rate of 100 mlL/min.
(5) And (3) the emulsion added with the oxidant enters from the bottom of the tubular reactor and is gradually conveyed to the top of the tubular reactor under the driving of a pump.
(6) And continuously pumping the reducing agent into the bottom of the reactor according to the proportion, wherein the flow rate is 350 mL/min.
(7) And gradually initiating the temperature rise polymerization of the emulsion added with the reducing agent in the reactor to 67 ℃ to form a required product, discharging the product from a discharge hole at the top of the reactor, and finally packaging to finish the preparation.
Fifth embodiment:
the continuous production process of the emulsion polymer is implemented according to the following steps:
(1) 200 parts of deionized water, 117.5 parts of acrylamide, 10 parts of functional monomer, 75 parts of N, N-methylene-bisacrylamide, 37.5 parts of acrylic acid and 60 parts of pH regulator are dissolved according to weight to form a water phase for later use.
(2) Uniformly stirring 330 parts of 7# white oil, 8060 parts of sorbitan monooleate polyoxyethylene ether Tween, 90 parts of oily emulsifier and 20 parts of trimeric monooleate by weight to form an oil phase for later use.
(3) And pumping 500 parts of the prepared water phase and 500 parts of the prepared oil phase into an online mixer by a metering pump in proportion according to the mass ratio for online emulsification to form stable emulsion. Wherein the water phase flow rate is 75L/min, the oil phase flow rate is 75L/min, and the total emulsion flow rate is 150L/min.
(4) At the rear end of the mixer, the composite oxidant was continuously added by a high precision metering pump at a flow rate of 150 mlL/min.
(5) And (3) the emulsion added with the oxidant enters from the bottom of the tubular reactor and is gradually conveyed to the top of the tubular reactor under the driving of a pump.
(6) The reducing agent is continuously pumped into the bottom of the reactor according to the proportion, and the flow rate is 450 mL/min.
(7) And gradually initiating the temperature rise polymerization of the emulsion added with the reducing agent in the reactor to 72 ℃ to form a required product, discharging the product from a discharge hole at the top of the reactor, and finally packaging to finish the preparation.
Sixth embodiment:
the continuous production process of the emulsion polymer is implemented according to the following steps:
(1) 265 parts of deionized water, 132 parts of acrylamide, 15 parts of functional monomer, 60 parts of N, N-methylene bisacrylamide, 30 parts of acrylic acid and 48 parts of pH regulator are dissolved according to weight to form a water phase for later use.
(2) 300 parts of 7# white oil, 8050 parts of sorbitan monooleate polyoxyethylene ether Tween, 75 parts of oily emulsifier and 25 parts of trimeric monooleate are uniformly stirred according to the weight to form an oil phase for later use.
(3) According to the mass ratio, 550 parts of the prepared water phase and 450 parts of the prepared oil phase are pumped into an online mixer by a metering pump in proportion for online emulsification to form stable emulsion. Wherein the water phase flow rate is 110L/min, the oil phase flow rate is 90L/min, and the total emulsion flow rate is 200L/min.
(4) At the rear end of the mixer, the composite oxidant was continuously added by a high precision metering pump at a flow rate of 200 mlL/min.
(5) And (3) the emulsion added with the oxidant enters from the bottom of the tubular reactor and is gradually conveyed to the top of the tubular reactor under the driving of a pump.
(6) The reducing agent is continuously pumped into the bottom of the reactor according to the proportion, and the flow rate is 700 mL/min.
(7) And gradually initiating the temperature rise polymerization of the emulsion added with the reducing agent in the reactor to 77 ℃ to form a required product, discharging the product from a discharge hole at the top of the reactor, and finally packaging to finish the preparation.
The seventh embodiment:
the continuous production process of the emulsion polymer is implemented according to the following steps:
(1) 294 parts of deionized water, 92 parts of acrylamide, 30 parts of functional monomer, 80 parts of N, N-methylene bisacrylamide, 40 parts of acrylic acid and 64 parts of pH regulator are dissolved according to weight to form a water phase for later use.
(2) 280 parts of 7# white oil, 8040 parts of sorbitan monooleate polyoxyethylene ether Tween, 60 parts of oily emulsifier and 20 parts of trimeric monooleate are uniformly stirred according to the weight to form an oil phase for later use.
(3) According to the mass ratio, 600 parts of the prepared water phase and 400 parts of the prepared oil phase are pumped into an online mixer by a metering pump in proportion for online emulsification to form stable emulsion. Wherein the water phase flow rate is 120L/min, the oil phase flow rate is 180L/min, and the total emulsion flow rate is 300L/min.
(4) At the rear end of the mixer, the composite oxidant was continuously added by a high precision metering pump at a flow rate of 300 mlL/min.
(5) And (3) the emulsion added with the oxidant enters from the bottom of the tubular reactor and is gradually conveyed to the top of the tubular reactor under the driving of a pump.
(6) And continuously pumping the reducing agent into the bottom of the reactor according to the proportion, wherein the flow rate is 1000 mL/min.
(7) And gradually initiating the temperature rise polymerization of the emulsion added with the reducing agent in the reactor to 85 ℃ to form a required product, discharging the product from a discharge hole at the top of the reactor, and finally packaging to finish the preparation.
Eighth embodiment:
in this embodiment, the particle size, expansion ratio and effective content of the emulsion polymer products produced by the emulsion polymer continuous production process according to the third to seventh embodiments were tested, and the test results are shown in the following table:
serial number Item Third embodiment Fourth embodiment Fifth embodiment Sixth embodiment Seventh embodiment
1 Particle size/um 42.35 77.25 103.2 152.5 187.2
2 Expansion multiple/multiple 3.3 2.5 1.5 1.6 1.2
3 Effective content/%) 20.53 23.26 24.19 23.43 20.22
According to the table, the particle size range of the emulsion polymer produced by the embodiments is 42.35-187.2 um, the expansion factor is 1.2-3.3 times, the effective content is 20.22-24.19%, and the content of each component of the emulsion polymer can not be exhausted, so that after a large number of experiments in a laboratory, the applicant finds that the particle size of the produced emulsion polymer is 40-200 micrometers, the expansion factor is 1-4 times, the effective content can reach more than 20%, and the cross-linked polymer has higher strength, better temperature and salt resistance and higher blocking rate than common cross-linked gel in the water plugging and flooding adjusting process.
The effective content is the ratio of the mass of the product after washing with absolute ethyl alcohol, vacuum-filtering with a positive air suction pump, and drying at 105 ℃ to the initial mass.
Ninth embodiment:
the embodiment provides a continuous production device of emulsion polymer, which comprises a tubular continuous reactor 1, as shown in figure 2, wherein the tubular continuous reactor 1 is provided with a bottom feeding hole and a top discharging hole, the outer wall of the tubular continuous reactor 1 is sleeved with a jacket for circulating a heat transfer medium, the inner cavity of the tubular continuous reactor 1 is provided with a plurality of temperature sensors for monitoring the temperature of reactants and a plurality of push type stirrers for pushing the reactants, and all the temperature sensors and all the push type stirrers are uniformly arranged at intervals along the flowing direction of the reactants;
a discharge port at the top of the tubular continuous reactor 1 is connected with three parallel pipelines, wherein one pipeline is an emptying pipeline 2 connected with an emptying valve in series, the other pipeline is a pressure measuring pipeline 3 provided with a pressure detector, and the third pipeline is a discharge pipeline;
the bottom feed inlet of the tubular continuous reactor 1 is connected with two parallel pipelines, wherein one pipeline is provided with a first flowmeter 4 and a first metering pump 5 which are mutually linked, the other pipeline is a manifold 6, one end of the manifold 6 is communicated with the bottom feed inlet of the tubular continuous reactor 1, the other end of the manifold 6 is connected with two parallel branch pipelines, one branch pipeline is sequentially provided with a second metering pump 7 and a second flowmeter 8 along the medium flowing direction, and the other branch pipeline is sequentially provided with a static mixer 9 and a third flowmeter 10 along the medium flowing direction;
wherein, the first flow meter 4, the first metering pump 5, the second metering pump 7, the second flow meter 8, the third flow meter 10 and all temperature sensors are connected to the PLC.
The application method of the continuous production device of the emulsion polymer comprises the following steps:
adding the water phase and the oil phase into a static mixer 9 together, mixing the water phase and the oil phase into emulsion in the static mixer 9, and allowing the emulsion to enter a manifold 6 through a third flow meter 10;
the composite oxidant sequentially enters a header 6 through a second metering pump 7 and a second flowmeter 8;
the emulsion and the composite oxidant are converged in a manifold 6 and then enter a tubular continuous reactor 1 through a bottom feed inlet;
the reducing agent sequentially flows through a first metering pump 5 and a first flowmeter 4 and then enters the tubular continuous reactor 1 through a bottom feeding hole;
and (2) heating and polymerizing the emulsion, the composite oxidant and the reducing agent in the tubular continuous reactor 1, stirring and shearing the mixture by a push type stirrer during reaction to form an emulsion type polymer product, outputting the emulsion type polymer product from a top discharge hole, and finally packaging to finish the preparation of the emulsion type polymer product.
As shown in fig. 3, the function of the propeller agitator is to agitate and shear the reactant, and at the same time, the reactant may be pushed upward, in this embodiment, the propeller agitator is divided into a push-up four-blade propeller agitator 11 and a flat-push four-blade propeller agitator 12, the push-up four-blade propeller agitator 11 and the flat-push four-blade propeller agitator 12 are distributed at intervals along the flowing direction of the reactant, the interval distance is 0.3-0.6 m (adjustable), and the characteristics of large agitating shear strength, no dead angle, and strong thrust can be realized under the blade combination condition, thereby ensuring the first-in first-out of the material and realizing the continuous polymerization.
The initiator is controlled by adopting a high-precision metering pump and a flow meter, so that the proportion balance of the initiator and the emulsion is ensured.
6 groups of temperature measuring points are uniformly distributed in the reactor, and the opening degree of a cold/hot water valve in a jacket can be controlled by monitoring the temperature in the reactor in real time, so that the transfer of polymerization heat is controlled, and the continuous polymerization is ensured.
The pressure detector on the upper part of the reactor can monitor the internal pressure of the reactor in real time, control the pressure relief in the reactor and realize safe production.
The temperature data collected by all the temperature sensors are transmitted to the PLC, and the PLC adjusts the opening degree of a medium valve in the jacket according to the received temperature data; and each metering pump is in linkage fit with the flowmeter (dotted lines in fig. 2), so that accurate output flow is realized.
The continuous production process of the emulsion polymer has the effects of stirring and back mixing inside and is suitable for a high-viscosity emulsion system.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.

Claims (10)

1. A continuous production device of emulsion polymer comprises a tubular continuous reactor (1) which is provided with a bottom feeding hole and a top discharging hole, and the outer wall of the tubular continuous reactor (1) is sleeved with a jacket for circulating heat transfer medium, and is characterized in that a plurality of temperature sensors for monitoring the temperature of reactants and a plurality of push type stirrers for pushing the reactants are arranged in the inner cavity of the tubular continuous reactor (1), and all the temperature sensors and all the push type stirrers are uniformly arranged at intervals along the flowing direction of the reactants;
a discharge port at the top of the tubular continuous reactor (1) is connected with three parallel pipelines, wherein one pipeline is an emptying pipeline (2) connected with an emptying valve in series, the other pipeline is a pressure measuring pipeline (3) provided with a pressure detector, and the third pipeline is a discharge pipeline;
the bottom feed inlet of the tubular continuous reactor (1) is connected with two parallel pipelines, wherein one pipeline is provided with a first flowmeter (4) and a first metering pump (5) which are mutually linked, the other pipeline is a manifold (6), one end of the manifold (6) is communicated with the bottom feed inlet of the tubular continuous reactor (1), the other end of the manifold (6) is connected with two branch pipelines which are connected in parallel, one branch pipeline is sequentially provided with a second metering pump (7) and a second flowmeter (8) along the medium flowing direction, and the other branch pipeline is sequentially provided with a static mixer (9) and a third flowmeter (10) along the medium flowing direction;
the first flow meter (4), the first metering pump (5), the second metering pump (7), the second flow meter (8), the third flow meter (10) and all the temperature sensors are connected to the PLC.
2. An apparatus for continuously producing an emulsion polymer according to claim 1, wherein the propeller-type agitator is divided into a push-up four-blade propeller-type agitator (11) and a push-down four-blade propeller-type agitator (12), and the push-up four-blade propeller-type agitator (11) and the push-down four-blade propeller-type agitator (12) are arranged at intervals in the flow direction of the reactants.
3. A process for continuously producing an emulsion polymer by using the continuous production apparatus according to claim 1 or 2, comprising the steps of:
s1, preparing a water phase;
s2, preparing an oil phase;
s3, pumping the water phase and the oil phase into a static mixer to be mixed into emulsion, and enabling the emulsion to enter a manifold through a discharge port;
s4, weighing the composite oxidant, and continuously pumping the composite oxidant into a header through a metering pump;
s5, mixing the emulsion and the composite oxidant in a manifold, and then jointly feeding the mixture into a tubular continuous reactor;
s6, weighing a reducing agent, and continuously pumping the reducing agent to the tubular continuous reactor through a metering pump;
and S7, heating and polymerizing the emulsion, the composite oxidant and the reducing agent in the tubular continuous reactor to form an emulsion polymer, outputting the emulsion polymer from a discharge port of the tubular continuous reactor, and packaging the output to finish the production of the emulsion polymer.
4. The continuous process for producing an emulsion polymer according to claim 3, wherein the preparation of the aqueous phase in S1 comprises the steps of preparing raw materials and a preparation method, and comprises the steps of:
(1) preparing raw materials, which comprises the following components in parts by weight:
150-300 parts of deionized water;
90-150 parts of acrylamide;
10-30 parts of functional monomer;
50-80 parts of N, N-methylene bisacrylamide;
25-40 parts of acrylic acid;
40-64 parts of a pH regulator;
(2) preparation method
Weighing deionized water, acrylamide, a functional monomer, N-methylene bisacrylamide, acrylic acid and a pH regulator according to the mass parts, adding all the raw materials into a container, and uniformly stirring to form a water phase.
5. A continuous process for the production of an emulsion polymer according to claim 4, wherein: the functional monomer is one or a mixture of glycidyl methacrylate, ethyl methacrylate and vinyl versatate; the pH regulator is one or more of NaOH, NaHCO3 and citric acid.
6. The continuous process for producing an emulsion polymer according to claim 3, wherein the preparation of the oil phase in S2 comprises the steps of preparing raw materials and a preparation method, and comprises the steps of:
(1) preparing raw materials, which comprises the following components in parts by weight:
280-360 parts of 7# white oil;
40-80 parts of sorbitan monooleate polyoxyethylene ether;
60-120 parts of an oily emulsifier;
20-50 parts of trimeric monooleate;
(2) preparation method
Weighing 7# white oil, sorbitan monooleate polyoxyethylene ether, oily emulsifier and trimeric monooleate according to the mass parts, adding all the raw materials into a container, and uniformly stirring to form an oil phase.
7. A continuous process for producing an emulsion polymer as claimed in claim 6, wherein the oily emulsifier is one or more of sorbitan monooleate SPan80, diethylene glycol monooleate, and polyoxyethylene oleyl alcohol ether.
8. A continuous process for the production of an emulsion polymer as claimed in claim 3, wherein the complex oxidant is a mixture of one or more of ammonium persulphate, hydrogen peroxide and ferric chloride; the reducing agent is sodium bisulfite.
9. An application of a continuous production device of emulsion polymer, which is characterized in that the continuous production device of emulsion polymer is as claimed in claim 1 or 2, and the continuous production device of emulsion polymer is used for the continuous production process of emulsion polymer as claimed in any one of claims 3 to 8, and the specific application method is as follows:
adding the water phase and the oil phase into a static mixer (9) together, mixing the water phase and the oil phase into emulsion in the static mixer (9), and enabling the emulsion to enter a manifold (6) through a third flowmeter (10);
the composite oxidant sequentially enters a header (6) through a second metering pump (7) and a second flowmeter (8);
the emulsion and the composite oxidant are converged in a manifold (6) and then enter a tubular continuous reactor (1) through a bottom feed inlet;
the reducing agent sequentially flows through a first metering pump (5) and a first flowmeter (4) and then enters a tubular continuous reactor (1) through a bottom feeding hole;
and (2) heating and polymerizing the emulsion, the composite oxidant and the reducing agent in the tubular continuous reactor (1), stirring and shearing the mixture by a push type stirrer during reaction to form an emulsion type polymer product, outputting the emulsion type polymer product from a discharge port at the top, and finally packaging to finish the preparation of the emulsion type polymer product.
10. Use of an apparatus for the continuous production of an emulsion polymer according to claim 9, wherein the temperature data collected by all the temperature sensors is transmitted to a PLC, and the PLC adjusts the opening degree of the medium valve in the jacket according to the received temperature data.
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