CN106749973B - Continuous production equipment and production method of polycarboxylate superplasticizer - Google Patents
Continuous production equipment and production method of polycarboxylate superplasticizer Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 238000010924 continuous production Methods 0.000 title claims abstract description 30
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 30
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 68
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 32
- 230000000977 initiatory effect Effects 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 13
- 238000004321 preservation Methods 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 57
- 239000003999 initiator Substances 0.000 claims description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000012546 transfer Methods 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 7
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- QNNVICQPXUUBSN-UHFFFAOYSA-N 2-sulfanylpropan-1-ol Chemical compound CC(S)CO QNNVICQPXUUBSN-UHFFFAOYSA-N 0.000 claims description 2
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 claims description 2
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 210000003298 dental enamel Anatomy 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004568 cement Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000109 continuous material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention discloses continuous production equipment and a production method of a polycarboxylate superplasticizer. The continuous production method comprises the following steps: in the material preparation and mixing stage, the solution A, the solution B and the solution C enter a pipeline group through a flow meter and a material preparation pump; in the composite initiation stage, the solution D and the monomer E enter a pipeline group together with the early-stage mixed material through a magnetic pump and a flowmeter, and normal-temperature ultraviolet composite initiation polymerization is carried out; in the normal temperature heat preservation stage, materials in the early stage are subjected to normal temperature heat preservation through a pipeline group, and polymerization is fully performed; and in the neutralization and discharging stage, the liquid caustic soda solution F enters the pipeline group together with the early-stage polymer through a magnetic pump and a flowmeter, and is discharged after neutralization, so that the polycarboxylate superplasticizer is finally obtained. The production process of the invention is simple, can greatly improve the production efficiency and the productivity, and reduce the investment of production equipment and the energy consumption of production; and the polymerization conversion rate is greatly improved, and the intermittent production mode of the polycarboxylic acid water reducing agent is really converted into the continuous production mode.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a method and a technology for producing a polycarboxylic acid water reducer by using normal-temperature ultraviolet composite-initiated continuous production equipment.
Background
In recent years, along with the development of concrete technology, the application of the polycarboxylic acid high-performance water reducing agent is increasingly popularized, and the polycarboxylic acid high-performance water reducing agent is gradually and widely applied to various projects due to the advantages of low mixing amount, high water reducing rate, excellent slump retaining performance, low shrinkage, energy conservation, environmental protection and the like. The polycarboxylic acid molecule is usually a comb-like polymer compound copolymerized from an unsaturated small molecule containing a carboxylic acid group, an unsaturated large molecule containing a polyoxyethylene group, and an unsaturated small molecule containing other functional groups. The polycarboxylic acid water reducing agent not only has excellent performance, but also has the environmental protection characteristic in production and use and low content of harmful substances, and is known as the development direction of concrete admixtures in the future.
At present, the synthesis of the polycarboxylate superplasticizer is basically carried out in a specific reaction kettle or a similar container, macromonomer polyether is adopted for priming, materials such as an initiator, acrylic acid or slump retaining monomer and functional monomer are added dropwise under a certain temperature condition, and the active monomers are copolymerized to synthesize polycarboxylate superplasticizer products with different structures or different functions. At present, polycarboxylic acid water reducing agent manufacturers at home and abroad generally adopt an intermittent polymerization production device for production. Generally, the polymerization production device comprises a polymerization reaction kettle, a plurality of dripping tanks are respectively connected outside the polymerization reaction kettle through pipelines, and materials are continuously dripped into the reaction kettle from the dripping tanks to carry out polymerization reaction. A polycarboxylate water reducing agent high efficiency reation kettle has been introduced in chinese patent CN204395957U, and inside multistage puddler and the stirring vane of having set up of its reation kettle to the stirring vane layering is arranged, and every layer of blade all can stir the polycarboxylic acid solution in the reation kettle, and the solution shape of avoiding from top to bottom is different, and mixing effect and reaction effect are all fine. Chinese patent CN204768671U describes a polymerization reactor for producing a polycarboxylate superplasticizer, wherein a temperature system is arranged in the reactor, and the temperature system comprises a temperature detection system inside the polymerization reactor, an external temperature control system and a peripheral program temperature modulation component. Wherein the polymerization reaction kettle can provide proper reaction temperature according to the requirements of different stages of reaction, thereby improving the reaction efficiency and increasing the product yield.
However, the intermittent device and the production method have complex structures, the reaction kettle body and corresponding pipelines occupy larger space, the production time is longer, the production efficiency is low, a temperature control system is required to strictly control the temperature, the energy consumption is larger, and the performances of each batch of the polycarboxylic acid water reducing agent are different, so that improvement is urgently needed. There is an urgent need to develop a large-scale continuous production apparatus and method to solve the above problems. Chinese patent CN102942659A describes a method for producing a polycarboxylate water reducer by a tubular reaction device, which changes the intermittent production of the polycarboxylate water reducer into approximate continuous production, adds prepared raw materials and auxiliary materials into the tubular reaction device for polymerization, and then the product enters a storage tank for aging and neutralization. The method changes the reaction kettle into a tubular reaction device, improves the production scale and efficiency, but still needs batch aging in a storage tank or neutralization at the discharge outlet of the tubular reaction device in the later stage to obtain the polycarboxylic acid water reducing agent, is not a complete continuous production process, and limits the production capacity of large-scale production by using a neutralization aging tank. Moreover, the tubular equipment provided by the method is a single pipeline, and is not convenient to maintain and install. To the problem in the above-mentioned patent, chinese patent CN103537241A has improved it, provides a single channel tubular reaction unit of production polycarboxylate water-reducing agent, including material process, heat preservation process and neutralization dilution process, whole reaction process goes on in single channel reaction tube, and the reaction unit of each stage is whole or partly in constant temperature equipment, and polycarboxylate water-reducing agent discharges from the discharge gate after the reaction, need not to carry out other subsequent processing. The production process is simplified, and the production efficiency and the productivity are greatly improved. However, the above patent does not pay attention to the conversion rate of the polymerization product in the polymerization process, and the conversion rate of the polymerization product is only 60 to 75% compared with the conversion rate of the intermittently produced polycarboxylic acid of 90% or more, and in addition, both of the above two pipeline type production apparatuses are required to be wholly or partially immersed in a constant temperature water area, which results in large energy consumption.
Disclosure of Invention
The invention aims to provide continuous production equipment and method for producing a polycarboxylate superplasticizer by normal-temperature ultraviolet composite initiation aiming at the defects of the prior art. Mainly solves the technical problems of the following three aspects: (1) an aging tank or a reaction kettle is additionally arranged in the continuous production process of the polycarboxylic acid water reducing agent; (2) the continuous production equipment for the polycarboxylate superplasticizer needs to be completely or partially soaked in a constant temperature device, and the equipment is complex and is not easy to maintain; (3) the continuous production of the polycarboxylate superplasticizer has low polymerization conversion efficiency.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a continuous production device for a polycarboxylate superplasticizer comprises a series of pipeline groups and related devices which are connected in series and are used for continuous material flow and reaction, and the pipeline groups in series can be divided into four stages according to different stages of material flow:
the first stage is a material preparing and mixing stage and comprises a flow meter, a material preparing pump and a pipeline group, wherein materials sequentially pass through the flow meter and the material preparing pump and enter the pipeline group;
the second stage is a composite initiation stage, which comprises a magnetic pump, a flowmeter, a pipeline group and an ultraviolet light source embedded in the pipeline group, wherein newly added materials, namely materials entering the second stage enter the pipeline group together with materials obtained by the reaction of the magnetic pump, the flowmeter and the first stage, and normal-temperature ultraviolet composite initiation polymerization is carried out;
the third stage is a normal temperature heat preservation stage which comprises a pipeline group, a material flow buffer tank and a centrifugal pump, wherein the material obtained in the second stage reaction is subjected to normal temperature heat preservation polymerization through the pipeline group, then enters the material flow buffer tank, and is used for adjusting the material flow entering the fourth stage and enters the next stage through the centrifugal pump;
the fourth stage is a neutralization discharging stage and comprises a magnetic pump, a flowmeter and a pipeline group, wherein the materials entering the fourth stage enter the pipeline group together with the materials obtained by the reaction of the magnetic pump, the flowmeter and the third stage, and are discharged after neutralization and mixing;
the pipeline group is a series of pipelines connected in series; the inner walls of all the pipeline groups are provided with spoilers, wherein the spoilers and the material flow direction form a 90-150 degree angle.
The cross section of the pipeline can be round, oval, rectangular, star-shaped or flat.
The material of the pipeline group is a plastic pipe, a stainless steel pipe with the inner wall coated with polytetrafluoroethylene, a low-carbon steel pipe with the inner wall coated with enamel or a ceramic pipe;
the pipeline groups are installed according to actual space and can be connected in any form;
the length of the pipeline group is selected according to the polymerization degree of the materials, and is generally 200-500 meters, and the diameter of the pipeline group is generally 0.05-0.08 meter; the length ratio of the pipeline groups in the four stages is 1: 5-9: 1-2: 1 to 2.
The pipeline groups can be connected in a linear type or in a tightly folded type according to the actual space installation.
A continuous production method of a polycarboxylate superplasticizer comprises the following steps:
(1) respectively preparing polyether macromonomer solutions A, Fe2+Salt solution B, H2O2Transferring the aqueous solution C, the ascorbic acid-chain transfer agent-ultraviolet initiator mixed solution D, the active monomer E and the liquid alkali solution F into a storage tank to be fed;
wherein the polyether macromonomer solution A, Fe2+Salt solutions B and H2O2The water solution C is sequentially pumped into the pipeline group of the first stage to be mixed, and flows into the pipeline group of the second stage continuously;
(2) adding the active monomer E and the ascorbic acid-chain transfer agent-ultraviolet light initiator mixed solution D into the composite initiation polymerization pipeline group of the second stage in batches, and carrying out polymerization reaction with the material obtained by the reaction of the first stage;
(3) then the polymerization product enters a normal-temperature heat-preservation pipeline group in the third stage, and polymerization is fully carried out;
(4) and finally, neutralizing the polymerization material and the liquid caustic soda solution F in a neutralization discharge pipeline group in the fourth stage, and discharging to finally obtain the polycarboxylic acid water reducing agent.
According to the process requirement, a feed inlet is arranged at the starting end of the material mixing and preparing pipeline group in the first stage and used for mixing the polyether macromonomer solution A, Fe2+Salt solutions B and H2O2Pumping the aqueous solution C into the pipeline groups in sequence;
the composite initiation pipeline group at the second stage is provided with a plurality of feeding holes at different positions, and the feeding holes are used for adding the active monomer E, the ascorbic acid-chain transfer agent-ultraviolet initiator mixed solution D into the composite initiation polymerization pipeline group at the second stage in batches, wherein the number of the feeding holes at the second stage is generally 3-8, and the feeding amount of each feeding hole is equal;
and a feed inlet for the liquid caustic soda solution F is arranged at the starting end of the neutralization discharge pipeline in the fourth stage.
A plurality of ultraviolet light sources are uniformly distributed on the inner wall of the pipeline group in the second stage composite initiation stage, wherein the first ultraviolet light source is arranged at the starting end of the pipeline group in the second stage, and then the ultraviolet light sources are arranged at intervals of 2 meters; the ultraviolet light is generated by the following light sources: the light of the mercury lamp, the xenon lamp, the deuterium lamp and the ultraviolet LED lamp is ultraviolet light with the wavelength of 295-400 nm, and the power of a light source is 20-500 w.
The raw materials need to be prepared into a standard solution with a certain concentration: wherein the mass concentration of the polyether macromonomer solution A is 60 percent, and Fe2+The mass concentration of the salt solution B is 0.1 percent, and H2O2The mass concentration of the aqueous solution C is 5%, the mass concentration of the ascorbic acid solution is 1-1.5%, the mass concentration of the chain transfer agent solution is 1-1.5%, the mass concentration of the ultraviolet light initiator solution is 1-1.5%, and the mass concentration of the liquid alkali solution F is 35%;
wherein the ascorbic acid-chain transfer agent-ultraviolet light initiator mixed solution D is formed by mixing three solutions of ascorbic acid solution, chain transfer agent solution and ultraviolet light initiator solution in any proportion within the mass concentration range.
The material inlet pipeline has a certain inletMaterial flow rate: wherein the feeding flow rate of the polyether macromonomer solution A is 100-500 kg/h, Fe2+The feeding flow rate of the salt solution B is 1.2-5.5 kg/H, and H2O2The feeding flow rate of the aqueous solution C is 1.5-8 kg/h, the feeding flow rate of the ascorbic acid-chain transfer agent-ultraviolet initiator mixed solution D is 50-250 kg/h, the feeding flow rate of the active monomer E is 10.5-35 kg/h, and the feeding flow rate of the liquid alkali solution F is 11-36 kg/h.
The polyether macromonomer A is selected from any one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, butenyl polyoxyethylene ether, methyl butenyl polyoxyethylene ether, vinyl polyoxyethylene ether and hydroxybutyl vinyl polyoxyethylene ether; wherein the weight average molecular weight of the polyether macromonomer A is 1000-5000;
said Fe2+Salt B is ferrous sulfate heptahydrate;
the reactive monomer E is acrylic acid;
the ultraviolet initiator is any one of bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide and ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate;
the chain transfer agent is any one of 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptopropanol, 3-mercaptopropanol, mercaptoacetic acid and mercaptoethanol;
the liquid caustic soda solution F is a sodium hydroxide solution.
The invention has the following beneficial effects:
the production equipment for producing the polycarboxylate superplasticizer by normal-temperature ultraviolet composite initiation is mainly formed by sequentially connecting pipeline groups in series, has simple process flow, can greatly improve the production efficiency and the productivity, and reduces the investment of production equipment and the production energy consumption; the normal-temperature composite initiation polymerization is adopted, the pipeline group does not need to be soaked in a constant-temperature device, the ultraviolet initiation polymerization also greatly improves the conversion rate of the polymerization, and the intermittent production mode of the polycarboxylate superplasticizer is really converted into the continuous production mode.
Drawings
FIG. 1 is a schematic structural diagram of a continuous production apparatus with composite initiation of normal temperature and ultraviolet light.
The specific notations in fig. 1 are: 11, 22 and 42 flow meters, 12 stock pumps, 13, 23, 31 and 43 pipeline groups, 14 spoilers, 21 and 41 magnetic pumps, 24 ultraviolet light sources, 32 material flow buffer tanks and 33 centrifugal pumps.
Detailed Description
The present invention will be described in detail with reference to the following examples for better understanding of the contents of the present invention, but the contents of the examples do not limit the scope of the present invention.
The weight average molecular weight and the polymerization conversion rate of the polycarboxylic acid water reducing agent described in the examples were measured by using a high performance gel chromatograph (GPC). Wherein the separation column adopts Shodex SB806+803 two gel chromatographic columns connected in series, the column temperature is 40 ℃, and the mobile phase is 0.1M NaNO3The flow rate of the aqueous solution is 1.0ml/min, and the sample amount is 20 mul of 0.5 percent aqueous solution; a detector: a refractive index detector of Shodex RI-71 type; standard curve preparation used polyethylene glycol GPC standards (Sigma-Aldrich, MW 1010000, 478000, 263000, 118000, 44700, 18600, 6690, 1960, 628, 232).
The continuous production equipment of the polycarboxylate superplasticizer comprises a series of pipeline groups and related devices which are connected in series and are used for the continuous flow and reaction of materials; the series pipeline group can be divided into four parts according to different stages of material flow, wherein the first stage is a material preparing and mixing stage and comprises a flow meter 11, a material preparing pump 12 and a pipeline group 13, the material sequentially passes through the flow meter 11 and the material preparing pump 12 and enters the pipeline group 13, a spoiler 14 is arranged on the inner wall of the pipeline group 13, and the pipeline groups in the following stages have the same structure as the stage; the second stage is a composite initiation stage, which comprises a magnetic pump 21, a flowmeter 22, a pipeline group 23 and an ultraviolet light source 24 embedded in the pipeline group, wherein the materials enter the pipeline group 23 together with the early-stage mixed materials through the magnetic pump 21 and the flowmeter 22, and normal-temperature ultraviolet composite initiation polymerization is carried out; the third stage is a normal temperature heat preservation stage, which comprises a pipeline group 31, a material flow buffer tank 32 and a centrifugal pump 33, wherein the reacted materials are subjected to normal temperature heat preservation through the pipeline group 31, are fully polymerized and enter the material flow buffer tank, and the tank is used for adjusting the material flow in the later stage and enters the next stage through the centrifugal pump 33; the fourth stage is a neutralization discharging stage and comprises a magnetic pump 41, a flow meter 42 and a pipeline set 43, wherein materials entering the fourth stage enter the pipeline set 43 together with the early-stage polymer through the magnetic pump 41 and the flow meter 42, and are discharged after neutralization and mixing.
The whole production process comprises the following steps: respectively preparing polyether macromonomer solutions A, Fe with certain concentrations2+Salt solution B, H2O2Transferring the aqueous solution C, the ascorbic acid-chain transfer agent-ultraviolet initiator mixed solution D, the active monomer E and the liquid alkali solution F into a storage tank to be fed; wherein the polyether macromonomer solution A, Fe2+Salt solutions B and H2O2Mixing the aqueous solution C in the mixing pipeline group of the first stage, and continuously flowing into the pipeline group of the second stage; sequentially adding the active monomer E and the ascorbic acid-chain transfer agent-ultraviolet initiator mixed solution D into the composite initiation polymerization pipeline group in the second stage in batches, and carrying out polymerization reaction with the mixed material in the first stage; then the polymerization product enters a normal-temperature heat-preservation pipeline group in the third stage, and polymerization is fully carried out; and finally, neutralizing and discharging the polymer material and the liquid caustic soda solution F in a neutralization discharge pipeline group in the fourth stage to finally obtain the polycarboxylic acid water reducing agent.
The active monomer E and the ascorbic acid-chain transfer agent-ultraviolet light initiator mixed solution D in the composite initiation polymerization stage need to be sequentially fed in batches at the same time, so that the continuous polymerization reaction kinetics are met, the polymerization conversion efficiency tends to be maximum, and the feeding amount can be adjusted according to the actual situation so as to obtain the required structure and performance; in addition, the number of the feeding ports and the distance between the feeding ports can be increased or decreased according to the actual process requirements, and the structure and the performance of the polycarboxylic acid can also be adjusted according to the increase or decrease of the number of the feeding ports and the distance between the feeding ports.
Example 1
The pipeline group adopted in the embodiment is a plastic pipe with the length of 200 meters and the diameter of 0.05 meter, and the length ratio of the pipelines in four stages is 1: 5: 1: 1, wherein the ultraviolet power of the composite initiation polymerization stage is 20w, the number of the feeding holes in the stage is 3, and the feeding holes in the stage are distributed at equal intervals, namely the feeding holes in the second stage are evenly distributed on the tube group in the second stage, the 1 st feeding hole is at the beginning of the second stage, then 1 feeding hole is distributed at intervals of 25 meters, and the end of the second stage is not provided with the feeding holes.
Preparing required raw materials into a specification solution: 60 mass% allyl polyoxyethylene ether (Mw 1000), 0.1 mass% ferrous sulfate solution, and 5 mass% H2O2The solution, a 1% by mass ascorbic acid solution, a 1% by mass 2-mercaptopropionic acid, a 1% by mass bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide mixed solution, and a 35% by mass sodium hydroxide solution. Wherein the feeding flow of the polyether macromonomer solution A is 100kg/h, Fe2+The feeding flow rate of the salt solution B is 1.2kg/h, the feeding flow rate of the hydrogen peroxide solution C is 1.5kg/h, the feeding flow rate of the ascorbic acid-chain transfer agent-ultraviolet initiator mixed solution D is 50kg/h, the feeding flow rate of the active monomer E is 10.5kg/h, and the feeding flow rate of the liquid caustic soda solution F is 11 kg/h. The composite initiation stage has 3 material inlets, the feeding flow rate of each material inlet consists of two parts, the first part is the feeding flow rate 50/3 ═ 16.66kg/h of the ascorbic acid-chain transfer agent-ultraviolet light initiator mixed solution D, and the second part is the feeding flow rate 10.5/3 ═ 3.5kg/h of the reactive monomer E. And (3) controlling the feeding speed to uniformly add the materials into the pipeline group, and simultaneously starting ultraviolet light to carry out continuous production. And when the raw materials are insufficient, supplementing in time.
The detailed synthesis conditions and production equipment parameters for this example are set forth in tables 1 and 2.
Examples 2 to 10
The production equipment and the production process in the embodiments 2 to 10 are the same as those in the embodiment 1 except that the synthesis conditions and the production equipment parameters are different, and the detailed synthesis conditions and the production equipment parameters are listed in tables 1 and 2.
Comparative examples 1 to 2
Comparative examples 1 to 2 correspond to examples 1 to 2, respectively, except that the ultraviolet light source in the stage of composite initiation polymerization was not turned on. The detailed synthesis conditions and production equipment parameters are shown in tables 1 and 2.
Comparative example 3
A polycarboxylic acid water reducing agent prepared by a batch reactor is added with 185.0g of distilled water, 275.5g of allyl polyoxyethylene ether and 3.4g of 30% hydrogen peroxide in a 1L glass round-bottom flask provided with a thermometer, a stirrer, a dropping funnel and a nitrogen guide tube, stirred, heated and dissolved, and the round-bottom flask is purged by nitrogen to remove oxygen in the system. Under the protection of nitrogen, the temperature is raised to 40 ℃, 54.0g of acrylic acid, 1.26g of 3-mercaptopropionic acid and 100.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 3 hours. Simultaneously, initiator solution of 160.0g of distilled water and 0.92g of ascorbic acid is dropwise added at a constant speed for 3.5 h. And after all the solution is dripped, continuously keeping the temperature for 2h at constant temperature, then cooling to about 40 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.0, and obtaining the polycarboxylic acid water reducing agent.
TABLE 1 Synthesis conditions in examples and comparative examples
TABLE 2 production plant parameters in the examples and comparative examples
Application examples
The performances of the concrete samples in the examples 1 to 10 and the comparative examples 1 to 3 are compared, and the fluidity of the cement paste and the water reducing rate of the concrete are measured according to the relevant regulations of GB8076-2008 'concrete admixture'. The weight average molecular weight and the polymerization conversion efficiency of the sample were measured simultaneously by using a high performance gel chromatograph (GPC). Wherein, the fluidity of the cement paste is tested, 300g of cement is weighed by adopting 52.5 P.II cement in the small open-field in the south of the Yangtze river, the water adding amount is 87g, the solid mixing amount of the water reducing agent is 0.12 percent of the weight of the cement, and the initial fluidity and the fluidity of the cement paste after 60min are tested; the concrete water reducing rate test is carried out at 25 ℃, the test cement adopts 52.5 P.II cement of small open field in south of the Yangtze river, the solid mixing amount of the water reducing agent is fixed to be 0.2 percent of the weight of the cement, and the water consumption is adjusted to ensure that the initial slump of the fresh concrete is 21.0 +/-1 cm. The results of the above experiments are shown in Table 3.
TABLE 3 comparison of the Properties of the examples and comparative examples
From the test results, the water reducing agents prepared in comparative examples 1 to 10 and comparative examples 1 to 3 can be seen as follows:
(1) the conversion efficiency of the samples obtained in the examples 1-10 adopting normal temperature ultraviolet composite initiation polymerization is over 95 percent, which shows that the conversion efficiency of the continuously produced products can be obviously improved by adopting the production equipment and the process;
(2) under the condition that an ultraviolet light source is not turned on, the conversion efficiency, the paste cleaning performance and the water reducing rate performance of the samples of the comparative examples 1-2 are correspondingly lower than those of the corresponding examples 1-2, which shows that the polymerization initiated by ultraviolet light can assist in improving the polymerization efficiency initiated at normal temperature, and the product performance is obviously improved; (3) compared with the sample of the comparative example 3 produced in an intermittent manner, the samples of the examples 1 to 10 produced in a continuous manner have equivalent polymerization conversion efficiency, pulp purification performance and water reduction rate performance, and can meet the performance requirements of the intermittent production.
Claims (10)
1. The continuous production equipment of the polycarboxylate superplasticizer is characterized by comprising a series of pipeline groups and related devices which are connected in series and are used for continuously flowing materials and reacting, wherein the pipeline groups in series are divided into four stages according to different stages of material flowing:
the first stage is a material preparing and mixing stage and comprises a flow meter (11), a material preparing pump (12) and a pipeline group (13), wherein materials sequentially pass through the flow meter (11) and the material preparing pump (12) and enter the pipeline group (13);
the second stage is a composite initiation stage, which comprises a magnetic pump (21), a flowmeter (22), a pipeline group (23) and an ultraviolet light source (24) embedded in the pipeline group, wherein newly added materials, namely the materials entering the second stage enter the pipeline group (23) through the magnetic pump (21), the flowmeter (22) and the materials obtained by the reaction of the first stage, and the materials are subjected to normal-temperature ultraviolet composite initiation polymerization;
the third stage is a normal temperature heat preservation stage and comprises a pipeline group (31), a material flow buffer tank (32) and a centrifugal pump (33), the materials obtained in the second stage are subjected to normal temperature heat preservation polymerization through the pipeline group (31) and then enter the material flow buffer tank (32), and the tank is used for adjusting the material flow entering the fourth stage and enters the next stage through the centrifugal pump (33);
the fourth stage is a neutralization discharging stage and comprises a magnetic pump (41), a flowmeter (42) and a pipeline group (43), materials entering the fourth stage enter the pipeline group (43) through the magnetic pump (41) and the flowmeter (42) and materials obtained by the reaction in the third stage, and the materials are discharged after neutralization and mixing;
the inner walls of all the pipeline groups are provided with spoilers (14), wherein the flow direction of the spoilers and the material flow is 90 degrees ~ 150 degrees;
in the second stage, the normal-temperature ultraviolet composite initiation polymerization adopts a composite initiation system of an oxidation reduction system and an ultraviolet initiation system.
2. The continuous production equipment of the polycarboxylate water reducer as claimed in claim 1, wherein the cross-sectional shape of the pipeline is circular, elliptical or rectangular.
3. The continuous production equipment of the polycarboxylate water reducer as claimed in claim 2, wherein the pipeline group is made of a plastic pipe, a stainless steel pipe with an inner wall coated with polytetrafluoroethylene, a low-carbon steel pipe with an inner wall coated with enamel or a ceramic pipe;
the pipeline groups are installed according to actual space and can be connected in any form;
the length of the pipeline group is 200 ~ 500 m, the diameter of the pipeline group is 0.05 ~ 0.08.08 m, and the length ratio of the pipeline groups in the four stages is 1: 5 ~ 9: 1 ~ 2: 1 ~ 2 in sequence.
4. The continuous production equipment of the polycarboxylate water reducer as claimed in claim 3, wherein said pipe sets are connected in a straight line type or a close folding type according to actual space installation.
5. A continuous production method of a polycarboxylate water reducer by using the continuous production equipment of any one of claims 1 to 4 is characterized by comprising the following production processes:
(1) respectively preparing polyether macromonomer solutions A, Fe2+Salt solution B, H2O2Transferring the aqueous solution C, the ascorbic acid-chain transfer agent-ultraviolet initiator mixed solution D, the active monomer E and the liquid alkali solution F into a storage tank to be fed;
wherein the polyether macromonomer solution A, Fe2+Salt solutions B and H2O2The water solution C is sequentially pumped into the pipeline group of the first stage to be mixed, and flows into the pipeline group of the second stage continuously;
(2) adding the active monomer E and the ascorbic acid-chain transfer agent-ultraviolet light initiator mixed solution D into the composite initiation polymerization pipeline group of the second stage in batches, and carrying out polymerization reaction with the material obtained by the reaction of the first stage;
(3) then the polymerization product enters a normal-temperature heat-preservation pipeline group in the third stage, and polymerization is fully carried out;
(4) and finally, neutralizing the polymerization material and the liquid caustic soda solution F in a neutralization discharge pipeline group in the fourth stage, and discharging to finally obtain the polycarboxylic acid water reducing agent.
6. The continuous production method of the polycarboxylate water reducer as claimed in claim 5, wherein a feed inlet is arranged at the beginning end of the material mixing pipe group in the first stage for feeding the polyether macromonomer solution A, Fe2+Salt solutions B and H2O2The aqueous solution C is pumped into the pipeline group (13) in sequence;
a plurality of feeding holes in different positions are arranged on the composite initiation pipeline group in the second stage and are used for adding the active monomer E, the ascorbic acid-chain transfer agent-ultraviolet light initiator mixed solution D into the pipeline group (23) in batches, wherein the number of the feeding holes in the second stage is 3 ~ 8, and the feeding amount of each feeding hole is equal;
and a feed inlet for the liquid caustic soda solution F is arranged at the starting end of the neutralization discharge pipeline group in the fourth stage.
7. The continuous production method of the polycarboxylate water reducer as claimed in claim 6, wherein a plurality of ultraviolet light sources are uniformly distributed on the inner wall of the pipeline set in the second stage of the composite initiation stage, wherein the first ultraviolet light source is arranged at the beginning end of the pipeline set in the second stage, and then one ultraviolet light source is arranged at intervals of 2 meters, and the ultraviolet light is generated by a mercury lamp, a xenon lamp, a deuterium lamp and an ultraviolet LED lamp, and the light is ultraviolet light with the wavelength of 295 ~ 400nm and the power of the light source is 20 ~ 500 w.
8. The continuous production method of the polycarboxylate water reducer as claimed in claim 7, wherein the mass concentration of the polyether macromonomer solution A is 60%, and Fe2+The mass concentration of the salt solution B is 0.1 percent, and H2O2The mass concentration of the aqueous solution C is 5%, the mass concentration of the ascorbic acid solution is 1 ~ 1.5.5%, the mass concentration of the chain transfer agent solution is 1 ~ 1.5.5%, the mass concentration of the ultraviolet photoinitiator solution is 1 ~ 1.5.5%, and the mass concentration of the liquid alkali solution F is 35%;
wherein the ascorbic acid-chain transfer agent-ultraviolet light initiator mixed solution D is formed by mixing three solutions of ascorbic acid solution, chain transfer agent solution and ultraviolet light initiator solution in any proportion within the mass concentration range.
9. The continuous production method of the polycarboxylate water reducer as claimed in claim 8, wherein the feeding flow rate of the polyether macromonomer solution A is 100 ~ 500kg/h, Fe2+The feeding flow rate of the salt solution B is 1.2 ~ 5.5.5 kg/H, H2O2Aqueous solutionThe feeding flow rate of C is 1.5 ~ 8kg/h, the feeding flow rate of ascorbic acid-chain transfer agent-ultraviolet photoinitiator mixed solution D is 50 ~ 250kg/h, the feeding flow rate of active monomer E is 10.5 ~ 35kg/h, and the feeding flow rate of liquid alkali solution F is 11 ~ 36 kg/h.
10. The continuous production method of the polycarboxylate water reducer as claimed in claim 9, wherein the polyether macromonomer in the solution A is selected from any one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, butenyl polyoxyethylene ether, methyl butenyl polyoxyethylene ether, vinyl polyoxyethylene ether and hydroxybutyl vinyl polyoxyethylene ether, wherein the weight average molecular weight of the polyether macromonomer A is 1000 ~ 5000;
fe in the solution B2+The salt is ferrous sulfate heptahydrate;
the reactive monomer E is acrylic acid;
the ultraviolet initiator is any one of bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide and ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate;
the chain transfer agent is any one of 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptopropanol, 3-mercaptopropanol, mercaptoacetic acid and mercaptoethanol;
the liquid caustic soda solution F is a sodium hydroxide solution.
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