CN115430406B - Preparation process and application of polymer microporous material - Google Patents

Preparation process and application of polymer microporous material Download PDF

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Publication number
CN115430406B
CN115430406B CN202211126029.5A CN202211126029A CN115430406B CN 115430406 B CN115430406 B CN 115430406B CN 202211126029 A CN202211126029 A CN 202211126029A CN 115430406 B CN115430406 B CN 115430406B
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stirring
oil
cover
microporous material
rod
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CN115430406A (en
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陈光辉
贺玮
方敏
陈亚红
周一帆
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Zhejiang Lanjing Technology Co ltd
Zhejiang Lanjing Technology Co ltd Hangzhou Branch
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Zhejiang Lanjing Technology Co ltd
Zhejiang Lanjing Technology Co ltd Hangzhou Branch
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/58—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention relates to a preparation process and application of a polymer microporous material, which solves the problems that the polymer microporous material in the prior art is not applied to marine environment-friendly adsorption and the application effect is not ideal, and the technical scheme is as follows: firstly, preparing modified epoxy resin, and carrying out melt grafting modification to improve melt viscoelasticity and crystallization performance of the modified epoxy resin; then during the foaming process of adding the nucleating agent, the nucleating agent influences the cell structure by heterogeneous nucleation factors, so that bubbles are heterogeneous nucleated to provide nucleation density; meanwhile, the reaction device is improved, so that raw materials are stirred more uniformly in the reaction vessel, the stirring efficiency is better, the reaction is more complete, and the material utilization rate is improved; the lipophilic and hydrophobic microporous material with good adsorption performance is prepared by improving the three aspects in sequence, is used for environment-friendly (such as lakes and oceans) emergency treatment, has good adsorption effect and is easy to recycle and treat.

Description

Preparation process and application of polymer microporous material
Technical Field
The invention relates to a preparation process and application of a polymer microporous material, in particular to a preparation process and application of a polymer microporous material with high oil absorption and low water absorption.
Background
The adsorption material comprises: natural inorganic adsorbent materials, natural organic adsorbent materials and synthetic organic adsorbent materials.
Natural inorganic adsorption materials comprise clay, lime, graphite, active carbon and the like, the natural inorganic adsorption materials are low in price, raw materials are easy to obtain, but the natural inorganic adsorption materials are large in size and high in transportation cost, and the inorganic materials are mostly incombustible and disposable, so that the treatment of the materials after adsorption is difficult.
Natural organic adsorbents are composed of natural products (such as cellulose of wood fiber, cornstalk, straw, wood dust, bark, peanut skin, etc.) and rubber, and can remove oils and organic matters which are oil-phase from water. The natural organic adsorption material has the advantages of low cost, no toxicity, easy obtainment and the like, but is difficult to regenerate.
The synthetic organic adsorption material has the advantages of polyurethane, polypropylene and resin with a large number of meshes, and has the advantages of large specific surface area, lipophilicity, hydrophobicity and the like, so that the synthetic organic adsorption material has natural advantages in application to the treatment of the aqueous waste oil. But it is less applicable in environmental emergency treatment and yet to be developed.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a preparation process and application of a polymer microporous material, wherein modified epoxy resin is prepared and modified by melt grafting so as to improve melt viscoelasticity and crystallization performance of the polymer microporous material; then during the foaming process of adding the nucleating agent, the nucleating agent influences the cell structure by heterogeneous nucleation factors, so that bubbles are heterogeneous nucleated to provide nucleation density; meanwhile, the reaction device is improved, so that raw materials are stirred more uniformly in the reaction vessel, the stirring efficiency is better, the reaction is more complete, and the material utilization rate is improved; the lipophilic and hydrophobic microporous material with good adsorption performance is prepared by improving the three aspects in sequence, is used for environment-friendly (such as lakes and oceans) emergency treatment, has good adsorption effect and is easy to recycle and treat.
The technical aim of the invention is mainly solved by the following technical scheme: a process for preparing a polymeric microporous material, comprising the steps of:
s1: preparing modified epoxy resin: in a first reaction unit;
s2: preparing a mixed solution A:
putting polyether polyol into a first reaction device with inert gas atmosphere, and melting the polyether polyol and the modified epoxy resin under the condition of heating and pressurizing to prepare a mixed solution A;
s3: preparing an auxiliary reagent B:
mixing a nucleating agent, a catalyst, a foam stabilizer, a foaming agent, a surfactant, a reactive flame retardant and a crosslinking agent to prepare an auxiliary reagent B;
s4: preparation of mixture C:
the mixed solution A is dropped out of the first reaction device and then enters the second reaction device, isocyanate is put into the second reaction device and stirred, so that the mixed solution A and the isocyanate are uniformly mixed, and a mixture C is prepared;
s5: mixing the auxiliary reagent B with the mixture C, molding, reacting and foaming:
adding the auxiliary reagent B into a second reaction device, stirring to uniformly mix the auxiliary reagent B with the mixture C, and rapidly injecting or pouring the mixture into a mold to enable the mixture to be freely foamed;
S6: preparing a polymer microporous material:
and (3) standing the mould at a set temperature to fix and cure the foam, thus obtaining the oleophylic and hydrophobic polymer microporous material.
In step S3, during the foaming process with the addition of the nucleating agent, the nucleating agent acts on the cell structure in a heterogeneous nucleation manner.
As a further improvement and supplement to the technical scheme, the invention adopts the following technical measures:
the preparation step of step S1 (i.e., the preparation step of preparing the modified epoxy resin) includes:
s11, raw materials are put into a first reaction device:
adding epoxy resin, acrylic acid monomer, initiator and modifier into a first reaction device; wherein, the usage amount of the acrylic acid monomer is 20wt% of the usage amount of the epoxy resin; the usage amount of the initiator is 5wt% of the usage amount of the epoxy resin; the modifier is used in an amount of 5wt% of the epoxy resin to make-CH-or-CH-in the epoxy resin molecule 2 -initiating graft polymerization with acrylic monomers as active sites to form a modified epoxy resin containing carboxylic acid groups;
s12, reacting at a certain temperature and time:
raising the temperature of the first reaction device to 100-110 ℃, and keeping the temperature to enable the raw materials to react for 40min;
S13, preparing modified epoxy resin:
and (3) reducing the temperature of the first reaction device to 25 ℃, adding a proper amount of alkali, neutralizing the reaction product obtained in the step (S12), and regulating the pH value of the reaction product to 6.5-7 to obtain the water-soluble modified epoxy resin.
Further preferably, in the step S2, the temperature is 100-120 ℃, the pressure is 0.3-0.5MPa, and the stirring time is 20min;
in the step S3, the foaming agent is deionized water foaming agent; the nucleating agent acts on the foaming process in the step S4 in a heterogeneous nucleating mode and is used for influencing the cell structure;
in the step S4, the stirring speed is 2000r/min, and the stirring time is 1-2min;
in the step S5, the stirring speed is 2000r/min, and the stirring time is 8-10S;
in the step S6, standing for 5-10min, shaping the foam, removing the foam epidermis, placing the foam with the epidermis removed in an environment of 25-27 ℃ for 1-1.5 h, and curing the foam.
Further preferably, the components are prepared from the following components in parts by weight:
modified epoxy resin: 100 parts;
polyether polyol: 100 parts;
nucleating agent: 5-10 parts of a catalyst for accelerating crystallization rate and increasing crystallization density;
isocyanate: 40 parts;
catalyst: 4-5 parts;
foam stabilizer: 0.5-1 part of a porous ceramic material for ensuring that pores are fine and uniform, and when the porous ceramic material is in a low-viscosity stage, the pore walls are stable, and the pores can grow to a thickness suitable for pore opening, so that conditions are created for final pore opening;
Foaming agent: 6-10 parts;
and (2) a surfactant: 2-3 parts of a polymer microporous material solution, which can obviously reduce the surface tension, has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution;
reactive flame retardant: 8-10 parts of a flame retardant, which has less influence on the service performance of the polymer material and has lasting flame retardance;
crosslinking agent: 4-5 parts of an insoluble substance which reacts with the modified epoxy resin to form a bridge bond between the generated polymer molecular chains and become a three-dimensional structure.
For the technical scheme, the generation and application of the modified epoxy resin are improved points, the other improvement point is the application of the nucleating agent, and the other improvement point is embodied in the reaction device.
The first reaction device and the second reaction device are the same reaction device, the reaction device comprises a reaction container and a stirring device arranged in the reaction container, the inner wall of the reaction container is in an inverted frustum shape, a stirring blade assembly on the stirring device is radially arranged by taking a central axis of the inverted frustum shape as a center, rotating wind in the centrifugal direction generated during stirring of the stirring blade assembly collides with the inner wall of the reaction container and changes the moving direction to form reflected wind, the reflected wind is reflected to the center of the reaction container and moves towards the direction of the stirring blade assembly, and the reflected wind collides with the rotating wind, so that stirring is uniform.
The rotary wind formed by the stirring blade assembly rotates by taking a corresponding point on the axis of the stirring shaft as a rotation center and taking a plane perpendicular to the axis as a rotation plane.
The inner wall of reaction vessel is run into to the rotatory wind, is reflected back, and the plane that the reflection wind that the reflection was got back is located intersects with the plane that the rotatory wind is located for the reflection wind produces the collision with the rotatory wind, and reflection wind and rotatory wind all have stirring, smash about the material of stirring, simultaneously, the impact that the collision of reflection wind and rotatory wind produced can effectively smash the material fast, improves stirring efficiency and effect.
In order to further improve stirring efficiency and effect, agitating unit includes by actuating mechanism driven (mixing) shaft, the (mixing) shaft sets up the axis position of reaction vessel, the stirring vane subassembly sets up on the (mixing) shaft, the stirring vane subassembly divides the three-layer setting at least, and every layer sets up three sets of at least stirring vane subassembly is central symmetry setting, makes equipartition revolving wind and reflection wind increase mutual collision region in the inner chamber of reaction vessel.
The inlet end of the reaction container is a large-mouth end, a sealing cover is arranged on the reaction container, the sealing cover comprises a first cover and a second cover which are matched in an opening-closing manner, a linkage mechanism and a locking structure which are matched with the first cover and the second cover, the linkage mechanism enables the first cover and the second cover to be synchronously opened or closed, the linkage mechanism enables the driving mechanism to intermittently work, the first cover and the second cover are separated and opened, the inlet channel is opened for feeding, and the linkage mechanism enables the driving mechanism to stop working; the first cover and the second cover are moved to be closed in opposite directions, the inlet channel is closed to stop feeding, the linkage mechanism enables the driving mechanism to work, and the locking structure is used for enabling the first cover and the second cover to be closed stably.
The inlet end is large, which is not only beneficial to throwing materials, but also beneficial to arranging a linkage mechanism, a locking mechanism and a driving mechanism.
When the material is fed, the driving mechanism stops working, namely the stirring action stops, so that the material is prevented from being stirred and flying to the outside of the reaction container. When the feeding is stopped, the first cover and the second cover are closed, so that the stirring can be fully performed and the stirring is not easy to fly everywhere.
The linkage mechanism comprises: a rack and a first gear respectively arranged on the first cover and the second cover, a first rotating shaft driven by the first gear, an adjusting worm arranged on the first rotating shaft, a thread sleeve sleeved on the adjusting worm, the pull rod is fixed on the threaded sleeve, the rack is meshed with the first gear, and when the first cover and the second cover are synchronously opened or closed, the rack drives the first gear to rotate forwards or reversely; the pull rod is used for enabling the driving mechanism to work intermittently, the locking structure comprises an inserting block and an inserting groove which are respectively arranged on the splicing surfaces of the first cover and the second cover, and the inserting block is in inserting fit with the inserting groove.
The intermittent operation of the driving mechanism is specifically as follows:
when the first cover and the second cover are synchronously closed, the rack drives the first gear to rotate (at the moment, the first rotating shaft rotates along with the first gear, the thread bush rotates along with the first rotating shaft, the thread bush drives the pull rod to move downwards, the driving mechanism and the pull rod synchronously move downwards, the driving mechanism enables the stirring shaft to rotate, and the stirring mechanism starts stirring.
On the contrary, when the first cover and the second cover are synchronously opened, the rack drives the first gear to rotate (at the moment, the first rotating shaft rotates along with the first gear, the thread bush rotates along with the first rotating shaft, the thread bush drives the pull rod to move upwards, the driving mechanism and the pull rod synchronously move upwards, the driving mechanism does not drive the stirring shaft to rotate, and the stirring mechanism stops stirring.
Further preferably, the driving mechanism includes: the stirring device comprises a sliding rail arranged on a second cover, a motor arranged on the sliding rail, a second gear intermittently meshed with a driving wheel on the motor, a stirring shaft arranged on the second gear, and a pull rod, wherein the lower end of the pull rod is fixed on the motor and used for pushing the motor to move up or down along the sliding rail; when the stirring device moves downwards, the second gear is meshed with the driving wheel, the stirring shaft rotates, and the stirring device starts to work.
The stirring shaft is provided with a scraping plate mechanism, and in order to avoid mutual interference, the scraping plate mechanism and the stirring device are staggered in the circumferential direction. The scraper mechanism comprises a rotary table arranged on the stirring shaft, a fixing rod vertically arranged on the lower surface of the rotary table, a support rod pivoted on the fixing rod, and a strip scraper matched with the other end of the support rod, wherein the scraper is attached to the inner wall of the reaction container and is arranged in an up-down inclined direction, the support rod is propped against the scraper, the rotary table rotates along with the stirring shaft, the rotary table drives the fixing rod and the support rod to rotate, and the support rod drives the scraper to rotate.
In order to improve efficiency of the scraper mechanism, the scraper mechanisms are at least two groups, the axes of the stirring shafts are symmetrically arranged in a central symmetry mode, each group of scraper mechanisms share one turntable, each group of scraper mechanisms is provided with a supporting spring, the supporting springs are used for generating auxiliary supporting force for the scraper, one end of each supporting spring is fixed on the fixing rod, and the other end of each supporting spring is fixed on the scraper.
Preferably, the stirring vane assembly comprises a fixed seat fixedly arranged on the stirring shaft, a stirring rod pivoted at the outer end of the fixed seat, and a stirring sheet arranged on the stirring rod, wherein a chute is arranged in the stirring rod, a sliding block is arranged at the inner end of the stirring sheet, the sliding block is in sliding fit with the chute, a first spring is arranged in the chute, the inner end of the first spring is connected with the inner end of the chute, the outer end of the first spring is connected with the sliding block, and when the stirring vane assembly rotates, the stirring sheet moves outwards under the action of centrifugal force, and the first spring is stretched by tension; when stirring vane subassembly stops rotatory, first spring resets, the slider receives the effect of first spring, the stirring piece to remove in the spout, and accomodate in the spout, be favorable to avoiding the material to glue in the stirring piece, when stopping stirring, the stirring piece shrink enters into the spout, through the relative movement between stirring piece and the spout, makes the material on the stirring piece drop.
A second spring is arranged between the fixed seat and the stirring rod, the inner end of the second spring is fixed on the fixed seat and is close to the stirring shaft, the outer end of the second spring is fixed on the stirring rod, when the stirring blade assembly rotates, the stirring rod is radially arranged under the action of centrifugal force and forms the same straight line with the fixed seat, and the second spring is stretched by tensile force; when the stirring vane component stops rotating, the stirring rod loses centrifugal force, and under the reset action of the second spring and the dead weight action of the stirring rod, the stirring rod rotates downwards and collides with the stirring shaft until the stirring rod stops resting on the stirring shaft. The stirring rod is beneficial to avoiding the adhesion of materials to the stirring rod, when stirring is stopped, the stirring rod takes the inner end as a pivot point, the outer end is rotated downwards to drop and collide with the stirring rod, so that the materials on the stirring rod drop, the utilization rate of the materials is improved, and the waste is reduced.
The outlet end of the reaction vessel is a small-mouth end, an output mechanism is arranged on the small-mouth end, and the output mechanism comprises:
linkage disc: the upper end of the stirring shaft is arranged on the stirring shaft, the stirring shaft drives the stirring shaft to rotate, and the linkage disc is used as a linkage part to enable the conveying worm on the linkage disc to rotate;
Conveying worm: the linkage disc is arranged at the lower end of the linkage disc and is driven to rotate by the linkage disc;
conveying shell: the upper end of the conveying shell is fixed at the outlet part of the reaction container, the lower end of the conveying shell is provided with a liquid dropping port, and the conveying shell is covered on the periphery of the conveying worm, so that the inner cavity of the conveying shell is matched with the conveying worm to form a conveying channel;
and (3) a filtering assembly: which is arranged at the periphery of the linkage disc and is used for filtering unreacted or insufficiently reacted impurities, and comprises:
and (3) a filtering frame: is in two semicircular rings, and comprises an outer circle part, an inner circle part and a radial part connecting the outer circle part and the inner circle part; when the two filter frames are combined, the outer circle part is detachably arranged at the corresponding part of the reaction container, and the inner circle part is enmeshed with the periphery of the linkage disc;
and (3) a filter screen: the filter screen is semicircular, is detachably arranged in the filter frame and is used for filtering unreacted or insufficiently reacted impurities, and the filter screen is replaceable;
a magnet: the radial part is used for sucking two filter frames, so that the filter frames are spliced to form a circular ring shape.
Drip cap: the detachable type liquid dropping device is arranged at the lower end of the conveying shell and is used for opening or closing the liquid dropping opening.
The outlet end of the reaction vessel is a small-mouth end, forms a funnel shape, is convenient for converging materials, and ensures that the converged materials flow out of the reaction vessel with high efficiency.
The two filter frames on the filter assembly can be separated from each other, and the two filter frames can be conveniently detached from the reaction vessel.
The magnet is used for attracting the two filter frames, so that the inner rings of the two filter frames are used for holding the linkage disc, and the outer ring is detachably fixed on the reaction container, so that the disassembly and assembly are more convenient.
Another technical subject matter referred to herein is: use of a polymeric microporous material characterized by: the waste water treatment system applied to ocean Yun Cang comprises an oily waste water storage tank, an oil separating device connected with the oily waste water storage tank through a first pipeline, an oil detector matched with the oil separating device, and an oil adsorber connected with the oil separating device through a second pipeline, wherein the oil adsorber is filled with polymer microporous materials, and the polymer microporous materials are prepared by the preparation process of the polymer microporous materials.
The waste water treatment system is arranged in the bin body of the ocean cloud bin, when the oily waste water enters the oily waste water storage tank, the oil separation device and the oil detector are started, the oil separation device carries out oil skimming treatment on the oily waste water, oil skimming is discharged into the waste engine oil storage tank, the oily waste water flows back to the oily waste water storage tank or is discharged into the oil adsorber to carry out oil adsorption treatment, so that the oily waste water is discharged into the domestic waste water storage tank in the bin body after oil skimming and oil absorption are met, and the subsequent recovery treatment is facilitated.
The second pipeline comprises a main pipeline section and at least two branch pipeline sections communicated with an outlet of the main pipeline section, each branch pipeline section is provided with an electric valve, the outlet of each branch pipeline section is connected with one oil adsorber, the oil content detector is arranged on the main pipeline section and is in signal connection with the electric valves and the oil adsorbers, the oil content detector detects that the petroleum and hydrocarbon substance content in oil-containing water from the oil content separating device is more than 15mg/L, and then the electric valves and the oil adsorbers are opened; and when the content of petroleum hydrocarbon substances in the oily water is less than 15mg/L, the electric valve and the oil adsorber are closed. At least two oil adsorbers are arranged, so that the oil adsorption efficiency is improved, and the capacity sharing rate of each storage tank is improved.
The wastewater treatment system further comprises a domestic wastewater storage tank and a waste mineral oil storage tank, wherein the domestic wastewater storage tank is connected with the oil absorber through a third pipeline and is used for discharging qualified wastewater after oil absorber absorbs oil into the domestic wastewater storage tank, and the waste mineral oil storage tank is connected with the oil separating device through a fourth pipeline and is used for storing separated oil into the waste mineral oil storage tank through the fourth pipeline.
After oil skimming or oil absorption, standard sewage is discharged into the domestic sewage storage tanks, and after oil skimming treatment, the capacity of each storage tank can play a role in sharing, so that the reasonable utilization rate of the residual space of each storage tank is effectively improved, and the subsequent purification and recovery treatment are facilitated.
The invention has the beneficial effects that:
1. optimizing modified epoxy resin: by reacting-CH-or-CH-in the epoxy resin molecule 2 And (c) initiating graft polymerization with the acrylic monomer to form a modified epoxy resin containing carboxylic acid groups. The epoxy resin is grafted and modified to raise its melt viscoelasticity and improve its crystallization property, so that the resin has excellent water solubility.
2. Through an improved reaction device, the polymer microporous material with precisely controllable cell size and density and high aperture ratio is prepared through formula and process adjustment under the supercritical fluid state of inert gas.
3. The polymer microporous material has capillary effect, has strong adsorption and load characteristics, has high adsorption rate and difficult exudation, can adsorb greasy dirt with 8-10 times of the self weight, has high adsorption speed, and can effectively realize oil and water separation;
4. The density of the polymer microporous material is extremely small (about 30kg/m < 3 >), the polymer microporous material can float on the water surface, and the sudden organic chemical leakage pollution can be effectively treated by applying the offshore oil absorption;
5. the polymer microporous material has good chemical corrosion resistance and wear resistance, can be separated from oil dirt in a simple way after absorbing oil, and is convenient to recycle.
6. The polymer microporous material is applied to the ocean cloud bin, and is used as a filling material to be filled in an oil adsorber (the oil adsorber in the oil sewage emergency treatment device), so that the oil in the oil sewage can be absorbed and locked, the water is filtered, the oil-water separation effect is excellent, and the industrial practicability is good.
Drawings
FIG. 1 is a schematic structural view of a reaction apparatus according to the present invention.
FIG. 2 is a schematic cross-sectional view of A-A of FIG. 1.
Fig. 3 is a schematic view of the cross-sectional structure of B-B in fig. 1.
FIG. 4 is a schematic view of the cross-sectional structure of FIG. 1 taken along the direction C-C.
Fig. 5 is a schematic structural view showing a state in which a stirring blade assembly is opened in a stirring device according to the present invention.
FIG. 6 is a schematic view showing a state in which a stirring blade assembly is folded in a stirring device according to the present invention.
Fig. 7 is a schematic view of the structure of fig. 1 in a cross-section D-D.
Fig. 8 is a schematic structural view of a marine cloud deck according to the present invention.
Fig. 9 is a schematic view of the interior of the ocean cloud silo according to the present invention.
FIG. 10 is a table of adsorption curves for benzene-based chemicals for polymeric microporous materials.
FIG. 11 is a table of volume fractions of polymer microporous material adsorbing alcohols.
FIG. 12 is a table of volume fractions of polymeric microporous material adsorbing ketones.
FIG. 13 is a table of volume fractions of adsorbed esters of polymeric microporous materials.
FIG. 14 is a table of polymer microporous material adsorption alkane volume fraction curves.
FIG. 15 is a table of adsorption curves for polymeric microporous materials to pure liquid chemicals.
Fig. 16 is a bar graph of adsorption of a polymeric microporous material to an aqueous liquid chemical solution.
FIG. 17 is a table showing adsorption curves of polymeric microporous materials to aqueous solutions of water-soluble chemicals.
Fig. 18 is a bar graph of experimental results of polymeric microporous materials for inhibiting volatility to liquid chemicals.
1. A reaction device; 2. sealing cover; 3. a driving mechanism; 4. a bar scraping mechanism; 5. a reaction vessel; 6. a stirring device; 7. a filter assembly; 8. a linking disc; 9. a conveyor worm; 10. a conveying housing; 11. a drip cap; 12. ocean Yun Cang;
21. A first cover; 22. a slot; 23. a second cover; 24. inserting blocks; 25. a rack; 26. a first gear; 27. a first rotating shaft;
30. adjusting a worm; 31. a thread sleeve; 32. a slide rail; 33. a pull rod; 35. a motor; 37. A driving wheel; 38. a second gear; 39. a stirring shaft;
41. a turntable; 42. a fixed rod; 43. a support spring; 44. a support rod; 45. a scraper;
60. a stirring vane assembly; 61. a fixing seat; 62. stirring sheets; 63. a slide block; 64. a first spring; 65. a second spring; 66. a stirring rod;
71. a filter screen; 72. a magnet; 73. a filter frame;
12. ocean Yun Cang; 121. a domestic sewage storage tank; 122. a waste mineral oil storage tank; 123. an oily wastewater storage tank; 124. a filter; 125. an oil separating device; 126. an oil content detector; 127. a first electrically operated valve; 128. a second electrically operated valve; 129. an oil adsorber A; 130. an oil adsorber B; 131. a third electrically operated valve; 132. a fourth electrically operated valve; 133. a first pipeline; 134. a second pipeline; 135. A third pipeline; 136. a fourth pipeline;
Detailed Description
The technical scheme of the invention is further specifically described below through examples and with reference to the accompanying drawings.
Example 1: a process for preparing a polymeric microporous material, comprising the steps of:
s1: preparing modified epoxy resin: in a first reaction unit;
s2: preparing a mixed solution A:
putting polyether polyol into a first reaction device with inert gas atmosphere, and melting the polyether polyol and the modified epoxy resin under the condition of heating and pressurizing to prepare a mixed solution A;
s3: preparing an auxiliary reagent B:
mixing a nucleating agent, a catalyst, a foam stabilizer, a foaming agent, a surfactant, a reactive flame retardant and a crosslinking agent to prepare an auxiliary reagent B;
s4: preparation of mixture C:
the mixed solution A is dropped out of the first reaction device and then enters the second reaction device, isocyanate is put into the second reaction device and stirred, so that the mixed solution A and the isocyanate are uniformly mixed, and a mixture C is prepared;
s5: mixing the auxiliary reagent B with the mixture C, molding, reacting and foaming:
adding the auxiliary reagent B into a second reaction device, stirring to uniformly mix the auxiliary reagent B with the mixture C, and rapidly injecting or pouring the mixture into a mold to enable the mixture to be freely foamed;
s6: preparing a polymer microporous material:
and (3) standing the mould at a set temperature to fix and cure the foam, thus obtaining the oleophylic and hydrophobic polymer microporous material.
In step S3, during the foaming process with the addition of the nucleating agent, the nucleating agent acts on the cell structure in a heterogeneous nucleation manner.
As a further improvement and supplement to the technical scheme, the invention adopts the following technical measures:
the preparation step of step S1 (i.e., the preparation step of preparing the modified epoxy resin) includes:
s11, raw materials are put into a first reaction device:
adding epoxy resin, acrylic acid monomer, initiator and modifier into a first reaction device; wherein, the usage amount of the acrylic acid monomer is 20wt% of the usage amount of the epoxy resin; the usage amount of the initiator is 5wt% of the usage amount of the epoxy resin; the modifier is used in an amount of 5wt% of the epoxy resin to make-CH-or-CH-in the epoxy resin molecule 2 -initiating graft polymerization with acrylic monomers as active sites to form a modified epoxy resin containing carboxylic acid groups;
s12, reacting at a certain temperature and time:
raising the temperature of the first reaction device to 100-110 ℃, and keeping the temperature to enable the raw materials to react for 40min;
s13, preparing modified epoxy resin:
and (3) reducing the temperature of the first reaction device to 25 ℃, adding a proper amount of alkali, neutralizing the reaction product obtained in the step (S12), and regulating the pH value of the reaction product to 6.5-7 to obtain the water-soluble modified epoxy resin.
Further preferably, in the step S2, the temperature is 100-120 ℃, the pressure is 0.3-0.5MPa, and the stirring time is 20min;
in the step S3, the foaming agent is deionized water foaming agent; the nucleating agent acts on the foaming process in the step S4 in a heterogeneous nucleating mode and is used for influencing the cell structure;
in the step S4, the stirring speed is 2000r/min, and the stirring time is 1-2min;
in the step S5, the stirring speed is 2000r/min, and the stirring time is 8-10S;
in the step S6, standing for 5-10min, shaping the foam, removing the foam epidermis, placing the foam with the epidermis removed in an environment of 25-27 ℃ for 1-1.5 h, and curing the foam.
Further preferably, the components are prepared from the following components in parts by weight:
modified epoxy resin: 100 parts;
polyether polyol: 100 parts;
nucleating agent: 5-10 parts of a catalyst for accelerating crystallization rate and increasing crystallization density;
isocyanate: 40 parts;
catalyst: 4-5 parts;
foam stabilizer: 0.5-1 part of a porous ceramic material for ensuring that pores are fine and uniform, and when the porous ceramic material is in a low-viscosity stage, the pore walls are stable, and the pores can grow to a thickness suitable for pore opening, so that conditions are created for final pore opening;
foaming agent: 6-10 parts;
and (2) a surfactant: 2-3 parts of a polymer microporous material solution, which can obviously reduce the surface tension, has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution;
Reactive flame retardant: 8-10 parts of a flame retardant, which has less influence on the service performance of the polymer material and has lasting flame retardance;
crosslinking agent: 4-5 parts of an insoluble substance which reacts with the modified epoxy resin to form a bridge bond between the generated polymer molecular chains and become a three-dimensional structure.
For the technical scheme, the generation and application of the modified epoxy resin are improved points, the other improvement point is the application of the nucleating agent, and the other improvement point is embodied in the reaction device.
The first reaction device and the second reaction device are the same reaction device 1, the reaction device 1 comprises a reaction container 5 and a stirring device 6 arranged in the reaction container 5, the inner wall of the reaction container 5 is in an inverted frustum shape, a stirring blade assembly 60 on the stirring device 6 is radially arranged by taking a central axis of the inverted frustum shape as a center, rotating wind in a centrifugal direction generated during stirring of the stirring blade assembly 60 collides with the inner wall of the reaction container 5, the moving direction is changed to form reflected wind, the reflected wind is directed towards the center of the reaction container 5 and moves towards the direction of the stirring blade assembly 60, and the reflected wind collides with the rotating wind, so that stirring is uniform.
The rotational wind generated by the stirring blade assembly 60 rotates around a corresponding point on the axis of the stirring shaft 39 and around a plane perpendicular to the axis as a rotation plane.
The inner wall of reaction vessel 5 is hit to the rotatory wind, is reflected back, and the plane that the reflection wind that the reflection was got back is located intersects with the plane that the rotatory wind is located for the reflection wind produces the collision with the rotatory wind, and reflection wind and rotatory wind all have stirring, smash about the material of stirring, simultaneously, the impact that the collision of reflection wind and rotatory wind produced can effectively smash the material fast, improves stirring efficiency and effect.
In order to further improve the stirring efficiency and effect, the stirring device 6 comprises a stirring shaft 39 driven by the driving mechanism 3, the stirring shaft 39 is arranged at the central axis position of the reaction vessel 5, the stirring vane assembly 60 is arranged on the stirring shaft 39, the stirring vane assembly 60 is at least arranged in three layers, and each layer is at least provided with three groups of stirring vane assemblies 60 which are arranged in a central symmetry manner, so that the inner cavity of the reaction vessel 5 is uniformly distributed with rotary wind and reflected wind to increase the mutual collision area.
The inlet end of the reaction vessel 5 is a large-mouth end, a sealing cover 2 is arranged on the reaction vessel, the sealing cover 2 comprises a first cover 21 and a second cover 23 which are matched in an opening-closing manner, a linkage mechanism and a locking structure which are matched with the first cover 21 and the second cover 23, the linkage mechanism enables the first cover 21 and the second cover 23 to be synchronously opened or closed, the linkage mechanism enables the driving mechanism 3 to work intermittently, the first cover 21 and the second cover 23 are separated and opened, the inlet channel is opened for feeding, and the linkage mechanism enables the driving mechanism 3 to stop working; the first cover 21 and the second cover 23 are moved towards each other to be closed, the inlet channel is closed to stop feeding, the linkage mechanism enables the driving mechanism 3 to work, and the locking structure is used for enabling the first cover 21 and the second cover 23 to be closed stably.
The inlet end is large, which is not only beneficial to throwing materials, but also beneficial to arranging a linkage mechanism, a locking mechanism and a driving mechanism 3.
When the material is fed, the driving mechanism 3 stops working, namely the stirring action stops, and the material is prevented from being stirred and flying to the outside of the reaction vessel 5. When the feeding is stopped, the first cover 21 and the second cover 23 are closed, and the stirring can be fully performed, so that the stirring is not easy to fly everywhere.
The linkage mechanism comprises: the rack 25 and the first gear 26 are respectively arranged on the first cover 21 and the second cover 23, the first rotating shaft 27 is driven by the first gear 26, the adjusting worm 30 is arranged on the first rotating shaft 27, the threaded sleeve 31 is sleeved on the adjusting worm 30, the pull rod 33 is fixed on the threaded sleeve 31, the rack 25 is meshed with the first gear 26, and the rack 25 drives the first gear 26 to rotate forward or reversely when the first cover 21 and the second cover 23 are synchronously opened or closed; the pull rod 33 is used for intermittently operating the driving mechanism 3, the locking structure comprises an inserting block 24 and an inserting groove 22 which are respectively arranged on the splicing surfaces of the first cover 21 and the second cover 23, and the inserting block 24 is in inserting fit with the inserting groove 22.
The intermittent operation of the driving mechanism 3 is specifically as follows:
When the first cover 21 and the second cover 23 are synchronously closed, the rack 25 drives the first gear 26 to rotate (at the moment, the first rotating shaft 27 rotates along with the first gear 26, the thread bush 31 rotates along with the first rotating shaft 27, the thread bush 31 drives the pull rod 33 to move downwards, the driving mechanism 3 and the pull rod 33 synchronously move downwards, the driving mechanism 3 drives the stirring shaft 39 to rotate, and the stirring mechanism starts stirring.
On the contrary, when the first cover 21 and the second cover 23 are synchronously opened, the rack 25 drives the first gear 26 to rotate (set to rotate reversely at this time), the first rotating shaft 27 rotates along with the first gear 26, the threaded sleeve 31 rotates along with the first rotating shaft 27, the threaded sleeve 31 drives the pull rod 33 to move upwards, the driving mechanism 3 and the pull rod 33 synchronously move upwards, the driving mechanism 3 does not drive the stirring shaft 39 to rotate, and the stirring mechanism stops stirring.
Further preferably, the driving mechanism 3 includes: the stirring device comprises a sliding rail 32 arranged on the second cover 23, a motor 35 arranged on the sliding rail 32, a second gear 38 intermittently meshed with a driving wheel 37 on the motor 35, wherein the second gear 38 is arranged on a stirring shaft 39, the lower end of a pull rod 33 is fixed on the motor 35, the pull rod 33 is used for pushing the motor 35 to move up or down along the sliding rail 32, when the motor moves up, the second gear 38 is separated from the driving wheel 37, the stirring shaft 39 stops rotating, and the stirring device 6 stops working; when moving downwards, the second gear 38 is meshed with the driving wheel 37, the stirring shaft 39 rotates, and the stirring device 6 starts to work.
The stirring shaft 39 is provided with a scraper mechanism 4, and the scraper mechanism 4 and the stirring device 6 are arranged in a staggered manner in the circumferential direction so as to avoid mutual interference. The scraping plate mechanism 4 comprises a rotary plate 41 arranged on the stirring shaft 39, a fixed rod 42 vertically arranged on the lower surface of the rotary plate 41, a supporting rod 44 pivoted on the fixed rod 42, and a strip-shaped scraping plate 45 matched with the other end of the supporting rod 44, wherein the scraping plate 45 is attached to the inner wall of the reaction container 5 and is arranged in an up-down inclined direction, the supporting rod 44 is propped against the scraping plate 45, the rotary plate 41 rotates along with the stirring shaft 39, the rotary plate 41 drives the fixed rod 42 and the supporting rod 44 to rotate, and the supporting rod 44 drives the scraping plate 45 to rotate.
In order to improve the efficiency of the scraper mechanism 4, at least two groups of scraper mechanisms 4 are arranged in a central symmetry manner by taking the axis of the stirring shaft 39 as a symmetry center line, each group of scraper mechanisms 4 share one turntable 41, each group of scraper mechanisms 4 is provided with a supporting spring 43, the supporting springs 43 are used for generating auxiliary supporting force for the scraper 45, one end of each supporting spring 43 is fixed on the fixed rod 42, and the other end of each supporting spring 43 is fixed on the scraper 45.
Preferably, the stirring vane assembly 60 includes a fixed seat 61 fixedly disposed on the stirring shaft 39, a stirring rod 66 pivotally connected to an outer end of the fixed seat 61, a stirring plate 62 disposed on the stirring rod 66, a sliding groove disposed in the stirring rod 66, a sliding block 63 disposed at an inner end of the stirring plate 62, the sliding block 63 slidably engaged with the sliding groove, a first spring 64 disposed in the sliding groove, an inner end of the first spring 64 connected to an inner end of the sliding groove, an outer end of the first spring 64 connected to the sliding block 63, and when the stirring vane assembly 60 rotates, the stirring plate 62 moves outwards under centrifugal force, and the first spring 64 is stretched by a tensile force; when the stirring vane assembly 60 stops rotating, the first spring 64 is reset, the sliding block 63 is acted by the first spring 64, the stirring sheet 62 moves towards the inside of the chute and is accommodated in the chute, so that the stirring sheet 62 is prevented from being stuck to the stirring sheet 62, and when stirring is stopped, the stirring sheet 62 contracts to enter the chute, and the material on the stirring sheet 62 falls off through the relative movement between the stirring sheet 62 and the chute.
A second spring 65 is arranged between the fixed seat 61 and the stirring rod 66, the inner end of the second spring 65 is fixed on the fixed seat 61 and is close to the stirring shaft, the stirring rod 66 fixed at the outer end of the second spring 65 is radially arranged under the action of centrifugal force when the stirring vane assembly 60 rotates, the stirring rod 66 and the fixed seat 61 form the same straight line, and the second spring 65 is stretched by tensile force; when the rotation of the stirring blade assembly 60 is stopped, the stirring rod 66 loses centrifugal force, and the stirring rod 66 rotates downward and collides with the stirring shaft 39 until resting on the stirring shaft 39 under the restoring action of the second spring 65 and the self weight of the stirring rod 66. The stirring rod 66 is beneficial to avoiding the adhesion of materials to the stirring rod 66, when stirring is stopped, the stirring rod 66 takes the inner end as a pivot point, the outer end rotates downwards to drop and collides with the stirring rod 66, so that the materials on the stirring rod 66 drop, the utilization rate of the materials is improved, and the waste is reduced.
The outlet end of the reaction vessel 5 is a small-mouth end, and an output mechanism is arranged on the small-mouth end and comprises:
linkage disc 8: the upper end of the stirring shaft 39 is arranged on the stirring shaft 39, the stirring shaft 39 drives the stirring shaft to rotate, and the linkage disc 8 serves as a linkage part to enable the conveying worm 9 on the stirring shaft to rotate;
conveying worm 9: the device is arranged at the lower end of the linkage disc 8, and is driven to rotate by the linkage disc 8;
delivery casing 10: the upper end of the conveying shell is fixed at the outlet part of the reaction container 5, the lower end of the conveying shell is provided with a liquid dropping port, and the conveying shell 10 is covered on the periphery of the conveying worm 9, so that the inner cavity of the conveying shell 10 is matched with the conveying worm 9 to form a conveying channel;
filter assembly 7: which is provided at the periphery of the interlocking plate 8 for filtering impurities which are unreacted or insufficiently reacted, and includes:
a filter frame 73: is in two semicircular rings, and comprises an outer circle part, an inner circle part and a radial part connecting the outer circle part and the inner circle part; the outer circle parts of the two filter frames 73 are detachably arranged at the corresponding parts of the reaction container 5 when being spliced, and the inner circle parts are enmeshed with the periphery of the linkage disc 8;
filter screen 71: is semi-circular and detachably arranged in the filtering frame 73, is used for filtering unreacted or insufficiently reacted impurities, and the filtering net 71 is replaceable;
Magnet 72: the filter frame is arranged on the radial part and used for sucking two filter frames 73, so that the filter frames 73 are spliced to form a circular ring shape.
Drip port cap 11: and is removably disposed at the lower end of the delivery casing 10 for opening or closing the drip opening.
The outlet end of the reaction vessel 5 is a small-mouth end, forms a funnel shape, is convenient for converging materials, and enables the converged materials to flow out of the reaction vessel 5 with high efficiency.
The two filter frames 73 of the filter assembly 7 can be separated from each other, and the two filter frames 73 can be conveniently detached from the reaction vessel 5.
The magnet 72 is used for attracting the two filter frames 73, so that the inner rings of the two filter frames 73 are wrapped around the linkage disc 8, and the outer ring is detachably fixed on the reaction vessel 5, so that the disassembly and assembly are more convenient.
In the process of the preparation technology of the polymer microporous material, the preparation technology has the following characteristics:
(1) The conventional process of physical foaming is described in terms of extrusion foaming equipment and bubble nucleation theory, and mainly comprises the following five steps: melting of solid resin particles, gas (inert gas) injection, homogenized mixing with molten material, formation of bubble nuclei, bubble growth, and cell shaping. Either step has a significant impact on the structure and properties of the final foamed article. Therefore, in order to obtain the polymer foaming material with uniform foam cells and high foaming multiplying power, the technical scheme is purposefully improved in various aspects such as raw materials, formulas, equipment, process conditions and the like.
(2) Bubble nucleation mechanism: in the foaming process of adding the nucleating agent, the technical scheme mainly considers the influence on the cell structure by heterogeneous nucleation factors.
(3) Mechanism of unstable defects such as bubble merging, collapse and gas escape phenomena occurring during bubble growth: on the one hand, the high-crystallinity polyurethane foam has higher crystallinity, on the other hand, the macromolecular chains are of a linear structure, so that the macromolecular chains have higher activity only above the melting point of the macromolecular chains, and once the macromolecular chains exceed the melting point of the macromolecular chains, the viscosity of the macromolecular chains is rapidly reduced along with the rise of temperature, and the melt strength is lower because entanglement among macromolecules is weaker, and the strain hardening phenomenon is avoided in the process of stretching and flowing, cell walls are easy to crack and/or collapse in the foaming process, and a foamed product with uniform cell structure and high foaming multiplying power is difficult to obtain. In order to overcome the defects, the polymer foaming material with uniform cell structure and high foaming multiplying power is prepared, and on the basis of summarizing and analyzing the foaming principle of a polymer direct extrusion, the technical scheme adopts the following improvement modes:
(1) preparing modified epoxy resin, and performing melt grafting modification to improve melt viscoelasticity and crystallization performance of the modified epoxy resin;
(2) The reaction device is improved, so that the whole structure is suitable for gas injection, and the improvement of the stirring device improves the mixing capability of the mixed solution;
(3) in formulation aspect, heterogeneous nucleation of bubbles by addition of a nucleating agent to provide nucleation density; and a surfactant is added to improve the diffusion rate of the gas.
The prepared polymer microporous material is subjected to the following ten adsorptivity verification:
the existing various adsorption materials are single in adsorption to the liquid dangerous chemicals, and have large limitation, so that the use of the adsorption materials is greatly limited, and the adsorption materials with excellent performance have to have good adsorption performance to various dangerous chemicals. And (3) detecting the adsorption performance of the polymer microporous material on some common and representative hazardous chemicals in benzene, alcohols, ketones, lipids and alkanes by experiments, so as to determine the adsorption characteristics of the polymer microporous material on different types of hazardous chemicals, and provide a theoretical basis for practical application of the polymer microporous material.
The volatility, water solubility, toxicity, density, viscosity and other properties of different liquid hazardous chemicals are different, so that the adsorption effects of the polymer microporous material on different liquid hazardous chemicals can be different. According to the category of 16 liquid dangerous chemicals selected, the adsorption performance of the polymer microporous material on the liquid dangerous chemicals is tested, the adsorption performance of different liquid dangerous chemicals is compared, and the reasons for different adsorption effects of the polymer microporous material on the selected liquid dangerous chemicals are found out by combining the properties of the liquid dangerous chemicals, so that the liquid dangerous chemicals suitable for the treatment and adsorption of the polymer microporous material are deduced.
First kind: adsorption experiment of benzene liquid hazardous chemical substances:
as shown in FIG. 10, the adsorption volume multiple curves of the polymer microporous material on four benzene dangerous chemicals have approximately the same increasing trend, basically reach an adsorption saturation state about 15min, and slowly increase after 15 min. The adsorption volume multiple of the four dangerous chemicals is about 12ml/g at 60min, and the maximum adsorption volume multiple is 12.5 ml/g and the minimum adsorption volume multiple is 11.5 ml/g. The polymer microporous material has a faster adsorption rate to four selected hazardous chemicals, wherein the adsorption rate to styrene is the fastest, the adsorption volume multiple reaches 11ml/g in 5min, and the curve graph shows that an inflection point appears in 10min, which is faster than the time of the inflection point of the adsorption curve of benzene, toluene and xylene by 5min, namely the time required for reaching the adsorption saturation state is short.
Second kind: adsorption experiment on alcohol liquid dangerous chemicals:
as can be seen from FIG. 11, the increase trend of the adsorption volume multiple of the polymer microporous material to methanol and ethanol is basically consistent, the adsorption volume multiple of ethanol is slightly higher than that of methanol, and at 60min, the volume multiple of adsorbed ethanol is 8ml/g and the volume multiple of adsorbed methanol is 7.8 ml/g. The adsorption volume multiple of the polymer microporous material to glycol is lower and is only about 0.7 ml/g, and the volume multiple curve has no obvious increasing trend.
Third kind: adsorption experiment on ketone liquid hazardous chemicals:
the adsorption volume multiple curve of the polymer microporous material to ketone is shown in figure 12, the adsorption curve of the polymer microporous material to acetone and methyl isobutyl ketone has consistent increasing trend, and basically reaches an adsorption saturation state after about 20min, and has no obvious increasing trend after 20 min. The trend of the adsorption curve of 2-butanone is different from the trend of acetone and methyl isobutyl ketone, the adsorption curve of 2-butanone is in a slow growth state all the time, no obvious inflection point exists, the adsorption volume multiple increases rapidly before 15min, and the adsorption volume multiple increases slowly after 15 min. The polymer microporous material has the adsorption volume multiple of about 9.5ml/g for 60min of three ketone dangerous chemicals, the adsorption volume multiple of 10ml/g for methyl isobutyl ketone and about 9.5ml/g for 2-butanone.
Fourth kind: adsorption experiment of ester liquid dangerous chemicals:
as shown in FIG. 13, the adsorption volume multiple increase curves of the polymer microporous materials to esters are greatly different from each other, and at 60min, the adsorption volume multiple to ethyl acetate is about 10ml/g at most, the adsorption volume multiple to butyl titanate is about 8ml/g, the adsorption amount of dimethyl terephthalate is the lowest, and the volume multiple is only about 2 ml/g. Although the adsorption quantity of dimethyl phthalate is low, the saturated adsorption time of the polymer microporous material is not much different from that of ethyl acetate and butyl titanate, and the adsorption of three ester dangerous chemicals is about 20min and has an inflection point.
Fifth: adsorption experiment of alkane liquid hazardous chemical substances:
as shown in fig. 14, the adsorption volume multiples of the alkanes are all higher, and the volume multiple curve increases approximately the same. The adsorption volume multiple of the polymer microporous material to the normal hexane reaches 13ml/g at 10min, the curve of the adsorption volume multiple to the normal hexane also shows an inflection point at 10min, and after 15min, the adsorption volume multiple of the polymer microporous material to the cyclohexane is continuously increased to exceed the normal hexane. At 60min, the highest adsorption volume multiple of cyclohexane is 15ml/g; since the density of epichlorohydrin is at most 1.178 g/ml, and the densities of n-hexane and cyclohexane are 0.692 g/ml and 0.778g/ml, respectively, the adsorption volume multiple of epichlorohydrin calculated by the volume multiple formula is at least 8ml/g, and the adsorption volume multiple of n-hexane is 14ml/g.
Sixth: the adsorption effect of the polymer microporous material on different kinds of dangerous chemicals is compared:
the polymer microporous materials were tested for adsorption volume factors of paraxylene, methanol, ethylene glycol, acetone, cyclohexane and ethyl acetate at different times under the same experimental conditions, respectively, as shown in fig. 15.
As shown in fig. 15, the adsorption trend of the polymer microporous material to different kinds of dangerous chemicals is basically the same, the adsorption volume multiple of the polymer microporous material to the dangerous chemicals except ethylene glycol can reach more than 5ml/g at 1 min, after 20 min, the increase amplitude is very slow, the adsorption saturation state is basically reached, and the adsorption rate of the polymer microporous material to the dangerous chemicals is fast. However, polymeric microporous materials exhibit a certain variability in the adsorption capacity for different liquid hazardous chemicals, with a maximum adsorption volume multiple for cyclohexane of about 15 ml/g. The minimum adsorption volume multiple of ethylene glycol is 0.5 ml/g, the adsorption curve basically does not show an increasing trend, and because two hydroxyl groups are polar hydrophilic groups in the molecular structure of the ethylene glycol, the molecular polarity of the ethylene glycol is large, and the polymer microporous material is nonpolar and hydrophobic, so that the adsorption performance of the polymer microporous material on the ethylene glycol is poor, and the molecular structure of methanol also has one hydroxyl group, and the polarity of the methanol is also large. Thus, the adsorption performance of the polymer microporous material on methanol is relatively low, and the saturated adsorption volume multiple is about 8 ml/g.
Seventh: adsorption experiments of Polymer microporous Material on aqueous liquid chemical solutions
The adsorption performance of the polymer microporous material on the liquid chemical aqueous solution was studied through experiments, and chemical aqueous solutions with the solution volume fractions of 20% were prepared respectively, and the adsorption volume fractions of the polymer microporous material on the chemical aqueous solution are shown in fig. 16.
As can be seen from FIG. 16, the polymer microporous material has good adsorption performance for the aqueous solution of xylene, ethyl acetate and cyclohexane, can reach more than 10ml/g, has low adsorption performance for the aqueous solution of methanol, glycol and acetone, and has an adsorption volume multiple of less than 1 ml/g. The reason is that methanol, glycol and acetone are all dissolved in water, and the polymer microporous material is a hydrophobic material and does not selectively adsorb the aqueous solution of the soluble liquid dangerous chemical, so the polymer microporous material is not suitable for treating leakage accidents of the soluble liquid chemical in a water body.
Eighth: adsorption experiment of microporous Material after Water saturation on insoluble Water chemistry
The polymer microporous material is used as an adsorption material in water environment, has certain water absorbability, and is used for researching whether the polymer microporous material is in water body for a long time and is saturated or not to influence the adsorption of chemicals or not, the microporous material after the water absorbability is put into the chemicals for adsorption in experiments, and whether the water adsorbed in the microporous material is replaced with dangerous chemicals or not is observed, so that whether the polymer microporous material has preferential adsorption performance on dangerous chemicals or not between water and insoluble dangerous chemicals is researched.
The following table shows the adsorption of insoluble aqueous chemicals by microporous materials after saturation with water:
as shown in the above table, the polymer microporous material saturated with water will discharge a part of water adsorbed by itself after being placed in the chemical due to the adsorption of the chemical, i.e., the water adsorbed by the microporous material is displaced with the chemical, but the microporous material has different displacement drainage rates for different chemicals, and the displacement drainage rate is high for chemicals with high adsorption volume multiple, and the 1h average displacement drainage rate for the tested chemicals is 83.6%. Therefore, the polymer microporous material has strong selective adsorption performance on chemicals between water and insoluble water chemicals, and can be applied to the adsorption treatment of chemicals in water environment.
Ninth, the method comprises: adsorption experiments of Polymer microporous Material on Water-soluble chemical aqueous solutions
From the foregoing experiments, it is known that the polymeric microporous material has a good adsorption property for water-soluble chemicals, but because the polymeric microporous material has good hydrophobicity, if such chemicals are miscible with water in a water body, the polymeric microporous material can perform the following study on selective adsorption of leaked chemicals.
The experiments were carried out by preparing ethanol and acetone solutions with concentrations of 10%, 20%, 30%, 40%, 50%, 60%, 70%, and 80%, respectively, and the adsorption ratio of the microporous polymer material to the aqueous solutions of chemicals with different concentrations was tested by the experiments (the adsorption performance index of the microporous polymer material was measured by using the adsorption ratio instead of the adsorption volume ratio because the density was changed due to the change of the concentration of the solution), and the experimental results are shown in fig. 17.
As can be seen from fig. 17, the polymer microporous material does not selectively adsorb the aqueous solution of the soluble chemical, but the adsorption amount of the polymer microporous material to the aqueous solution of the water-soluble chemical is larger than that to pure water, and as the concentration of the solution increases, the adsorption volume multiple of the foam to the solution increases because the hazardous substances in the solution have affinity with the polymer microporous material, and the adsorption of the foam material to water is promoted while the hazardous substances are adsorbed by the polymer microporous material.
Tenth: and (3) carrying out retention performance analysis on volatile components of the volatile hazardous chemicals by using the polymer microporous material, and carrying out a release rate experiment:
some liquid chemicals have volatility and flammability, and after the liquid dangerous chemicals are adsorbed by the polymer microporous materials, the accumulation concentration of volatile components in a certain range of the liquid dangerous chemicals can be increased, so that safety accidents such as fire and explosion are easy to occur. To determine whether the polymeric microporous material has a retention and inhibition effect on its volatile components after adsorbing the volatile liquid chemicals, the volatilization rate of the liquid hazardous chemicals in the polymeric microporous material foam needs to be measured and compared with the open volatilization rate of the liquid hazardous chemicals to verify whether the polymeric microporous material is suitable for adsorbing the volatile liquid hazardous chemicals, and the experimental results are shown in fig. 18.
As can be seen from fig. 18, the four liquid hazardous substances of xylene, methanol, acetone and cyclohexane all have volatility, wherein the volatility of acetone is strongest, the volatility of xylene is relatively low, and the volatilization rate of the four liquid hazardous substances in the polymer microporous material is lower than the specific opening volatilization rate, because the polymer microporous material is internally provided with a plurality of interpenetrating micropores, the chemical has capillary locking effect, and the volatilization of the chemical is reduced.
Example 2: use of a polymeric microporous material characterized by: the waste water treatment system applied to the ocean cloud silo 12 comprises an oily waste water storage tank 123, an oil separating device 125 connected with the oily waste water storage tank 123 through a first pipeline 133 (the first pipeline 133 is also provided with a filter 124 in general), an oil content detector 126 matched with the oil separating device 125, and an oil adsorber (comprising an oil adsorber A129 and an oil adsorber B130 or comprising more oil adsorbers) connected with the oil separating device 125 through a second pipeline 134, wherein the oil adsorber is filled with the polymer microporous material, and the polymer microporous material is prepared by the preparation process of the polymer microporous material.
The wastewater treatment system is arranged in the bin body of the ocean cloud bin 12, when oil-containing wastewater enters the oil-containing wastewater storage tank 123, the oil separation device 125 and the oil detector 126 are started, the oil separation device 125 carries out oil skimming treatment on the oil-containing wastewater, the skimmed oil wastewater is discharged into the waste engine oil storage tank, the oil-containing wastewater flows back to the oil-containing wastewater storage tank 123 or is discharged into the oil adsorber to carry out oil adsorption treatment, so that the oil-containing wastewater is discharged into the domestic wastewater storage tank 121 in the bin body after oil skimming and oil absorption are met, and the subsequent recovery treatment is convenient.
The second pipeline 134 includes a main pipe section, at least two branch pipe sections communicated with the outlet of the main pipe section, each branch pipe section is provided with an electric valve (a first electric valve 127 and a second electric valve 128 respectively), the outlet of each branch pipe section is connected with one oil adsorber (an oil adsorber a129 and an oil adsorber B130), the oil detector 126 is arranged on the main pipe section, the oil detector 126 is in signal connection with the electric valve and the oil adsorber, the oil detector 126 detects that the content of petroleum hydrocarbon substances in the oil-containing water coming out from the oil separating device 125 is greater than 15mg/L, and then the electric valves and the oil adsorbers are opened; and when the content of petroleum hydrocarbon substances in the oily water is less than 15mg/L, the electric valve and the oil adsorber are closed. At least two oil adsorbers are arranged, so that the oil adsorption efficiency is improved, and the capacity sharing rate of each storage tank is improved.
The wastewater treatment system further comprises a domestic wastewater storage tank 121 and a waste mineral oil storage tank 122, wherein the domestic wastewater storage tank 121 is connected with the oil adsorber through a third pipeline 135 and is used for discharging qualified wastewater after the oil adsorber adsorbs oil into the domestic wastewater storage tank 121, and the waste mineral oil storage tank 122 is connected with the oil separation device 125 through a fourth pipeline 136 and is used for storing separated oil into the waste mineral oil storage tank 122 through the fourth pipeline 136.
After oil skimming or oil absorption, standard sewage is discharged into the domestic sewage storage tanks, and after oil skimming treatment, the capacity of each storage tank can play a role in sharing, so that the reasonable utilization rate of the residual space of each storage tank is effectively improved, and the subsequent purification and recovery treatment are facilitated.
The foregoing description is only of the preferred embodiments of the invention and is not intended to limit the invention. In the above-described embodiments, the present invention is susceptible to various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. A process for preparing a polymeric microporous material, comprising the steps of:
S1: preparing modified epoxy resin: in a first reaction unit;
s2: preparing a mixed solution A:
putting polyether polyol into a first reaction device with inert gas atmosphere, and melting the polyether polyol and the modified epoxy resin under the condition of heating and pressurizing to prepare a mixed solution A;
s3: preparing an auxiliary reagent B:
mixing a nucleating agent, a catalyst, a foam stabilizer, a foaming agent, a surfactant, a reactive flame retardant and a crosslinking agent to prepare an auxiliary reagent B;
s4: preparation of mixture C:
the mixed solution A is dropped out of the first reaction device and then enters the second reaction device, isocyanate is put into the second reaction device and stirred, so that the mixed solution A and the isocyanate are uniformly mixed, and a mixture C is prepared;
s5: mixing the auxiliary reagent B with the mixture C, molding, reacting and foaming:
adding the auxiliary reagent B into a second reaction device, stirring to uniformly mix the auxiliary reagent B with the mixture C, and rapidly injecting or pouring the mixture into a mold to enable the mixture to be freely foamed;
s6: preparing a polymer microporous material:
standing the mould at a set temperature to form and cure the foam, thus obtaining the oleophylic and hydrophobic polymer microporous material;
The preparation step of the step S1 comprises the following steps:
s11, raw materials are put into a first reaction device:
adding epoxy resin, acrylic acid monomer, initiator and modifier into a first reaction device; wherein, the usage amount of the acrylic acid monomer is 20wt% of the usage amount of the epoxy resin; the usage amount of the initiator is 5wt% of the usage amount of the epoxy resin; the usage amount of the modifier is 5wt% of the usage amount of the epoxy resin;
s12, reacting at a certain temperature and time:
raising the temperature of the first reaction device to 100-110 ℃, and keeping the temperature to enable the raw materials to react for 40min;
s13, preparing modified epoxy resin:
the temperature of the first reaction device is reduced to 25 ℃, a proper amount of alkali is added to neutralize the reactant prepared in the step S12, and the pH value of the reactant is regulated to 6.5-7, so that the water-soluble modified epoxy resin is prepared;
in the step S2, the temperature is 100-120 ℃, the pressure is 0.3-0.5MPa, and the stirring time is 20min;
in the step S3, the foaming agent is deionized water foaming agent; the nucleating agent acts on the foaming process in the step S5 in a heterogeneous nucleating mode and is used for influencing the cell structure;
in the step S4, the stirring speed is 2000r/min, and the stirring time is 1-2min;
in the step S5, the stirring speed is 2000r/min, and the stirring time is 8-10S;
In the step S6, standing for 5-10min, shaping the foam, removing the foam epidermis, placing the foam with the epidermis removed in an environment of 25-27 ℃ for 1-1.5 h, and curing the foam;
the components are prepared from the following components in parts by weight:
modified epoxy resin: 100 parts; polyether polyol: 100 parts; nucleating agent: 5-10 parts; isocyanate: 40 parts; catalyst: 4-5 parts; foam stabilizer: 0.5-1 part; foaming agent: 6-10 parts; and (2) a surfactant: 2-3 parts; reactive flame retardant: 8-10 parts of a lubricant; crosslinking agent: 4-5 parts;
the first reaction device and the second reaction device are the same reaction device (1), the reaction device (1) comprises a reaction container (5) and a stirring device (6) arranged in the reaction container (5), the inner wall of the reaction container (5) is in an inverted frustum shape, a stirring blade assembly (60) on the stirring device (6) is radially arranged by taking a central axis of the inverted frustum shape as a center, rotating wind in a centrifugal direction generated during stirring of the stirring blade assembly (60) collides with the inner wall of the reaction container (5) and changes the moving direction to form reflected wind, the reflected wind is reflected to the center of the reaction container (5) and moves towards the direction of the stirring blade assembly (60), and the reflected wind collides with the rotating wind so as to uniformly stir;
The stirring device (6) comprises a stirring shaft (39) driven by a driving mechanism (3), the stirring shaft (39) is arranged at the central axis position of the reaction vessel (5), the stirring blade assembly (60) is arranged on the stirring shaft (39), the stirring blade assembly (60) is at least arranged in three layers, and each layer is at least provided with three groups of stirring blade assemblies (60) which are arranged in a central symmetry manner, so that the inner cavity of the reaction vessel (5) is uniformly distributed with rotary wind and reflected wind to increase the mutual collision area;
the inlet end of the reaction container (5) is a large-mouth end, a sealing cover (2) is arranged on the reaction container, the sealing cover (2) comprises a first cover (21) and a second cover (23) which are matched in an opening-closing manner, a linkage mechanism and a locking structure which are matched with the first cover (21) and the second cover (23), the linkage mechanism enables the first cover (21) and the second cover (23) to be synchronously opened or closed, the linkage mechanism enables the driving mechanism (3) to work intermittently, the first cover (21) and the second cover (23) are separated and opened, an inlet channel is opened for feeding, and the linkage mechanism enables the driving mechanism (3) to stop working; the first cover (21) and the second cover (23) are moved towards each other to be closed, the inlet channel is closed to stop feeding, the linkage mechanism enables the driving mechanism (3) to work, and the locking structure is used for enabling the first cover (21) and the second cover (23) to be closed stably;
The linkage mechanism comprises: the device comprises a rack (25) and a first gear (26) which are respectively arranged on a first cover (21) and a second cover (23), a first rotating shaft (27) driven by the first gear (26), an adjusting worm arranged on the first rotating shaft (27), a threaded sleeve (31) sleeved on the adjusting worm (30), and a pull rod (33) fixed on the threaded sleeve (31), wherein the rack (25) is meshed with the first gear (26), and the rack (25) drives the first gear (26) to rotate forward or reversely when the first cover (21) and the second cover (23) are synchronously opened or closed; the pull rod (33) is used for enabling the driving mechanism (3) to work intermittently, the locking structure comprises an inserting block (24) and an inserting groove (22) which are respectively arranged on the splicing surfaces of the first cover (21) and the second cover (23), and the inserting block (24) is in inserting fit with the inserting groove (22);
the drive mechanism (3) includes: the stirring device comprises a sliding rail (32) arranged on a second cover (23), a motor (35) arranged on the sliding rail (32), a second gear (38) which is meshed with a driving wheel (37) on the motor (35) in an intermittent mode, wherein the second gear (38) is arranged on a stirring shaft (39), the lower end of a pull rod (33) is fixed on the motor (35), the pull rod (33) is used for pushing the motor (35) to move upwards or downwards along the sliding rail (32), and when the motor moves upwards, the second gear (38) is separated from the driving wheel (37), the stirring shaft (39) stops rotating, and the stirring device (6) stops working; when the stirring device moves downwards, the second gear (38) is meshed with the driving wheel (37), the stirring shaft (39) rotates, and the stirring device (6) starts to work;
The stirring device is characterized in that a scraping plate mechanism (4) is arranged on the stirring shaft (39), the scraping plate mechanism (4) and the stirring device (6) are staggered in the circumferential direction, the scraping plate mechanism (4) comprises a rotary plate (41) arranged on the stirring shaft (39), a fixed rod (42) arranged on the lower surface of the rotary plate (41) in a standing mode, a supporting rod (44) pivoted on the fixed rod (42), a strip-shaped scraping plate (45) matched with the other end of the supporting rod (44), the scraping plate (45) is attached to the inner wall of the reaction container (5) and is arranged in an up-down inclined direction, the supporting rod (44) is propped against the scraping plate (45), the rotary plate (41) rotates along with the stirring shaft (39), the rotary plate (41) drives the fixed rod (42) and the supporting rod (44) to rotate, and the supporting rod (44) drives the scraping plate (45) to rotate;
the stirring device comprises at least two groups of scraping plate (45) mechanisms, wherein the axis of a stirring shaft (39) is used as a symmetrical center line, the stirring shaft is arranged in a central symmetrical mode, each group of scraping plate (45) mechanisms share one rotary table (41), each group of scraping plate (45) mechanisms is provided with a supporting spring (43), the supporting springs (43) are used for generating auxiliary supporting force for the scraping plate (45), one end of each supporting spring (43) is fixed on a fixed rod (42), and the other end of each supporting spring is fixed on the scraping plate (45);
The stirring vane assembly (60) comprises a fixed seat fixedly arranged on the stirring shaft (39), a stirring rod (66) pivoted at the outer end of the fixed seat, a stirring sheet (62) arranged on the stirring rod (66), a sliding groove is formed in the stirring rod (66), a sliding block (63) is arranged at the inner end of the stirring sheet (62), the sliding block (63) is in sliding fit with the sliding groove, a first spring (64) is arranged in the sliding groove, the inner end of the first spring (64) is connected with the inner end of the sliding groove, the outer end of the first spring (64) is connected with the sliding block (63), and when the stirring vane assembly (60) rotates, the stirring sheet (62) moves outwards under the action of centrifugal force, and the first spring (64) is stretched by pulling force; when the stirring blade assembly (60) stops rotating, the first spring (64) is reset, the sliding block (63) is acted by the first spring (64), and the stirring blade (62) moves into the sliding groove and is accommodated in the sliding groove;
a second spring (65) is arranged between the fixed seat and the stirring rod (66), the inner end of the second spring (65) is fixed on the fixed seat and is close to the stirring shaft, the outer end of the second spring (65) is fixed on the stirring rod (66), when the stirring blade assembly (60) rotates, the stirring rod (66) is radially arranged under the action of centrifugal force and forms the same straight line with the fixed seat, and the second spring (65) is stretched by pulling force; when the stirring blade assembly (60) stops rotating, the stirring rod (66) loses centrifugal force, and under the reset action of the second spring (65) and the dead weight action of the stirring rod (66), the stirring rod (66) rotates downwards and collides with the stirring shaft (39) until the stirring rod is stopped on the stirring shaft (39).
2. The process for the preparation of a polymeric microporous material according to claim 1, characterized in that the outlet end of the reaction vessel (5) is a small mouth end on which an output mechanism is provided, said output mechanism comprising:
linkage disc (8): the upper end of the stirring shaft (39) is arranged on the stirring shaft (39), and the stirring shaft (39) drives the stirring shaft to rotate;
conveying worm (9): the device is arranged at the lower end of the linkage disc (8), and is driven to rotate by the linkage disc (8);
conveying shell (10): the upper end of the conveying shell is fixed at the outlet part of the reaction container (5), the lower end of the conveying shell is provided with a liquid dropping port, and the conveying shell is covered on the periphery of the conveying worm (9) so that the inner cavity of the conveying shell is matched with the conveying worm (9) to form a conveying channel;
filter assembly (7): which is arranged at the periphery of the linkage disc (8), and comprises:
filter frame (73): is in two semicircular rings, and comprises an outer circle part, an inner circle part and a radial part connecting the outer circle part and the inner circle part; the outer circle parts of the two filter frames (73) are detachably arranged at the corresponding parts of the reaction container (5) when being spliced, and the inner circle parts are enmeshed with the periphery of the linkage disc (8);
Filter screen (71): is semi-circular and is detachably arranged in the filtering frame (73) and is used for filtering unreacted or insufficiently reacted impurities;
magnet (72): the filter frames (73) are arranged on the radial parts and used for being attracted, so that the filter frames (73) are spliced to form a circular ring shape;
drip cap (11): the detachable type liquid dropping device is arranged at the lower end of the conveying shell and is used for opening or closing the liquid dropping opening.
3. Use of a polymeric microporous material characterized by: the waste water treatment system applied to the ocean Yun Cang (12) comprises an oily waste water storage tank (123), an oil separating device connected with the oily waste water storage tank (123) through a first pipeline, an oil detector (126) matched with the oil separating device, and an oil adsorber connected with the oil separating device through a second pipeline, wherein the oil adsorber is filled with the polymer microporous material, and the polymer microporous material is prepared by the preparation process of the polymer microporous material according to claim 1 or 2.
4. The use of a polymeric microporous material according to claim 3, wherein the second pipeline comprises a main pipeline section, at least two branch pipeline sections communicated with an outlet of the main pipeline section, each branch pipeline section is provided with an electric valve, an outlet of each branch pipeline section is connected with one oil adsorber, the oil detector (126) is arranged on the main pipeline section, the oil detector (126) is in signal connection with the electric valves and the oil adsorbers, and the electric valves and the oil adsorbers are opened when the oil detector (126) detects that the content of petroleum hydrocarbon substances in the oily water from the oil separating device is more than 15 mg/L; and when the content of petroleum hydrocarbon substances in the oily water is less than 15mg/L, the electric valve and the oil adsorber are closed.
5. The use of the polymeric microporous material according to claim 4, wherein the wastewater treatment system further comprises a domestic sewage storage tank (121) and a waste mineral oil storage tank (122), the domestic sewage storage tank (121) is connected with the oil adsorber through a third pipeline for discharging qualified sewage after the oil adsorber adsorbs oil into the domestic sewage storage tank (121), the waste mineral oil storage tank (122) is connected with the oil separation device through a fourth pipeline, and the separated oil is stored in the waste mineral oil storage tank (122) through a fourth pipeline.
CN202211126029.5A 2022-09-15 2022-09-15 Preparation process and application of polymer microporous material Active CN115430406B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07292027A (en) * 1994-04-28 1995-11-07 Kansai Paint Co Ltd Film-formable chelate-forming resin
CN1884336A (en) * 2006-05-23 2006-12-27 山东圣光化工集团有限公司 Acrylic acid-epoxy resin modified aqueous polyurethane preparation method
CN109529751A (en) * 2018-12-18 2019-03-29 江阴长盛化工有限公司 High-purity bisphenols S production sulfonating reaction kettle and its production method
CN111171260A (en) * 2020-01-19 2020-05-19 西南石油大学 Polyurethane foam material for efficient oil-water and emulsion separation and preparation method thereof
CN112982346A (en) * 2021-02-09 2021-06-18 浙江蓝景科技有限公司 Intelligent ocean cloud cabin equipment and ship water pollutant collecting and transferring system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07292027A (en) * 1994-04-28 1995-11-07 Kansai Paint Co Ltd Film-formable chelate-forming resin
CN1884336A (en) * 2006-05-23 2006-12-27 山东圣光化工集团有限公司 Acrylic acid-epoxy resin modified aqueous polyurethane preparation method
CN109529751A (en) * 2018-12-18 2019-03-29 江阴长盛化工有限公司 High-purity bisphenols S production sulfonating reaction kettle and its production method
CN111171260A (en) * 2020-01-19 2020-05-19 西南石油大学 Polyurethane foam material for efficient oil-water and emulsion separation and preparation method thereof
CN112982346A (en) * 2021-02-09 2021-06-18 浙江蓝景科技有限公司 Intelligent ocean cloud cabin equipment and ship water pollutant collecting and transferring system

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