CN111087190A - Aliphatic water reducer prepared from lignosulfonate wastewater and synthesis process thereof - Google Patents
Aliphatic water reducer prepared from lignosulfonate wastewater and synthesis process thereof Download PDFInfo
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- CN111087190A CN111087190A CN201911331825.0A CN201911331825A CN111087190A CN 111087190 A CN111087190 A CN 111087190A CN 201911331825 A CN201911331825 A CN 201911331825A CN 111087190 A CN111087190 A CN 111087190A
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- lignosulfonate
- wastewater
- water reducing
- reducing agent
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- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002351 wastewater Substances 0.000 title claims abstract description 81
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 61
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 48
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 28
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000012263 liquid product Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000001603 reducing effect Effects 0.000 abstract description 20
- 239000004567 concrete Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 7
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 7
- 235000019799 monosodium phosphate Nutrition 0.000 description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LSMQKPQSDSZFEZ-UHFFFAOYSA-N C=O.[C] Chemical group C=O.[C] LSMQKPQSDSZFEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- -1 carbon ions Chemical class 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NQMZUMSFJBKHAU-UHFFFAOYSA-N 4-hydroxy-3-(hydroxymethyl)butan-2-one Chemical compound CC(=O)C(CO)CO NQMZUMSFJBKHAU-UHFFFAOYSA-N 0.000 description 1
- LVSQXDHWDCMMRJ-UHFFFAOYSA-N 4-hydroxybutan-2-one Chemical compound CC(=O)CCO LVSQXDHWDCMMRJ-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical group [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to an aliphatic water reducing agent prepared from lignosulfonate wastewater and a synthesis process thereof, relating to the technical field of concrete water reducing agents and comprising the following raw materials in parts by weight: 10-30 parts of treated lignosulfonate wastewater; 10-30 parts of acetone; 40-70 parts of formaldehyde; 10-30 parts of sodium sulfite; 40-60 parts of deionized water. The aliphatic water reducing agent is prepared from the lignosulfonate wastewater, a new way for comprehensively utilizing the lignosulfonate wastewater is developed, the lignosulfonate wastewater is reasonably utilized as a resource, and the water reducing effect of the aliphatic water reducing agent is improved.
Description
Technical Field
The invention relates to the technical field of concrete water reducing agents, in particular to an aliphatic water reducing agent prepared from lignosulfonate wastewater and a synthesis process thereof.
Background
The high-efficiency water reducing agent is one of the main raw materials for producing high-strength and high-performance concrete. At present, in domestic markets, the used high-efficiency water reducing agent comprises a melamine resin water reducing agent, a sulfamic acid water reducing agent and an aliphatic high-efficiency water reducing agent besides a naphthalene water reducing agent, wherein the aliphatic high-efficiency water reducing agent is one of the most important non-naphthalene water reducing agents, and the production raw materials of the aliphatic water reducing agent comprise formaldehyde, sodium sulfite and the like.
The existing common lignosulfonate wastewater is used for preparing the lignosulfonate water reducing agent, so that the resource reasonable utilization of the lignosulfonate wastewater is realized. However, the existing lignosulfonate wastewater is supersaturated, and the complete digestion of the lignosulfonate wastewater cannot be completed by preparing the lignosulfonate water reducing agent by using the lignosulfonate wastewater, so that a new way is opened up for the comprehensive utilization of the lignosulfonate wastewater, and the resource utilization of the lignosulfonate wastewater is necessary.
Disclosure of Invention
The invention aims to provide an aliphatic water reducing agent prepared from lignosulfonate wastewater and a synthesis process thereof, opens up a new way for comprehensively utilizing the lignosulfonate wastewater, and realizes the resource reasonable utilization of the lignosulfonate wastewater.
The above object of the present invention is achieved by the following technical solutions:
the aliphatic water reducer prepared from lignosulfonate wastewater comprises the following raw materials in parts by weight:
by adopting the technical scheme, a new way for comprehensively utilizing the lignosulfonate wastewater is developed, and the lignosulfonate wastewater is reasonably utilized as resources. And the lignosulfonate contains more hydroxyl or amino and is subjected to condensation reaction with formaldehyde under an alkaline condition, so that more water reducing groups are introduced into the water reducing agent, the water reducing effect of the water reducing agent is improved, and the water reducing agent is endowed with a good water reducing effect. By treating the lignosulfonate wastewater, the content of lignosulfonate in unit volume is improved, so that the reaction efficiency and yield are improved, and the water reducing effect of the water reducing agent is improved.
The invention is further configured to: the water reducing agent is prepared from the following raw materials in parts by weight:
0.02-0.06 part of potassium persulfate.
Through adopting above-mentioned technical scheme, potassium persulfate is the acidity, can provide certain hydrogen ion for sodium sulfite hydrolyzes for sodium sulfite's hydrolysis improves work efficiency. And potassium persulfate and sodium sulfite can form an initiator of a redox system, so that the grafting rate and the reaction efficiency of lignosulfonate and sulfonic acid groups in the water reducing agent are improved, and the water reducing effect of the water reducing agent is improved. And the threshold energy of the polymerization reaction can be reduced, so that the reduction of the reaction rate is compensated, and the energy consumption is reduced.
The invention is further configured to: the treated lignosulfonate wastewater is prepared from the following raw materials in percentage by weight:
by adopting the technical scheme, the dilute sulfuric acid is used for adjusting the pH value of the lignosulfonate wastewater, so that lignosulfonate is hydrolyzed to generate lignosulfonic acid, thereby facilitating the subsequent extraction of lignosulfonate and improving the working efficiency. The extractant is used for extracting lignosulfonate in the lignosulfonate wastewater so as to separate the lignosulfonate from the inorganic salt. The back extractant is used for changing the lignosulfonate into a salt substance soluble in water, so that the lignosulfonate is separated from the extractant, and the later extractant is convenient to recycle.
The invention is further configured to: the extractant is prepared from the following raw materials in percentage by weight:
30-40% of carbon tetrachloride;
20-30% of n-octanol;
40-50% of tri-n-octylamine.
By adopting the technical scheme, the tri-n-octylamine is a commonly used aromatic sulfonic acid organic matter complexing agent, and can be complexed with aromatic sulfonic acid organic matters to form a complex, so that the lignosulfonate can be conveniently extracted. Carbon tetrachloride is a non-polar diluent, n-octanol is a polar diluent, and the extraction effect of the lignosulfonate can be improved by compounding the two diluents.
The invention is further configured to: the stripping agent comprises the following raw materials in percentage by weight:
by adopting the technical scheme, the sodium hydroxide is used for reacting with the lignosulfonic acid to generate salt substances, so that the lignosulfonate is separated from the extractant, and the extractant is convenient to recycle. The sodium dihydrogen phosphate and the disodium hydrogen phosphate are used for adjusting the stability of the pH value of the wastewater, and when the pH value is reduced, the disodium hydrogen phosphate can be hydrolyzed to improve the pH value of the wastewater. When the pH value of the wastewater becomes large, water is mixed in the sodium dihydrogen phosphate to reduce the pH value of the wastewater, so that the pH value of the wastewater is in a stable interval, and the reaction is convenient to carry out. And after the back extraction is finished, sodium dihydrogen phosphate and disodium hydrogen phosphate exist in the treated wastewater, so that the sodium dihydrogen phosphate and the disodium hydrogen phosphate exist in the liquid product of the aliphatic water reducing agent. When the water reducing agent is used, sodium dihydrogen phosphate and disodium hydrogen phosphate can be adsorbed on the surface of cement particles to inhibit hydration, and the sodium dihydrogen phosphate and the disodium hydrogen phosphate can inhibit the dissolution of calcium ions, so that the concrete has a good retarding effect.
A synthesis process for preparing an aliphatic water reducing agent from lignosulfonate wastewater comprises the following preparation processes:
s1, treating the lignosulfonate wastewater to prepare the treated lignosulfonate wastewater;
s2: mixing acetone, formaldehyde and the treated lignosulfonate wastewater in proportion, heating to 40-50 ℃, and reacting for 0.5-1.5h to prepare a first mixed solution;
s3: uniformly mixing sodium sulfite, potassium persulfate and deionized water according to a certain proportion, heating to 40-50 ℃, and reacting for 0.5-1.5h to prepare a second mixed solution;
s4: taking a second mixed solution with the weight of one half of the total weight of the second mixed solution, uniformly mixing the second mixed solution with the first mixed solution, heating to 40-50 ℃, and reacting for 0.5-1.5h to prepare a third mixed solution;
s5: heating the rest second mixed solution to 50-70 ℃, and dropwise adding the third mixed solution at a constant speed within 0.5-1.5 h; after the dropwise addition is finished, the temperature is raised to 90-100 ℃, and the reaction lasts for 1-3h, so that the aliphatic water reducing agent liquid product is prepared.
By adopting the technical scheme, in the step S2, the treated lignosulfonate wastewater is used for endowing the mixed solution with an alkaline condition, so that acetone and formaldehyde react in an alkaline medium, α -hydrogen acetone easily generates enol negative ions, α -hydrogen-free formaldehyde carbon groups provide positive carbon ions, the enol negative ions and the α -hydrogen-free formaldehyde carbon groups react to generate hydroxymethyl acetone or dimethylol acetone, and the reaction can react at 40-50 ℃, so that the formaldehyde and the acetone are effectively prevented from volatilizing, the loss of raw materials is effectively reduced, the production cost is reduced, the formaldehyde and the lignosulfonate react under the alkaline condition to perform hydroxymethylation, most of methoxy groups and sulfonic groups on macromolecules are removed, the activity of lignosulfonate is improved, and the organic synthesis reaction is improved.
In the step 3, sodium sulfite, potassium persulfate and deionized water are mixed to provide certain hydrogen ions for the hydrolysis of the sodium sulfite, so that the hydrolysis of the sodium sulfite is accelerated, and the working efficiency is improved. In the step 4, a part of acetone and formaldehyde can react with sodium bisulfite to generate hydroxyl sulfonate, and simultaneously release part of heat, so that the sulfonation degree of acetone and formaldehyde is improved, the reaction can be smoothly carried out when the aliphatic water reducing agent is generated by the reaction, the reaction efficiency is improved, more water reducing groups can be introduced, and the water reducing effect is improved. In the step 4, the third mixed solution is dropwise added into the remaining second mixed solution at a constant speed within 0.5-1.5h, so that the formaldehyde and the acetone can be in full contact reaction with the sodium bisulfite, the reaction efficiency and the yield are improved, the formaldehyde and the acetone are prevented from volatilizing, the loss of raw materials is effectively reduced, and the production cost is reduced.
The invention is further configured to: the treated lignosulfonate wastewater comprises the following preparation process:
1) mixing the lignosulfonate wastewater and dilute sulfuric acid according to a proportion to prepare a mixed solution A;
2) evaporating and concentrating the mixed solution A to prepare concentrated lignosulfonate wastewater; the pH value of the concentrated lignosulfonate wastewater is 1.3-1.5;
3) mixing the extractant and the concentrated lignosulfonate wastewater according to a certain proportion, uniformly stirring, standing until layering, and separating to obtain inorganic salt-containing liquid and a lignosulfonate-containing complex;
4) mixing the back extractant and the complex containing the lignosulfonate according to a certain proportion, stirring uniformly, standing until layering, and separating to obtain the treated lignosulfonate wastewater and the recyclable extractant.
By adopting the technical scheme, the dilute sulfuric acid is added, so that new impurity ions are not introduced, the operation of workers is facilitated, the dilute sulfuric acid can be directly mixed with the lignosulfonate wastewater, and the working efficiency is improved. After adding dilute sulfuric acid, concentrating the lignosulfonate wastewater to reduce water content, so that the reaction is carried out forward, and the synthesis of lignosulfonic acid is promoted. And the content of the lignosulfonate in unit volume is increased, so that the reaction efficiency and the yield are improved.
In conclusion, the beneficial technical effects of the invention are as follows:
1. according to the invention, the aliphatic water reducing agent is prepared from the lignosulfonate wastewater, so that a new way for comprehensively utilizing the lignosulfonate wastewater is developed, and the lignosulfonate wastewater is reasonably utilized as a resource;
2. the lignosulfonate wastewater is treated, so that the content of lignosulfonate in unit volume is increased, the reaction efficiency and yield are improved, and the water reducing effect of the water reducing agent is improved;
3. by adopting the synthesis process disclosed by the invention, formaldehyde and acetone can be prevented from being volatilized due to heating during reaction, so that the loss of raw materials is effectively reduced, the production cost is reduced, and the reaction can adopt higher temperature, so that the introduction amount of water reducing groups is increased, and the water reducing effect of the water reducing agent is improved.
Detailed Description
The invention discloses a synthesis process for preparing an aliphatic water reducing agent from lignosulfonate wastewater, which comprises the following preparation processes:
s1, treating the lignosulfonate wastewater, which comprises the following treatment processes:
1) mixing 50% of lignosulfonate wastewater and 6% of dilute sulfuric acid to prepare a mixed solution A; the mass concentration of the dilute sulfuric acid is 50 percent;
2) evaporating and concentrating the mixed solution A to prepare concentrated lignosulfonate wastewater; the pH value of the concentrated lignosulfonate wastewater is 1.3;
3) mixing 20% of an extracting agent with the concentrated lignosulfonate wastewater obtained in the step 2), uniformly stirring, standing until layering, and separating to obtain inorganic salt-containing liquid and a lignosulfonate-containing complex;
the extractant is prepared from the following raw materials in percentage by weight: uniformly mixing 40% of carbon tetrachloride, 30% of n-octanol and 30% of tri-n-octylamine to prepare an extracting agent;
4) mixing 24% of the back extractant with the complex containing the lignosulfonate obtained in the step 3), uniformly stirring, standing until layering, and separating to obtain treated lignosulfonate wastewater and a recyclable extractant;
the stripping agent is prepared from the following raw materials in percentage by weight: uniformly mixing 36% of sodium hydroxide, 10% of sodium dihydrogen phosphate, 20% of disodium hydrogen phosphate and 34% of deionized water to prepare a stripping agent; the mass concentration of the sodium hydroxide is 40 percent;
s2: mixing 10 parts of acetone, 40 parts of formaldehyde and 10 parts of treated lignosulfonate wastewater, heating to 40 ℃, and reacting for 1.5 hours to prepare a first mixed solution; the mass concentration of formaldehyde is 40%;
s3: uniformly mixing 10 parts of sodium sulfite, 0.5 part of potassium persulfate and 40 parts of deionized water, heating to 40 ℃, and reacting for 1.5 hours to obtain a second mixed solution;
s4: taking a second mixed solution with the weight of one half of the total weight of the second mixed solution, uniformly mixing the second mixed solution with the first mixed solution, heating to 40 ℃, and reacting for 1.5 hours to obtain a third mixed solution;
s6: heating the rest second mixed solution to 50 ℃, and dropwise adding the third mixed solution at a constant speed within 1.5 h; after the dropwise addition is finished, the temperature is raised to 90 ℃, and the reaction is carried out for 3 hours, so as to obtain the liquid product of the aliphatic water reducing agent with the solid content of 36%.
The lignosulfonate waste water used in the invention is a pulp waste liquid containing lignosulfonate.
The difference between the embodiments 2-5 and the embodiment 1 is that the water reducing agent comprises the following raw materials in parts by weight:
examples 6 to 9 differ from example 1 in that the treated lignosulfonate wastewater comprises the following raw materials in percentage by weight:
examples 10 to 13 differ from example 1 in that the extractant comprises the following raw materials in weight percent:
examples 14-17 differ from example 1 in that the stripping agent comprises the following raw materials in weight percent:
examples 18 to 21 are different from example 1 in that the heating temperature in step S2 is as shown in the following table:
| examples | Example 18 | Example 19 | Example 20 | Example 21 |
| Temperature/. degree.C | 43 | 45 | 47 | 50 |
Examples 22 to 25 differ from example 1 in that the reaction times in step S2 are as shown in the following table:
| examples | Example 22 | Example 23 | Example 24 | Example 25 |
| Time/h | 0.5 | 0.7 | 1 | 1.3 |
Examples 26 to 29 are different from example 1 in that the heating temperature in step S3 is as shown in the following table:
| examples | Example 26 | Example 27 | Example 28 | Example 29 |
| Temperature/. degree.C | 43 | 45 | 47 | 50 |
Examples 30 to 33 differ from example 1 in that the reaction times in step S3 are as shown in the following table:
| examples | Example 30 | Example 31 | Example 32 | Example 33 |
| Time/h | 0.5 | 0.7 | 1 | 1.3 |
Examples 34 to 37 are different from example 1 in that the heating temperature in step S4 is as shown in the following table:
| examples | Example 34 | Example 35 | Example 36 | Example 37 |
| Temperature/. degree.C | 43 | 45 | 47 | 50 |
Examples 38 to 41 differ from example 1 in that the reaction times in step S4 are as shown in the following table:
| examples | Example 38 | Example 39 | Example 40 | EXAMPLE 41 |
| Time/h | 0.5 | 0.7 | 1 | 1.3 |
Examples 42 to 45 are different from example 1 in that the first temperature rise temperature in step S5 is as shown in the following table:
| examples | Example 42 | Example 43 | Example 44 | Example 45 |
| Temperature/. degree.C | 55 | 60 | 65 | 70 |
Examples 46 to 49 differ from example 1 in that the dropping time in step S5 is as shown in the following table:
| examples | Example 46 | Example 47 | Example 48 | Example 49 |
| Time/h | 0.5 | 0.7 | 1 | 1.3 |
Examples 50 to 53 are different from example 1 in that the second temperature rise temperature in step S5 is shown in the following table:
| examples | Example 50 | Example 51 | Example 52 | Example 53 |
| Temperature/. degree.C | 93 | 95 | 97 | 100 |
Examples 54 to 57 differ from example 1 in that the reaction times in step S5 are as shown in the following table:
| examples | Example 54 | Example 55 | Example 56 | Example 57 |
| Time/h | 1 | 1.5 | 2 | 2.5 |
Examples 57 to 61 differ from example 1 in that the pH of the concentrated lignosulfonate wastewater in step 2) is as shown in the following table:
| examples | Example 58 | Example 59 | Example 60 | Example 61 |
| pH value | 1.35 | 1.4 | 1.45 | 1.5 |
Comparative example:
comparative example 1 differs from example 1 in that: the lignosulfonate wastewater is not treated, namely the lignosulfonate wastewater is directly adopted, and an aliphatic water reducing agent liquid product with the solid content of 25 percent can be obtained by the synthesis process.
Comparative example 2 differs from example 1 in that: the aliphatic water reducer in the comparative example comprises the following preparation processes:
s1: uniformly mixing 10 parts of sodium sulfite and 40 parts of deionized water, heating to 40 ℃, and reacting for 1.5 hours to obtain a first reaction solution;
s2: adding 10 parts of treated lignosulfonate wastewater and 10 parts of acetone into the reaction liquid I, heating to 50 ℃, and reacting for 1.5 hours to obtain a reactant II;
s3: and heating the reactant II to 50 ℃, dropwise adding 40 parts of formaldehyde into the reactant II, finishing dropwise adding at a constant speed within 1.5h, heating to 90 ℃ after dropwise adding, and reacting for 3h to obtain an aliphatic water reducing agent liquid product with the solid content of 20%.
Comparative example 3 differs from example 1 in that: the water reducing agent does not contain potassium persulfate, and the aliphatic water reducing agent liquid product with the solid content of 30 percent can be obtained by the synthesis process.
Comparing the water reducing agents prepared in the examples 1-5 and the comparative examples 1-3, testing the fluidity of the cement paste and the water reducing rate of the mortar according to GB/T8077, wherein the cement is 42.5R of conch cement, the water cement ratio is 0.29, and the mixing amount of the water reducing agent is 0.6%. The concrete mixing proportion is as follows: 330kg/m cement3742kg/m of sand3Stone 1113kg/m3(the nominal grain size of the crushed stones is 5mm-20mm, and the crushed stones adopt a secondary composition, wherein 5mm-10mm accounts for 40 percent, and 10mm-20mm accounts for 60 percent). The results of the measurements are shown in the following table:
| test sample | The water reducing rate of the mortar is% | Initial slump (mm) | Slump of 1h (mm) |
| Example 1 | 19.1 | 230 | 219 |
| Example 2 | 19.3 | 220 | 211 |
| Example 3 | 19.5 | 225 | 218 |
| Example 4 | 19.7 | 225 | 220 |
| Example 5 | 19.9 | 225 | 222 |
| Comparative example 1 | 16.6 | 225 | 190 |
| Comparative example 2 | 14.3 | 225 | 165 |
| Comparative example 3 | 18.7 | 230 | 215 |
From the above table, it is understood that the water reducing effect of the water reducing agent can be improved and the concrete can be provided with good slump retaining property by treating the lignosulfonate wastewater as compared with the comparative example 1 in examples 1 to 5. The content of the lignosulfonate in the unit volume of the lignosulfonate wastewater after treatment is improved, so that the reaction efficiency and the yield are improved, and the water reducing effect of the water reducing agent is improved.
As can be seen from comparison of examples 1 to 5 with comparative example 2, by adopting the synthesis process of the present invention, the water-reducing effect of the water-reducing agent can be improved, and good slump retention can be imparted to concrete. The synthesis process of the invention can prevent formaldehyde and acetone from volatilizing due to heating during reaction, thereby effectively reducing the loss of raw materials and improving the introduction amount of water reducing groups and the water reducing effect of the water reducing agent.
As can be seen from comparison of examples 1 to 5 with comparative example 3, the addition of potassium persulfate improves the water-reducing effect of the aliphatic water-reducing agent and imparts excellent slump retention to the concrete. The potassium persulfate is added to improve the hydrolysis reaction process of the sodium sulfite and reduce the threshold energy of the polymerization reaction, so that the generation and reaction process of the sodium bisulfite are improved, the introduction amount of the water reducing group is improved, and the water reducing effect of the water reducing agent is improved.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (7)
1. The utility model provides a make aliphatic water-reducing agent with lignosulfonate waste water which characterized in that: the health-care food is prepared from the following raw materials in parts by weight:
2. the aliphatic water reducing agent prepared from lignosulfonate wastewater according to claim 1, which is characterized in that: the water reducing agent is prepared from the following raw materials in parts by weight:
0.5-1 part of potassium persulfate.
3. The aliphatic water reducing agent prepared from lignosulfonate wastewater according to claim 1, which is characterized in that: the treated lignosulfonate wastewater is prepared from the following raw materials in percentage by weight:
4. the aliphatic water reducing agent prepared from lignosulfonate wastewater according to claim 3, which is characterized in that: the extractant is prepared from the following raw materials in percentage by weight:
30-40% of carbon tetrachloride;
20-30% of n-octanol;
40-50% of tri-n-octylamine.
5. The aliphatic water reducing agent prepared from lignosulfonate wastewater according to claim 4, which is characterized in that: the stripping agent comprises the following raw materials in percentage by weight:
6. a synthetic process for preparing an aliphatic water reducing agent by using lignosulfonate wastewater is characterized by comprising the following steps of: the preparation method comprises the following preparation processes:
s1, treating the lignosulfonate wastewater to prepare the treated lignosulfonate wastewater;
s2: mixing acetone, formaldehyde and the treated lignosulfonate wastewater in proportion, heating to 40-50 ℃, and reacting for 0.5-1.5h to prepare a first mixed solution;
s3: uniformly mixing sodium sulfite, potassium persulfate and deionized water according to a certain proportion, heating to 40-50 ℃, and reacting for 0.5-1.5h to prepare a second mixed solution;
s4: taking a second mixed solution with the weight of one half of the total weight of the second mixed solution, uniformly mixing the second mixed solution with the first mixed solution, heating to 40-50 ℃, and reacting for 0.5-1.5h to prepare a third mixed solution;
s5: heating the rest second mixed solution to 50-70 ℃, and dropwise adding the third mixed solution at a constant speed within 0.5-1.5 h; after the dropwise addition is finished, the temperature is raised to 90-100 ℃, and the reaction lasts for 1-3h, so that the aliphatic water reducing agent liquid product is prepared.
7. The synthesis process for preparing the aliphatic water reducing agent by using the lignosulfonate wastewater as claimed in claim 6, is characterized in that: the treated lignosulfonate wastewater comprises the following preparation process:
1) mixing the lignosulfonate wastewater and dilute sulfuric acid according to a proportion to prepare a mixed solution A;
2) evaporating and concentrating the mixed solution A to prepare concentrated lignosulfonate wastewater; the pH value of the concentrated lignosulfonate wastewater is 1.3-1.5;
3) mixing the extractant and the concentrated lignosulfonate wastewater according to a certain proportion, uniformly stirring, standing until layering, and separating to obtain inorganic salt-containing liquid and a lignosulfonate-containing complex;
4) mixing the back extractant and the complex containing the lignosulfonate according to a certain proportion, stirring uniformly, standing until layering, and separating to obtain the treated lignosulfonate wastewater and the recyclable extractant.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321227A (en) * | 2011-05-27 | 2012-01-18 | 江苏博特新材料有限公司 | Sulfonated-acetone condensate water reducing agent and preparation method thereof |
| CN102585103A (en) * | 2011-11-18 | 2012-07-18 | 重庆建研科之杰新材料有限公司 | Preparation method for low-bleeding water aliphatic high-efficiency water reducing agent |
| CN102633965A (en) * | 2012-05-07 | 2012-08-15 | 昆明理工大学 | Synthetic method of aliphatic-series sulfonate high-efficiency water reducer |
| CN110316891A (en) * | 2019-03-25 | 2019-10-11 | 华颢控股（集团）有限公司 | A kind of preparation method of H acid waste water extraction process and modified aliphatic water reducing agent |
-
2019
- 2019-12-21 CN CN201911331825.0A patent/CN111087190B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321227A (en) * | 2011-05-27 | 2012-01-18 | 江苏博特新材料有限公司 | Sulfonated-acetone condensate water reducing agent and preparation method thereof |
| CN102585103A (en) * | 2011-11-18 | 2012-07-18 | 重庆建研科之杰新材料有限公司 | Preparation method for low-bleeding water aliphatic high-efficiency water reducing agent |
| CN102633965A (en) * | 2012-05-07 | 2012-08-15 | 昆明理工大学 | Synthetic method of aliphatic-series sulfonate high-efficiency water reducer |
| CN110316891A (en) * | 2019-03-25 | 2019-10-11 | 华颢控股（集团）有限公司 | A kind of preparation method of H acid waste water extraction process and modified aliphatic water reducing agent |
Non-Patent Citations (3)
| Title |
|---|
| 张恩: "脂肪族磺酸盐高效减水剂的合成及应用性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
| 方云辉等: "脂肪族与木质素磺酸钠接枝共聚制备减水剂", 《新型建筑材料》 * |
| 韩全卫: "《混凝土脱模剂和相关工程材料的应用"，韩全卫，中国建材工业出版社，第89页，2008年9月30日）。》", 30 September 2008, 中国建材工业出版社 * |
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