CN101723860B - Method for preparing naphthalene series water reducing agent - Google Patents
Method for preparing naphthalene series water reducing agent Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 150000002790 naphthalenes Chemical class 0.000 title abstract description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000463 material Substances 0.000 claims abstract description 34
- 230000007062 hydrolysis Effects 0.000 claims abstract description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 18
- 238000006482 condensation reaction Methods 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 47
- 238000006277 sulfonation reaction Methods 0.000 claims description 34
- 238000009833 condensation Methods 0.000 claims description 20
- 230000005494 condensation Effects 0.000 claims description 20
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 19
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006386 neutralization reaction Methods 0.000 claims description 18
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical group C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 15
- 238000009413 insulation Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 29
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 7
- 239000000920 calcium hydroxide Substances 0.000 abstract description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a method for preparing a naphthalene series water reducing agent. The method comprises the following steps of naphthalene fusion, sulphonation reaction, steam hydrolysis naphthalene removal, recovery and reuse of naphthalene, condensation reaction and neutral reaction. Compared with the conventional production technology, the process of the invention has the advantages that: the consumption of sulfuric acid is reduced by adjusting a material charging ratio of sulfuric acid to material naphthalene at the step of sulphonation reaction; the step of the recovery and reuse of naphthalene is added, so that the raw materials are fully utilized; and in the following step of neutral reaction, only a small amount of alkali solution is added and the addition of calcium hydroxide is unnecessary, so that the filter step is eliminated, and deposition loss and entrainment loss of the products are avoided.
Description
(1) technical field
The present invention relates to a kind of preparation method of concrete admixture, the preparation method of especially a kind of high dense type naphthalene water reducer or its homology dispersion agent.
(2) background technology
Because the needs of industrial development, people have proposed more and more higher requirement to concrete performance, and a prerequisite that realizes concrete high-performance is to use high efficiency water reducing agent, it not only can improve execution conditions, improve the concrete anti-compression folding strength, but also can strengthen the concrete freeze proof performance such as impervious, be considered to the necessary BSA of concrete.At present, applied high efficiency water reducing agent major part is naphthalene water reducer at home.But in its production process, owing to adopting the excessive vitriol oil as sulphonating agent, brought 18～20% sodium sulfate for final product, excess sulfuric acid sodium exists, and can separate out because of sulfate crystal in winter and the lower place of temperature construction is caused extremely adverse influence.Therefore, the research of the content of sulfuric acid, the high dense type naphthalene series high-efficiency water-reducing agent of production is exactly a very valuable job in the reduction naphthalene water reducer.The neutralization of the useful calcium hydroxide of the method for common reduction and Physical temperature-lowering method, the former can reduce benefit by product wrapping at precipitation process, and filtration difficulty and produce waste residue, and latter's operability is not used for by force and almost suitability for industrialized production.
In the high dense type naphthalene series high-efficiency water-reducing agent suitability for industrialized production of prior art, all be to carry out in the steps below: in the molten NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of molten naphthalene still, lower liquid NAPTHALENE FLAKES. (INDUSTRIAL GRADE） that measures of certain temperature and sulfuric acid are NAPTHALENE FLAKES. (INDUSTRIAL GRADE） in molar ratio: the ratio of sulfuric acid=1: 1.3～2.0 is squeezed into the sulfonation reaction still, carry out sulfonation at 120～160 ℃, sulfonation was lowered the temperature about 3 hours, squeeze into hydrolysis kettle at 80～120 ℃ of reaction 30～45min that are hydrolyzed, hydrolysis finishes cooling and squeezes into condensation kettle, drip formaldehyde about 80 ℃ and carry out condensation reaction, drip and finish in condensation reaction more than 100 ℃ about 5～6 hours, carry out neutralization reaction with still input liquid sodium hydroxide and calcium hydroxide in squeezing into after the cooling, after filtration, filtrate becomes the liquid naphthalene series high-efficiency water-reducing agent, and drying gets the solid naphthalene series high-efficiency water-reducing agent again.The major defect of this production technique is: excess sulfuric acid is more in the production process, only neutralize with liquid caustic soda, can cause in the finished product sodium sulphate content to exceed standard and affect quality, need to add in addition the further excessive sulfuric acid of neutralization of calcium hydroxide, thereby the generation contaminate environment that causes calcium sulfate waste residues, and precipitation process product wrapping, filter residue entrained product all can reduce productivity effect, must carry out the press filtration separation for removing calcium sulfate waste residues in addition, cause artificial, energy consumption, wastage of material, be unfavorable for saving energy and reduce the cost.In addition, there is NAPTHALENE FLAKES. (INDUSTRIAL GRADE） residual in the product, environment is had disadvantageous effect.
(3) summary of the invention
The production technique that the purpose of this invention is to provide a kind of high dense type naphthalene water reducer, but by the high dense type naphthalene water reducer of this technique direct production, easy and simple to handle, the non-secondary pollution discharging has improved resource utilization, successful.
The technical solution used in the present invention is:
A kind of preparation method of naphthalene water reducer, described method comprises:
(1) naphthalene or its homologue with molten state places xanthator, and in 120～140 ℃ of lower 98% vitriol oils that drip metering, sulfonation reaction is carried out in 160～165 ℃ of insulations after dropwising, and obtains the sulfonation material; Described naphthalene or its homologue are 1～2: 1 with the ratio of vitriol oil amount of substance;
(2) step (1) sulfonation material is changed over to hydrolysis and take off in the naphthalene device, be cooled to 120～160 ℃, pass into 120～160 ℃ of water vapour and be hydrolyzed, unreacted free naphthalene is deviate from the water vapour azeotropic, and residue is beta-naphthalenesulfonic-acid;
(3) step (2) beta-naphthalenesulfonic-acid changes the condensation device over to, and adding water regulation system acidity is 16～18, is cooled to 80～120 ℃ of formaldehyde that drip metering, is warming up to 90～135 ℃ after dropwising, and carries out condensation reaction under 0～0.2MPa, obtains the condensation material; Described beta-naphthalenesulfonic-acid is 1: 0.9～1.1 with the ratio of formaldehyde amount of substance;
(4) step (3) condensation material changes neutralising arrangement over to, it is 7.5～9.0 that 60～100 ℃ of lower adding alkali lye carry out neutralization reaction to pH value, reaction finishes namely to get described liquid naphthalene water reducer, can obtain the high dense type naphthalene series high-efficiency water-reducing agent finished product of solid by further drying treatment;
Described alkali lye is sodium hydroxide solution, sodium hydrogen carbonate solution or sodium carbonate solution.
The production technique of the dense type naphthalene water reducer of described height, key step comprise that molten naphthalene, sulfonation reaction, steam hydrolysis take off the recovery of naphthalene, naphthalene, condensation reaction and neutralization reaction.Compared to existing production technology, this technique reduces the sulfuric acid consumption by the feed ratio of sulfuric acid and raw naphthalene material in the adjusting sulfonation reaction step; And increase naphthalene recovery step, raw material is taken full advantage of; And follow-up neutralization procedure only need add a small amount of alkali lye and get final product, and does not need to add in addition calcium hydroxide, thereby has save filter progress, has avoided precipitation and the entrainment loss of product.
The unreacted free naphthalene of described step (2) deviates from by interchanger to be cooled to 95 ℃ with the water vapor azeotropic, is cooled to 40 ℃ through slicing machine again, and the solid industrial naphthalene that obtains reclaims the preparation that is used for naphthalene water reducer.
Concrete, described method is as follows:
(1) NAPTHALENE FLAKES. (INDUSTRIAL GRADE） with molten state places sulphonation kettle, and in 120～140 ℃ of lower 98% vitriol oils that drip metering, sulfonation reaction is carried out in 160～165 ℃ of insulations after dropwising, and obtains the sulfonation material; Described naphthalene or its homologue are 1～1.5: 1 with the ratio of vitriol oil amount of substance;
(2) step (1) sulfonation material is changed over to hydrolysis and take off in the naphthalene still, be cooled to 120～160 ℃, pass into 120～160 ℃ of water vapour 45min～60min that is hydrolyzed, unreacted free naphthalene is deviate from the water vapour azeotropic, and residue is beta-naphthalenesulfonic-acid;
(3) step (2) beta-naphthalenesulfonic-acid changes condensation kettle over to, adding water regulation system acidity is 16～18, is cooled to 80～120 ℃ of formaldehyde that drip metering, is warming up to 90～135 ℃ after dropwising, regulating the still pressure is that 0～0.2MPa carries out condensation reaction 4h～6h, obtains the condensation material; Described beta-naphthalenesulfonic-acid is 1: 0.93～0.97 with the ratio of formaldehyde amount of substance;
(4) step (3) condensation material changes neutralising arrangement over to, it is 7.5～9.0 that 60～100 ℃ of lower adding liquid caustic soda carry out neutralization reaction to pH value, reaction finishes namely to get described liquid naphthalene water reducer, can obtain the high dense type naphthalene series high-efficiency water-reducing agent finished product of solid by further drying treatment.
Beneficial effect of the present invention is mainly reflected in:
(1) the inventive method has reduced feeding intake of invalid sulfuric acid, has avoided producing with the calcium hydroxide neutralization in the traditional technology link of waste residue, has reduced the factor that causes environmental pollution, has saved the environmental pollution treatment expense, has improved productivity effect and social benefit;
(2) the present invention utilizes steam hydrolysis to take off naphthalene, and excessive NAPTHALENE FLAKES. (INDUSTRIAL GRADE） complete recovery has reduced residual in product of NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, has improved resource utilization, has reduced raw materials cost.
(3) the closed operation is adopted in condensation reaction of the present invention, has avoided the volatilization of formaldehyde in the production process, thereby has improved production environment.
(4) description of drawings
Fig. 1 is technological process of production schematic diagram of the present invention.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
Shown in the technical process of Fig. 1, the production technique of high dense naphthalene water reducer comprises that mainly molten naphthalene, sulfonation reaction, steam hydrolysis take off the steps such as the recovery of naphthalene, naphthalene, condensation reaction, neutralization reaction.
Concrete grammar is as follows:
(1) fusing naphthalene.3000kg (23.4kmol) NAPTHALENE FLAKES. (INDUSTRIAL GRADE） concentrated in the melting kettle melts, 100 ℃ the liquid NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of molten state.
(2) sulfonation reaction.The liquid NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of above-mentioned steps (1) gained molten state is squeezed in the sulphonation kettle by volume pump, simultaneously 2000Kg 98% vitriol oil (20.4kmol) is squeezed into sulfuric acid high position tank (NAPTHALENE FLAKES. (INDUSTRIAL GRADE）: sulfuric acid mol ratio=1.15: 1), be warmed up to 140 ℃ in the still, in 30～45min, in the sulfonation reaction still, evenly drip the vitriol oil that measures, drip and finish to get the sulfonation material at 160 ℃～165 ℃ insulation sulfonation 3h.
(3) steam hydrolysis takes off naphthalene.Change the sulfonation material of above-mentioned steps (2) gained over to hydrolysis and take off the naphthalene still, be cooled to 145 ℃, pass into 145 ℃ high-temperature vapor in the still and be hydrolyzed and take off naphthalene, hydrolysis time is 45min～60min, and unreacted free NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is deviate from the water vapour azeotropic.Residue is beta-naphthalenesulfonic-acid (being the sulfonation material) in the still.
(4) recovery of naphthalene.With the unreacted free NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of deviating from the water vapour azeotropic in the above-mentioned steps (3), be cooled to liquid NAPTHALENE FLAKES. (INDUSTRIAL GRADE） about 95 ℃ through interchanger, be cooled to about 40 ℃ through slicing machine again, make NAPTHALENE FLAKES. (INDUSTRIAL GRADE） solidify section, cover is used for next batch production.
(5) condensation reaction:
The sulfonation material that above-mentioned steps (3) is residual changes condensation kettle over to, and adding water regulation system acidity is 18, and simultaneously 1540kg37% formaldehyde (19kmol) being squeezed into the formaldehyde header tank [is that mol ratio is beta-naphthalenesulfonic-acid: formaldehyde=1: 0.93.】。Cool to 90 ℃, drip formaldehyde in 45min～60min, off-response still emptying valve is warmed up to 115 ℃, guarantees still pressure＜0.2Mpa.Be incubated in 115～120 ℃ of scopes in front two hours, be incubated in 120～135 ℃ of scopes in rear three hours, be incubated altogether 5h, insulation finishes to get the condensation material,
(6) neutralization reaction:
After condensation reaction finishes, with above-mentioned steps (5) condensation material by transfering material pump turn expect in and still; Simultaneously, will be stored in alkali lye storage tank concentration by the alkali lye volume pump is during 30% liquid caustic soda 3300Kg pumps into and in the still, carries out neutralization reaction; Can by in the control and the pH value of still control liquid caustic soda volume pump flow to reach product P H value be 8.0, neutralization reaction finishes namely to get the high dense type naphthalene series high-efficiency water-reducing agent product of liquid, further drying obtains the dense type naphthalene water reducer finished product of solid height.
Embodiment 2:
With the 460Kg NAPTHALENE FLAKES. (INDUSTRIAL GRADE） that reclaims among 2560Kg NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and the embodiment 1,37% formaldehyde consumption in the step (5) changes 1550Kg into, the high dense type naphthalene series high-efficiency water-reducing agent finished product of liquid that step (6) finishes gained with neutralization reaction directly advances to spray the tower spraying drying and obtains the high dense type naphthalene series high-efficiency water-reducing agent finished product of solid, and other steps are all constant.
(1) fusing naphthalene
Concentrate in the melting kettle with NAPTHALENE FLAKES. (INDUSTRIAL GRADE） 2560kg with according to the naphthalene 460kg that the described method of example 1 reclaims and to melt, 100 ℃ the liquid NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (23.6kmol) of molten state;
(2) sulfonation reaction:
The liquid NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of above-mentioned steps (1) gained molten state is squeezed in the sulphonation kettle by volume pump, NAPTHALENE FLAKES. (INDUSTRIAL GRADE） in molar ratio simultaneously: the ratio of sulfuric acid=1.3: 1 is squeezed into sulfuric acid high position tank to 98% vitriol oil, be warmed up to 145 ℃ in the still, in 45min, in the sulfonation reaction still, evenly drip the vitriol oil that measures, drip and finish to get the sulfonation material at 160 ℃～165 ℃ insulation sulfonation 3h;
(3) steam hydrolysis takes off naphthalene:
Change the sulfonation material of above-mentioned steps (2) gained over to hydrolysis and take off the naphthalene still, be cooled to 155 ℃, pass into 155 ℃ high-temperature vapor in the still and be hydrolyzed and take off naphthalene, hydrolysis time is 45min～60min, and unreacted free NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is deviate from the water vapour azeotropic.Residue is beta-naphthalenesulfonic-acid (both sulfonation material) in the still;
(4) recovery of naphthalene:
The unreacted free NAPTHALENE FLAKES. (INDUSTRIAL GRADE） that above-mentioned steps (3) is deviate from the water vapour azeotropic is cooled to liquid NAPTHALENE FLAKES. (INDUSTRIAL GRADE） about 95 ℃ through interchanger, be cooled to about 50 ℃ through slicing machine again, make NAPTHALENE FLAKES. (INDUSTRIAL GRADE） solidify section, recovery is in next batch production after the dehydration of NAPTHALENE FLAKES. (INDUSTRIAL GRADE） process.
(5) condensation reaction:
The sulfonation material that above-mentioned steps (3) is residual changes condensation kettle over to, adds suitable water take regulation system acidity as 18.Be in molar ratio simultaneously beta-naphthalenesulfonic-acid: 1: 0.93 ratio formaldehyde of formaldehyde=enters the formaldehyde header tank.Cool to 85 ℃, drip formaldehyde in 45min～60min, off-response still emptying valve is warmed up to 110 ℃, guarantees still pressure＜0.2Mpa.Be incubated in 110～115 ℃ of scopes in front two hours, be incubated in 115～125 ℃ of scopes in rear three hours, be incubated altogether 5h, insulation finishes to get the condensation material,
(6) neutralization reaction:
After condensation reaction finishes, with above-mentioned steps (5) condensation material transfering material pump turn expect in and still; Simultaneously, during the liquid caustic soda that will be stored in the alkali lye storage tank by the alkali lye volume pump pumps into and in the still, carry out neutralization reaction to pH value 7.5, neutralization reaction finishes namely to get the high dense type naphthalene series high-efficiency water-reducing agent finished product of liquid, directly advances to spray the tower spraying drying and gets the high dense type naphthalene series high-efficiency water-reducing agent finished product of solid
Embodiment 3 (Comparative Examples):
In molten 2400Kg (18.75kmol) NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of molten naphthalene still, the liquid NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of molten state is squeezed in the sulphonation kettle, add 2659Kg (26.59kmol) vitriol oil and carry out sulfonation (naphthalene: the vitriol oil=1: 1.4) at 120～160 ℃, about sulfonation 3 hours, squeeze into hydrolysis kettle and be cooled to 120 ℃, add the 1100Kg tap water reaction 45～60min that is hydrolyzed in the still, hydrolysis finishes cooling and squeezes into condensation kettle, the formaldehyde 1400Kg (17.27kmol) of dropping 37% carries out condensation reaction about 80 ℃, drip and finish in condensation reaction more than 100 ℃ about 5～6 hours, drop into calcium hydroxide 525Kg with still in squeezing into after the cooling stirred one hour in batches, adding 3000Kg liquid sodium hydroxide (concentration 30%) accent Ph value is 7.5～9 again, remove after filtration approximately 1300Kg of calcium sulfate filter residue, namely get the liquid naphthalene series high-efficiency water-reducing agent.
Embodiment 4:
By embodiment 1～3 prepared naphthalene series high-efficiency water-reducing agent, according to GB/T8077-2000 to the water reducer of gained carry out sodium sulphate content, volume 0.4% the time flowing degree of net paste of cement and mortar in the water-reducing rate test of volume when being 0.6%, according to GB8076-1997 the water reducer of gained is carried out the concrete crushing strength test, measuring result such as table 1:
Table 1
Conclusion: from above-described embodiment and detected result as can be known, among the dense naphthalene water reducer preparation method of height of the present invention, at a large amount of sulphuric acids that reduce, when not producing calcium sulfate waste residues, the product quality indicator value does not only descend, even exceeds the quality index value of former traditional technology products obtained therefrom.
Claims (3)
1. the preparation method of a naphthalene water reducer, described method comprises:
(1) naphthalene or its homologue with molten state places xanthator, and in 120～140 ℃ of lower 98% vitriol oils that drip metering, sulfonation reaction is carried out in 160～165 ℃ of insulations after dropwising, and obtains the sulfonation material; Described naphthalene or its homologue are 1～2: 1 with the ratio of vitriol oil amount of substance;
(2) step (1) sulfonation material is changed over to hydrolysis and take off in the naphthalene device, be cooled to 120～160 ℃, pass into 120～160 ℃ of water vapour and be hydrolyzed, unreacted free naphthalene is deviate from the water vapour azeotropic, and residue is beta-naphthalenesulfonic-acid;
(3) step (2) beta-naphthalenesulfonic-acid changes the condensation device over to, and adding water regulation system acidity is 16～18, is cooled to 80～120 ℃ of formaldehyde that drip metering, is warming up to 90～135 ℃ after dropwising, and carries out condensation reaction under 0～0.2MPa, obtains the condensation material; Described beta-naphthalenesulfonic-acid is 1: 0.9～1.1 with the ratio of formaldehyde amount of substance;
(4) step (3) condensation material changes neutralising arrangement over to, and it is 7.5～9.0 that 60～100 ℃ of lower adding alkali lye carry out neutralization reaction to pH value, and reaction finishes namely to get described naphthalene water reducer; Described alkali lye is sodium hydroxide solution, sodium hydrogen carbonate solution or sodium carbonate solution.
2. the method for claim 1, it is characterized in that the unreacted free naphthalene of described step (2) deviates from by interchanger to be cooled to 95 ℃ with the water vapor azeotropic, be cooled to 40 ℃ through slicing machine again, the solid industrial naphthalene that obtains reclaims the preparation that is used for naphthalene water reducer.
3. the method for claim 1 is characterized in that described method is as follows:
(1) NAPTHALENE FLAKES. (INDUSTRIAL GRADE） with molten state places sulphonation kettle, and in 120～140 ℃ of lower 98% vitriol oils that drip metering, sulfonation reaction is carried out in 160～165 ℃ of insulations after dropwising, and obtains the sulfonation material; Described NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is 1～1.5: 1 with the ratio of vitriol oil amount of substance;
(2) step (1) sulfonation material is changed over to hydrolysis and take off in the naphthalene still, be cooled to 120～160 ℃, pass into 120～160 ℃ of water vapour 45min～60min that is hydrolyzed, unreacted free naphthalene is deviate from the water vapour azeotropic, and residue is beta-naphthalenesulfonic-acid;
(3) step (2) beta-naphthalenesulfonic-acid changes condensation kettle over to, adding water regulation system acidity is 16～18, is cooled to 80～120 ℃ of formaldehyde that drip metering, is warming up to 90～135 ℃ after dropwising, regulating the still pressure is that 0～0.2MPa carries out condensation reaction 4h～6h, obtains the condensation material; Described beta-naphthalenesulfonic-acid is 1: 0.93～0.97 with the ratio of formaldehyde amount of substance;
(4) step (3) condensation material changes neutralising arrangement over to, and it is 7.5～9.0 that 60～100 ℃ of lower adding alkali lye carry out neutralization reaction to pH value, and reaction finishes namely to get described naphthalene water reducer.
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