CN105669926B - A kind of preparation method of high-content naphthalene water reducer - Google Patents
A kind of preparation method of high-content naphthalene water reducer Download PDFInfo
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- CN105669926B CN105669926B CN201610042466.7A CN201610042466A CN105669926B CN 105669926 B CN105669926 B CN 105669926B CN 201610042466 A CN201610042466 A CN 201610042466A CN 105669926 B CN105669926 B CN 105669926B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0237—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing sulfur
-
- 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
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
- C04B24/226—Sulfonated naphtalene-formaldehyde condensation products
-
- 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 a kind of preparation method of high-content naphthalene water reducer, comprise the following steps：It is dry after sulfonating reaction, hydrolysis, condensation reaction, neutralization, wherein：Sulfonating reaction is in the reaction kettle with rectifying, the sulfuric acid that mass percent concentration is 50~93% rectifying and is subjected to sulfonating reaction together with naphthalene, sulfuric acid carries out sulfonating reaction with naphthalene, while generates water, and sulfuric acid concentration declines, pass through rectifying recovered water, the sulfuric acid concentration in kettle is improved, naphthalene returns to evaporate continues sulfonating reaction into reaction kettle, since rectifying recovered water, sulfonation generation water reach balance in whole process, temperature in the kettle stabilization is between 160~175 DEG C, until sulfuric acid reaction consumption is complete in kettle；Preparation method using the present invention, technique simple and stable, parameter are easily-controllable, and obtained naphthalene water reducer properties of product are stable, quality is good.
Description
Technical field
The invention belongs to building material field, is related to a kind of preparation method of chemical admixture, and in particular to a kind of height contains
Measure the preparation method of naphthalene water reducer.
Background technology
Cement water reducing agent is under concrete workability and cement consumption permanence condition, can reduce mixing water amount, carry
High concrete intensity, saves the additive of cement consumption.Naphthalene water reducer is usage amount maximum on domestic market, using most
A kind of extensive high efficiency water reducing agent.According to statistics, the two generation water-reducing agents such as naphthalene system in 2009 account for all synthesis water-reducing agent total outputs
67.5%, 2010 are 67.1%, and 2011 are 66.5%, although proportion declines year by year, its price is relatively cheap, and
It is good with early strength agent, retarder compound property, multi-functional composite superplasticizer can be formed, it is commercially still wide at present
It is general.
The preparation method of naphthalene water reducer is mainly included after sulfonation, hydrolysis, condensation, neutralization etc. are reacted through being dried to obtain at present
Product.This method obtains that naphthalene water reducer concentration is low, and the sodium sulphate (accounting for pulvis) about containing quality 20~25%, makes concrete collapse
Degree of falling loss increases, and is unsuitable for gravitational grouting and prepares pump concrete, influences construction speed and quality.The low naphthalene system of concentration
Na in water-reducing agent product2SO4Crystallization can be produced below 15 DEG C, seriously affects concrete metering pump precision and water-reducing effect.For
Reduce the crystallization degree in product and reduce crystalline polamer, increase process that low temperature filters in many production technologies by Na2SO4
Remove.
To manufacture the low high-quality naphthalene water reducer of sulphates content, industrially generally using calcium desulfurization method come sulfuric acid
Salt.Na is reduced as patent CNl03755203A is provided in a kind of naphthalene water reducer preparation process2SO4Method：By sulfonation,
Hydrolysis, condensation, neutralize the low dense naphthalene water reducer of four processes synthesis, then through calcium sulfate precipitation separation process, is prepared highly concentrated
Naphthalene water reducer.But produce another question and be exactly：Resulting calcium sulfate waste residues, serious pollution of ecological environment, at the same time
Also increase equipment and production cost.
CNl04497250A proposes the dosage using the binary azeotropic method reduction concentrated sulfuric acid, makes sulfuric acid sulfonation reaction thorough, from
And reduce Na in product2SO4The content of content.But in fact many data show that naphthalene and water do not have azeotropism, and experiment also indicates that
Naphthalene cannot form azeotropic with water, and distillation water-scavenging capability is limited during preparing water-reducing agent.In addition at a high temperature of 140~160 DEG C,
With naphthalene oxidation reaction easily occurs for the concentrated sulfuric acid, and the side reactions such as secondary sulfonation occur for the naphthalene sulfonic acids being previously generated, and make the utilization of naphthalene
Rate declines；Due to the dehydration of the concentrated sulfuric acid, under high temperature, the naphthalene sulfonic acids generated in advance also further reacts generation sulfone etc. easily with naphthalene
Side reaction occurs, and makes the performance of water-reducing agent reduce.
Accelerating agent is made using ethanol Na is isolated from naphthalene water reducer2SO4, it is suitable in higher temperature (75 DEG C) and uses up
Carried out under conditions of water-reducing agent total concentration that may be high, added by the 20% of aqua quality and promote analysis agent, Na can be made2SO4Content is down to
Less than 3%
The content of the invention
For above-mentioned traditional high concentration and high efficiency naphthalene water reducer production waste material is difficult, oxidation, secondary sulphur in technical process
Change etc.
Defect, the present invention provide a kind of method that high concentration and high efficiency naphthalene water reducer is produced using low-concentration sulfuric acid as raw material.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of high-content naphthalene water reducer, it is characterised in that comprise the following steps：
（1）Sulfonation：
In the reaction kettle with rectifying, by mass percent concentration be 50~93% sulfuric acid together with naphthalene rectifying go forward side by side
Row sulfonating reaction, sulfuric acid carries out sulfonating reaction with naphthalene, while generates water, and sulfuric acid concentration declines, and by rectifying recovered water, improves kettle
Interior sulfuric acid concentration, naphthalene returns to evaporate continues sulfonating reaction into reaction kettle, since rectifying recovered water, sulfonation generate in whole process
Water reaches balance, and temperature in the kettle stabilization is between 160~175 DEG C, until sulfuric acid reaction consumption is complete in kettle；
(2) hydrolyze：
After sulfonating reaction, remaining α-naphthalenesulfonicacid adds water that hydrolysis occurs, and hydrolysis time is 0~0.5h, temperature
For l00~140 DEG C；
(3) it is condensed：In the hydrolysis product that step (2) is obtained, add paraformaldehyde and condensation reaction occurs for water；
(4) neutralize：Step (3) condensation reaction products are adjusted into pH value to 6-8, drying, up to high-content naphthalene water reducer.
Further setting is as follows：
In step (1)：The molar ratio of naphthalene and sulfuric acid is l：0.95~1.15；Sulfonating reaction temperature is preferably 160~165
DEG C, the time is 2~10.0h.
In step (1)：Sulfonating reaction is carried out at the same time with rectifying and dewatering process, to ensure the concentration of sulfonating agent sulfuric acid.
Under latm, the sulfuric acid boiling point of mass concentration 60% is 142 DEG C, and the sulfuric acid boiling point of mass concentration 70% is 170 DEG C, when
When temperature in the kettle is 160~165 DEG C, the concentration of sulfuric acid is 65~68%, and the sulfuric acid of the concentration can be used as sulfonating agent by naphthalene sulfonation
For corresponding sulfonic acid.
The present invention need not select the concentrated sulfuric acid, work as sulphur due to being carried out at the same time using sulfonating reaction with rectifying and dewatering process
When acid concentration does not reach concentration needed for sulfonating reaction, by rectifying and dewatering, water is light component, in distillation process, from rectifying column
Top produces, and the sulfuric acid concentration in kettle rises, and temperature in the kettle rises；When most 160~175 DEG C of temperature in the kettle rising, sulfuric acid and naphthalene
Generation sulfonating reaction, while water is generated, at this time, sulfuric acid concentration declines, in this way, due to rectifying recovered water, sulfonation in whole process
Generation water reaches balance, and temperature in the kettle stabilization is between 160~175 DEG C, until sulfuric acid reaction consumption is complete in kettle.
In step (1)：In distillation process, a recovered water in rectifying tower top distillate, upper strata naphtalene oil return evaporate into reaction kettle into
Row sulfonating reaction.
Since naphthalene has higher vapour pressure in various temperature, part naphthalene also vaporizes entrance at the same time in rectifying removal process
Tower top.The fusing point of naphthalene is up to 80 DEG C, and the mixed vapour that rectifying tower top comes out need to use 80~95 DEG C of hot water cooling, and by distillate
Insulation is at 80~85 DEG C, phenomena such as preventing from blocking.In addition naphthalene and water are needed after being condensed together with a gun barrel, general
The hydromining of tank middle and lower part goes out, and the naphthalene of tank middle and upper part is returned sulfonating reaction kettle, carries out further sulfonating reaction.
In the step (2)：It is 0~0.5h that the time of hydrolysis is very short, and temperature is 100~140 DEG C, you can with not
Step (when hydrolysis time is 0) is hydrolyzed, and directly carries out the condensation of step (3).
Since sulfonating reaction is a reversible reaction, the stability of α-naphthalenesulfonicacid is poor, and hydrolysis rate is more than beta-naphthalenesulfonic-acid.It is low
In rectifying concentration process, α-naphthalenesulfonicacid is also hydrolyzed concentration sulphuric acid at the same time, therefore after sulfonation, α-naphthalenesulfonicacid content is low,
Beta-naphthalenesulfonic-acid content is high.Therefore it is different from traditional water-reducing agent production, can be without hydrolysis, or hydrolysis time is very
It is short, it can be completed within the 0.5h times.
The present invention operation principle and have the beneficial effect that：
L, the present invention uses low-concentration sulfuric acid as raw material, and dilute sulfuric acid rectifying concentration is combined using with sulfonating reaction, raw
Produce high concentration and high efficiency naphthalene water reducer；
The rectifying of the invention together with naphthalene by dilute sulfuric acid, in distillation process, water is light component, is produced from rectifying tower top, kettle
Interior sulfuric acid concentration rises, and rectifying kettle temperature rises.As the h 2 so 4 concentration ＞ 63% in kettle, the temperature in kettle is about 150~
l 75℃.At a temperature of this, with naphthalene sulfonating reaction occurs for sulfuric acid, while generates water, declines sulfuric acid concentration.Whole process is essence
Recovered water is evaporated, sulfonation generation water reaches balance, makes the temperature stabilization in kettle between 150~175 DEG C without further up.
As sulfuric acid reaction runs out of in kettle, sulfonating reaction generation water no longer occurs, system temperature just can be further up, so as to avoid
Sulphuric acid concentration need high temperataure phenomena (180 DEG C of ＞), be gradually increasing dilute sulfuric acid concentration additionally, due to rectifying and dewatering effect and protect
Sulfonation ability is demonstrate,proved, makes naphthalene sulfonating reaction thorough；Therefore ask can be real without adding excessive sulfuric acid with quantitative reaction for naphthalene and sulfuric acid
It is existing energy-saving.
2nd, it is sulfonating agent to use the relatively weak low-concentration sulfuric acid of non-oxidation ability, sulfonation ability (concentration is 50~93%)；It is low
The sulfuric acid of concentration it also avoid the possibility that naphthalene sulfonic acids further reacts generation sulfone with naphthalene.
3rd, the ratio of naphthalene of the invention and sulfonating agent sulfuric acid is controlled in l：(0.95~1.15), the more traditional l of ratio：(1.3
~1.4) have and significantly decline, so that the content of sodium sulphate is reduced to less than 10% in product, product matter can be greatly improved
Amount, adapts to the requirement of winter construction.
4th, the hydrolysis time of step (2) of the present invention is short, it might even be possible to need not without hydrolysing step, and directly into
The condensation of row step (3), has so saved process and time.
It is described further below in conjunction with embodiment.
Embodiment：
Embodiment l：
134g crude naphthalenes (purity >=95%, 1.0mol), 114g sulfuric acid (mass concentrations are added into reaction bulb：90%,
1.05mol), the rectifying column of 20cm is carried on reaction bulb, is warming up to 160~170 DEG C of reactive distillation 3h, during which recovered water 16g, instead
A certain amount of water is added after answering, 0.5h is hydrolyzed at 110 DEG C, Controlled acidity is 28% after hydrolysis.After cooling to 90 DEG C, add
34.4g paraformaldehydes (purity >=96%, 1.1mol is in terms of formaldehyde) and 58.5g water, are gradually warming up to 100~105 DEG C, keep the temperature 4h,
In insulating process plus water management polymerize under suitable viscosity.Liquid caustic soda is added after reaction adjusts pH=6~8, it is dry, obtain
Naphthalene water reducer.
Embodiment 2：
Add 134g crude naphthalenes (purity >=95%, 1.0mol), 178.0g sulfuric acid (mass concentrations into reaction bulb：55%,
1.0mol), 135 DEG C are warming up to start back to evaporate, recovered water, continue rectifying and be warming up to 165~175 DEG C of reaction 9h, after reaction,
Acidity is measured as 26%.95 DEG C are cooled to, adds 30.7g paraformaldehydes (purity >=99%, lmol is in terms of formaldehyde) and 54.0g water,
100~110 DEG C are gradually warming up to, 8h is kept the temperature, adds water management to polymerize under suitable viscosity in insulating process.After reaction plus
Enter liquid caustic soda and adjust pH=6~8, it is dry, obtain naphthalene water reducer.
Embodiment 3：
134.7g crude naphthalenes (purity >=95%, 1.0mol), the 147.0g concentrated sulfuric acid (mass concentrations are added into reaction bulb：
70%, 1.05mol), 170~175 DEG C of reaction 1.5h are warming up to, a certain amount of water is added after reaction, is hydrolyzed at 120 DEG C
0.5h, Controlled acidity is 26% after hydrolysis.After cooling to 90 DEG C, adding 40.6g paraformaldehydes, (purity >=96%, 1.3mol is with first
Aldehyde meter) and 40.6g water, 115~120 DEG C are gradually warming up to, 8h is kept the temperature, adds water management to gather under suitable viscosity in insulating process
Close.Liquid caustic soda is added after reaction adjusts pH=6~8, it is dry, obtain naphthalene water reducer.
Comparative example l：High-concentration naphthalene based water reducer is prepared using the technology of CNl03755203A.
It is 10-25 parts of chloroazotic acid in parts by weight, 35-50 parts of crude naphthalene, 12-16 parts of formaldehyde, 3-5 parts of sodium hydroxide matches somebody with somebody
Than taking each raw material, low dense naphthalene water reducer is synthesized by four sulfonation, hydrolysis, condensation, neutralization processes, then through calcium sulfate precipitation point
From process, highly concentrated naphthalene water reducer is prepared.6-8 parts of calcium sulfate solid waste is obtained at the same time, it is necessary to landfill disposal.
Comparative example 2：High-concentration naphthalene based water reducer is prepared using the technology of CNl04497250A.
L, in parts by weight, 160 parts of liquid industrial naphthalenes are added into reaction kettle, when stirring and being warming up to 135 DEG C, are opened
To begin that the sulfuric acid that 120 parts of concentration are 98% is added dropwise, control adds speed, temperature is no more than 165 DEG C, insulation binary azeotropic reflux 4h,
Controlled acidity is 25%；" azeotropic ", which obtains 18 parts of waste water (dilute sulfuric acid solution), at the same time needs extra process.
2nd, step 1 resulting material is cooled to 115 DEG C, then 23 parts of water is added into reaction kettle, be to slowly warm up to 130 DEG C,
Naphthalene is recycled using binary azeotropic method, Controlled acidity stops hydrolyzing for 26%；
3rd, step 2 resulting material is cooled to 110 DEG C, starts that 100 parts of formaldehyde are added dropwise, control rate of addition, 3 interior drops when small
Add complete, when then insulation condensation 5 is small, recycle formaldehyde at the same time in this step process；
4th, add 170 parts of alkali neutralizations to step 3 gained condensation product, be then drying to obtain finished product.
Using and performance detection：
Naphthalene water reducer prepared by 1-3 of the embodiment of the present invention, high-concentration naphthalene based water reducer is prepared with the prior art, respectively
Performance Indexs measure and statistics are carried out, as shown in table l：
Cement：P II 52.5, Zhejiang spike Cement Co., Ltd, fine aggregate：Sand, 0~5mm of particle diameter.Coarse aggregate：Lime
Rock rubble, 5~lOmm of particle diameter.GB8077-2000 is pressed in experiment《Methods for testing uniformity of concrete admixture》Regulation carry out, its
Middle sodium sulphate presses the gravimetric detemination in standard.
Table l：The embodiment of the present invention is compareed with the performance of the prior art
。
As shown in table l：Naphthalene water reducer prepared by the present invention, the high-concentration naphthalene based water reducer phase prepared with the prior art
Than：
L, sulfuric acid dosage is few, and the sulfuric acid concentration used is low.
It is sulfonation that the present invention, which uses the relatively weak low-concentration sulfuric acid of non-oxidation ability, sulfonation ability (concentration is 50~93%),
Agent；The sulfuric acid of low concentration it also avoid the possibility that naphthalene sulfonic acids further reacts generation sulfone with naphthalene.
2nd, sodium sulphate content is low, and fluidity is high.
The naphthalene of the present invention and the ratio of sulfonating agent sulfuric acid are controlled in l：(0.95~1.15), the more traditional l of ratio：(1.3~
1.4) have and significantly decline, so that the content of sodium sulphate is reduced to less than 10% in product, fluidity higher, can significantly carry
High yield quality, adapts to the requirement of winter construction.
3rd, produced without solid waste or acid-bearing wastewater.
The present invention overcomes traditional handicraft to be also easy to produce calcium sulfate solid waste and the technological deficiency of acid-bearing wastewater, has more preferable ring
Guaranteed cost.
Claims (4)
1. a kind of preparation method of high-content naphthalene water reducer, it is characterised in that comprise the following steps：
（1）Sulfonation：In the reaction kettle with rectifying, by sulfuric acid rectifying together with naphthalene that mass percent concentration is 50~93%
And sulfonating reaction is carried out, sulfuric acid carries out sulfonating reaction with naphthalene, while generates water, and sulfuric acid concentration declines, and by rectifying recovered water, carries
Sulfuric acid concentration in high kettle, naphthalene returns to evaporate continues sulfonating reaction into reaction kettle, due to rectifying recovered water, sulfonation in whole process
Generation water reaches balance, and temperature in the kettle stabilization is between 160~175 DEG C, until sulfuric acid reaction consumption is complete in kettle；Wherein, naphthalene
Molar ratio with sulfuric acid is 1:0.95~1.15；Sulfonating reaction temperature is 160~165 DEG C, and the time is 2~10.0h, sulfonating reaction
It is carried out at the same time with rectifying and dewatering process, to ensure the concentration of sulfonating agent sulfuric acid；
（2）Hydrolysis：After sulfonating reaction, remaining α-naphthalenesulfonicacid adds water that hydrolysis occurs, and hydrolysis time is 0~0.5h,
Temperature is 100~140 DEG C；
（3）Condensation：By step（2）In the hydrolysis product of acquisition, add paraformaldehyde and condensation reaction occurs for water；
（4）Neutralize：By step（3）Condensation reaction products adjust pH value to 6-8, drying, up to high-content naphthalene water reducer.
A kind of 2. preparation method of high-content naphthalene water reducer as claimed in claim 1, it is characterised in that：Step（1）In：Essence
During evaporating, a recovered water in rectifying tower top distillate, upper strata naphtalene oil returns to evaporate carries out sulfonating reaction into reaction kettle.
A kind of 3. preparation method of high-content naphthalene water reducer as claimed in claim 1, it is characterised in that：Rectifying tower top comes out
Mixed vapour cooled down with 80~95 DEG C of hot water, and distillate is kept the temperature at 80~85 DEG C, prevents clogging, naphthalene and
Water be condensed together after with a gun barrel, the hydromining of tank middle and lower part is gone out, and it is anti-that the naphthalene of tank middle and upper part is returned sulfonation
Kettle is answered, carries out further sulfonating reaction.
A kind of 4. preparation method of high-content naphthalene water reducer as claimed in claim 1, it is characterised in that：The step
（2）In：The time of hydrolysis is 0, i.e., without hydrolysing step, and directly carries out step（3）Condensation.
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| CN106432661B (en) * | 2016-09-18 | 2019-04-02 | 江苏苏博特新材料股份有限公司 | A kind of modified naphthalene series water-reducing agent and preparation method thereof |
| CN106746861B (en) * | 2016-12-23 | 2020-01-31 | 平顶山奥思达科技有限公司 | naphthalene series water reducing agent and preparation process thereof |
| CN107573471B (en) * | 2017-08-31 | 2019-10-29 | 浙江吉盛化学建材有限公司 | A kind of production technology of FDN high efficiency water reducing agent |
| CN108530271A (en) * | 2018-05-31 | 2018-09-14 | 山西豪仑科化工有限公司 | A kind of naphthalene method of sulfonating of coproduction 1- naphthols and beta naphthal |
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| CN102351458B (en) * | 2011-07-14 | 2013-08-07 | 兰州大学 | Method for preparing water reducer by using low distillate section of neutral wash oil instead of industrial naphthalene |
| CN104557537B (en) * | 2014-12-04 | 2016-06-08 | 江门谦信化工发展有限公司 | In a kind of tower, reactive distillation produces the method for butyl acrylate |
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