CN102464464B - Preparation method of naphthalene series water reducer - Google Patents
Preparation method of naphthalene series water reducer Download PDFInfo
- Publication number
- CN102464464B CN102464464B CN201010537832.9A CN201010537832A CN102464464B CN 102464464 B CN102464464 B CN 102464464B CN 201010537832 A CN201010537832 A CN 201010537832A CN 102464464 B CN102464464 B CN 102464464B
- Authority
- CN
- China
- Prior art keywords
- naphthalene
- sulfonation
- homologue
- reaction
- condensation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 150000002790 naphthalenes Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 139
- 239000000463 material Substances 0.000 claims abstract description 38
- 230000005494 condensation Effects 0.000 claims abstract description 28
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 19
- 238000006482 condensation reaction Methods 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 17
- 238000006277 sulfonation reaction Methods 0.000 claims description 77
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000009833 condensation Methods 0.000 claims description 26
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 16
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 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
- 239000000126 substance Substances 0.000 claims description 3
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing 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
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000011084 recovery Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical group C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- RRDQTXGFURAKDI-UHFFFAOYSA-N formaldehyde;naphthalene-2-sulfonic acid Chemical compound O=C.C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 RRDQTXGFURAKDI-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Abstract
The invention provides a production method of a low-cost light-color naphthalene series water reducer. According to the invention, a naphthalene homologue replaces part of naphthalene and is used as a sulfonated raw material. Naphthalene and the naphthalene homologue are respectively sulfonated; and the sulfonated materials are mixed for subsequent condensation, hydrolysis and neutralization reactions. By the adoption of the technology, the raw material cost of the naphthalene series high-efficiency water reducer can be reduced. In addition, the product is light in color and is especially applicable to be used as a concrete water reducer and a naphthalene series water reducer.
Description
(1) technical field
The production method of the light naphthalene water reducer of a kind of low cost.
(2) background technology
Naphthalene water reducer is the water reducer kind that domestic consumption is maximum.The production technique of general naphthalene water reducer is to use NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and sulfuric acid to carry out sulfonation reaction, and then carries out condensation reaction generation beta-naphthalenesulfonic-acid formaldehyde condensation compound with formaldehyde, and last and liquid caustic soda carries out neutralization reaction and generates corresponding naphthalene water reducer.NAPTHALENE FLAKES. (INDUSTRIAL GRADE） holds at high price in recent years, add the market competition of water reducer industry fierceness, make water reducer manufacturer start progressively improvement of production process, reduce costs, the most general way is to use cheap naphthalene homologue to substitute NAPTHALENE FLAKES. (INDUSTRIAL GRADE） at present, as methylnaphthalene, naphtalene oil, washing oil, crude anthracene etc., Hu Xianghong etc. < < take NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and thick methylnaphthalene as main raw material in synthetic naphthalene series high-efficiency water-reducing agent > > by the mixture of the NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of certain proportioning and methylnaphthalene and vitriol oil generation sulfonation reaction, finally obtain naphthalene water reducer.But use the most colors of the resulting naphthalene water reducer of naphthalene and homologue mixing sulfonation thereof burned black, and second-rate, be difficult to meet client's requirement.
(3) summary of the invention
For reducing the production cost of naphthalene series high-efficiency water-reducing agent, keep even improving the quality of water reducer simultaneously, the invention provides a kind of production technique of light naphthalene series high-efficiency water-reducing agent.
The technical solution used in the present invention is:
A preparation method for naphthalene water reducer, described method comprises:
(1) naphthalene of molten state and naphthalene homologue are placed in respectively to different xanthators, add respectively the vitriol oil or oleum, in 140～170 ℃ of insulations, carry out sulfonation reaction, obtain sulfonation material; The mass ratio of described naphthalene and naphthalene homologue is 1～10: 1; The mass ratio of described naphthalene or its homologue and the vitriol oil is independently respectively 1: 1～1.5; Described naphthalene homologue is from one of following: naphtalene oil, carbolineum, washing oil, acenaphthene, methylnaphthalene;
(2) step (1) sulfonation material is mixed, proceed in the de-naphthalene device of hydrolysis, be cooled to 120～160 ℃, pass into 120～160 ℃ of water vapour and be hydrolyzed, unreacted naphthalene and naphthalene homologue are deviate from water vapour azeotropic, and residual sulfonated bodies carries out next step reaction; The material that azeotropic is deviate from is cooled to below 100 ℃ through interchanger, feed liquid layering, and lower floor's naphthalene and homologue thereof are pressed into raw materials recovery groove, can be used for next batch and produce;
(3) step (2) sulfonated bodies proceeds to condensation device, adding water regulation system acidity (acidity refers to the percentage concentration of sulfuric acid in reaction system) is herein 18～24%, be cooled to 80～120 ℃ of formaldehyde that drip metering, after dropwising, be warming up at 90～135 ℃ and carry out condensation reaction, obtain condensation material; Described sulfonated bodies is 1: 0.9～1.1 with the ratio of formaldehyde amount of substance;
(4) step (3) condensation material proceeds to neutralising arrangement, at 60～100 ℃, adding alkali lye to carry out neutralization reaction to pH value is 7.5～9.0, reaction finishes and obtains described liquid naphthalene water reducer, by further drying treatment, obtains the high dense type naphthalene series high-efficiency water-reducing agent finished product of solid; Described alkali lye is sodium hydroxide solution, sodium hydrogen carbonate solution or sodium carbonate solution.
Use naphthalene homologue to replace part naphthalene as sulfonation raw material, and respectively naphthalene, naphthalene homologue are carried out to sulfonation, then will after sulfonation mixing of materials, carry out follow-up condensation, hydrolysis and neutralization reaction.By this technique, not only can reduce the raw materials cost of naphthalene series high-efficiency water-reducing agent, and product look light, being particularly useful as cement water reducing agent and naphthalene is that dispersion agent is used.
Preferably, described step (1) sulfonation reaction temperature is 150～165 ℃, 1～2 hour time.
Preferably, in described step (1), the mass ratio of naphthalene and naphthalene homologue is 2～5: 1.
The production method of naphthalene series high-efficiency water-reducing agent of the present invention, compared to the conventional technique by the alternative NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of naphthalene homologue, its beneficial effect is mainly reflected in:
(1) NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and its homologue respectively after sulfonation remix carry out the operations such as condensation, neutralization, the product look obtaining is light, and effect is good;
(2) homologue product price is cheap, replaces the amount of NAPTHALENE FLAKES. (INDUSTRIAL GRADE） more, and water reducer cost is just lower;
(3) homologue sulfonation temperature is low compared with NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, and the sulfonation time is short, has both saved energy consumption, can avoid again producing a large amount of many sulfonated bodiess, and product colour is shoaled;
(4) utilize water vapour to take off naphthalene, then carry out recovery, reduced residual in product of naphthalene, improved resource utilization, reduced raw materials cost.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1:
Sulfonation reaction:
Take respectively NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (naphthalene content is 95%) 2000kg, 98% vitriol oil 2300kg, 1. NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is dropped into sulfonation reaction still, be warming up to 140 ℃, in 45 minutes, to sulfonation reaction still, evenly add the vitriol oil, reinforced 165 ℃～170 ℃ sulfonation reactions of finishing control temperature 2 hours, the sulfonation NAPTHALENE FLAKES. (INDUSTRIAL GRADE） obtaining is standby.
Take respectively carbolineum 400kg, 2. 98% vitriol oil 450kg, drop into sulfonation reaction still by carbolineum, be warming up to 140 ℃, in 30 minutes, to sulfonation reaction still, evenly add the vitriol oil, reinforced 150～155 ℃ of sulfonation reactions of finishing control temperature 1.5 hours, the sulfonated naphthalene homologue obtaining is standby.
The de-naphthalene of hydrolysis:
Above-mentioned sulfonation NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and sulfonated naphthalene homologue are squeezed into condensation reaction still simultaneously, compound is cooled to 120～160 ℃, to the high-temperature water vapor that passes into 120～160 ℃ in the still de-naphthalene that is hydrolyzed, hydrolysis time is 45～60min, unreacted free naphthalene and homologue thereof are deviate from water vapor azeotropic, through interchanger, be cooled to 95 ℃ of left and right layering ，Jiang lower floor naphthalenes and homologue is pressed into raw materials recovery groove, by the number of its naphthalene content, for next batch, produce.
Condensation reaction:
Sulfonation material after above-mentioned de-naphthalene, adding water regulation system acidity is 20～22%, is cooled to 100 ℃, in 45～60 minutes, add 37% formaldehyde solution, the mol ratio of controlling formaldehyde and sulfonation compound is 1: 0.9～1,95～105 ℃ of insulation condensations of temperature 5 hours, and the condensation material obtaining is standby.
Neutralization reaction:
By above-mentioned condensation material by transfering material pump turn expect in and still, add 30% the NaOH aqueous solution, at 80～90 ℃, carry out neutralization reaction, adjusting pH value is 7～8, obtain the high dense type naphthalene series high-efficiency water-reducing agent of liquid, by further drying treatment, can obtain the high dense naphthalene series high-efficiency water-reducing agent finished product of solid.
Embodiment 2:
Sulfonation reaction:
Take respectively NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (naphthalene content is 95%) 1650kg, 98% vitriol oil 1780kg, 1. NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is dropped into sulfonation reaction still, be warming up to 150 ℃, in 30 minutes, to sulfonation reaction still, evenly add the vitriol oil, reinforced 165 ℃ of sulfonation reactions of finishing control temperature 1.5 hours, the sulfonation NAPTHALENE FLAKES. (INDUSTRIAL GRADE） obtaining is standby.
Take respectively washing oil 750kg, 2. 98% vitriol oil 950kg, drop into sulfonation reaction still by washing oil, be warming up to 130 ℃, in 30 minutes, to sulfonation reaction still, evenly add the vitriol oil, reinforced 155 ℃ of sulfonation reactions of finishing control temperature 1.5 hours, the sulfonated naphthalene homologue obtaining is standby.
The de-naphthalene of hydrolysis:
Above-mentioned sulfonation NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and sulfonated naphthalene homologue are squeezed into condensation reaction still simultaneously, compound is cooled to 125 ℃, to the high-temperature water vapor that passes into 155 ℃ in the still de-naphthalene that is hydrolyzed, hydrolysis time is 45min, unreacted free naphthalene and homologue thereof are deviate from water vapor azeotropic, through interchanger, be cooled to 95 ℃ of left and right layering ，Jiang lower floor naphthalenes and homologue is pressed into raw materials recovery groove, the number of naphthalene content is produced for next batch on schedule.
Condensation reaction:
Sulfonation material after above-mentioned de-naphthalene, adding water regulation system acidity is 21%, is cooled to 100 ℃, in 45～60 minutes, add 37% formaldehyde solution, the mol ratio of controlling formaldehyde and sulfonation compound is 1: 0.98,110 ℃ of insulation condensations of temperature 4.5 hours, and the condensation material obtaining is standby.
Neutralization reaction:
By above-mentioned condensation material by transfering material pump turn expect in and still, add 30% the NaOH aqueous solution, at 90 ℃, carry out neutralization reaction, adjusting pH value is 7～8, obtain the high dense type naphthalene series high-efficiency water-reducing agent of liquid, by further drying treatment, can obtain the high dense naphthalene series high-efficiency water-reducing agent finished product of solid.
Embodiment 3:
Sulfonation reaction:
Take respectively NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (naphthalene content is 92%) 1700kg, 98% vitriol oil 1850kg, 1. NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is dropped into sulfonation reaction still, be warming up to 150 ℃, in 30 minutes, to sulfonation reaction still, evenly add the vitriol oil, reinforced 165 ℃ of sulfonation reactions of finishing control temperature 1.5 hours, the sulfonation NAPTHALENE FLAKES. (INDUSTRIAL GRADE） obtaining is standby.
Take respectively industrial acenaphthylene 700kg, 2. 98% vitriol oil 800kg, drop into sulfonation reaction still by industrial acenaphthylene, be warming up to 140 ℃, in 30 minutes, to sulfonation reaction still, evenly add the vitriol oil, reinforced 150 ℃ of sulfonation reactions of finishing control temperature 1.5 hours, the sulfonated naphthalene homologue obtaining is standby.
The de-naphthalene of hydrolysis:
Above-mentioned sulfonation NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and sulfonated naphthalene homologue are squeezed into condensation reaction still simultaneously, compound is cooled to 120 ℃, to the high-temperature water vapor that passes into 155 ℃ in the still de-naphthalene that is hydrolyzed, hydrolysis time is 45min, unreacted free naphthalene and homologue thereof are deviate from water vapor azeotropic, through interchanger, be cooled to 90 ℃ of left and right layering ，Jiang lower floor naphthalenes and homologue is pressed into raw materials recovery groove, the number of naphthalene content is produced for next batch on schedule.
Condensation reaction:
Sulfonation material after above-mentioned de-naphthalene, adding water regulation system acidity is 21%, is cooled to 110 ℃, in 45 minutes, add 37% formaldehyde solution, the mol ratio of controlling formaldehyde and sulfonation compound is 1: 0.95,110 ℃ of insulation condensations of temperature 5 hours, and the condensation material obtaining is standby.
Neutralization reaction:
By above-mentioned condensation material by transfering material pump turn expect in and still, add 30% the NaOH aqueous solution, at 90 ℃, carry out neutralization reaction, adjusting pH value is 7～8, obtain the high dense type naphthalene series high-efficiency water-reducing agent of liquid, by further drying treatment, can obtain the high dense naphthalene series high-efficiency water-reducing agent finished product of solid.
Embodiment 4:
Sulfonation reaction:
Take respectively NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (naphthalene content is 87%) 1800kg, 98% vitriol oil 1960kg, 1. NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is dropped into sulfonation reaction still, be warming up to 140 ℃, in 45min, to sulfonation reaction still, evenly add the vitriol oil, reinforced 165 ℃ of sulfonation reactions of finishing control temperature 1.5 hours, the sulfonation NAPTHALENE FLAKES. (INDUSTRIAL GRADE） obtaining is standby.
Take respectively methylnaphthalene 600kg, 2. 98% vitriol oil 740kg, drop into sulfonation reaction still by methylnaphthalene, be warming up to 140 ℃, in 30 minutes, to sulfonation reaction still, evenly add the vitriol oil, reinforced 150 ℃ of sulfonation reactions of finishing control temperature 1.5 hours, the sulfonated naphthalene homologue obtaining is standby.
The de-naphthalene of hydrolysis:
Above-mentioned sulfonation NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and sulfonated naphthalene homologue are squeezed into condensation reaction still simultaneously, compound is cooled to 120 ℃, to the high-temperature water vapor that passes into 155 ℃ in the still de-naphthalene that is hydrolyzed, hydrolysis time is 45min, unreacted free naphthalene and homologue thereof are deviate from water vapor azeotropic, through interchanger, be cooled to 90 ℃ of left and right layering ，Jiang lower floor naphthalenes and homologue is pressed into raw materials recovery groove, the number of naphthalene content is produced for next batch on schedule.
Condensation reaction:
Sulfonation material after above-mentioned de-naphthalene, adding water regulation system acidity is 22%, is cooled to 110 ℃, in 45 minutes, add 37% formaldehyde solution, the mol ratio of controlling formaldehyde and sulfonation compound is 1: 0.95,110 ℃ of insulation condensations of temperature 5 hours, and the condensation material obtaining is standby.
Neutralization reaction:
By above-mentioned condensation material by transfering material pump turn expect in and still, add 30% the NaOH aqueous solution, at 90 ℃, carry out neutralization reaction, adjusting pH value is 7～8, obtain the high dense type naphthalene series high-efficiency water-reducing agent of liquid, by further drying treatment, can obtain the high dense naphthalene series high-efficiency water-reducing agent finished product of solid.
Comparative example 1:
Sulfonation reaction:
Take respectively methylnaphthalene 600kg, the NAPTHALENE FLAKES. (INDUSTRIAL GRADE） 1800kg of content 87%, drops into sulfonation reaction still, be warming up to 140 ℃, in 30min, to sulfonation reaction still, evenly add 98% vitriol oil 2700kg, reinforced 165 ℃ of sulfonation reactions of finishing control temperature 1.5 hours, the mixing sulfonation naphthalene series substance obtaining is standby.
The de-naphthalene of hydrolysis:
Above-mentioned sulfonation NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and sulfonated naphthalene homologue are squeezed into condensation reaction still simultaneously, compound is cooled to 120 ℃, and to the high-temperature water vapor that passes into 155 ℃ in the still de-naphthalene that is hydrolyzed, hydrolysis time is 45min, unreacted free naphthalene and homologue thereof are deviate from water vapor azeotropic, recycle.
Condensation reaction:
Sulfonation material after above-mentioned de-naphthalene, adding water regulation system acidity is 22%, is cooled to 110 ℃, in 45 minutes, add 37% formaldehyde solution, the mol ratio of controlling formaldehyde and sulfonation compound is 1: 0.95,110 ℃ of insulation condensations of temperature 5 hours, and the condensation material obtaining is standby.
Neutralization reaction:
By above-mentioned condensation material by transfering material pump turn expect in and still, add 30% the NaOH aqueous solution, at 90 ℃, carry out neutralization reaction, adjusting pH value is 7～8, obtain the high dense type naphthalene series high-efficiency water-reducing agent of liquid, by further drying treatment, can obtain the high dense naphthalene series high-efficiency water-reducing agent finished product of solid.
Comparative example 2:
Sulfonation reaction:
3000kg (23.4kmol) NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is concentrated in melting kettle and melted, 100 ℃ of liquid NAPTHALENE FLAKES. (INDUSTRIAL GRADE） that obtain molten state, by volume pump, squeeze in sulphonation kettle, 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) simultaneously, in still, be warmed up to 140 ℃, in 30～45min, in sulfonation reaction still, evenly drip the vitriol oil measuring, drip and finish, at 160 ℃～165 ℃ insulation sulfonation 3h, to obtain sulfonation material.
Steam hydrolysis takes off naphthalene:
The sulfonation material of above-mentioned gained is proceeded to the de-naphthalene still of hydrolysis, be cooled to 145 ℃, to the high-temperature vapor that passes into 145 ℃ in the still de-naphthalene that is hydrolyzed, hydrolysis time is 45min～60min, and unreacted free NAPTHALENE FLAKES. (INDUSTRIAL GRADE） is deviate from water vapour azeotropic.In still, residue is beta-naphthalenesulfonic-acid (being sulfonation material).
Condensation reaction:
Above-mentioned residual sulfonation material is proceeded to condensation kettle, and adding water regulation system acidity is 18, and 1540kg37% formaldehyde (19kmol) is squeezed into formaldehyde header tank [is that mol ratio is beta-naphthalenesulfonic-acid: formaldehyde=1: 0.93 simultaneously.】。Cool to 90 ℃, drip formaldehyde in 45min～60min, off-response still emptying valve, is warmed up to 115 ℃, guarantees still pressure < 0.2Mpa.Within first two hours, within the scope of 115～120 ℃, be incubated, within latter three hours, within the scope of 120～135 ℃, be incubated, be incubated altogether 5h, insulation finishes to obtain condensation material,
Neutralization reaction:
After condensation reaction finishes, by above-mentioned condensation material by transfering material pump turn expect in and still; Meanwhile, by alkali lye volume pump by be stored in liquid caustic soda 3300Kg that alkali lye storage tank concentration is 30% pump in and in still, carry out neutralization reaction; Can by controlling 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 and obtains the high dense type naphthalene series high-efficiency water-reducing agent product of liquid, the further dry dense type naphthalene water reducer finished product of solid height that obtains.
Application Example:
The high efficiency water reducing agent standard that water reducer (comparative example 1) prepared by prepared water reducer, naphthalene and the naphthalene homologue mixing sulfonation of embodiment 1～4 and the NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of all take are prepared as raw material (comparative example 2), according to GB/T8077 < < Methods for testing uniformity of concrete admixture > >, carry out comparison and detection, the results are shown in Table 1.Note: detecting cement is Dongguan, Shangyu conch cement R42.5.
Table 1
As shown in Table 1, adopt the production method of naphthalene series high-efficiency water-reducing agent of the present invention, resulting product homogeneity is better, basic suitable with the product performance of all using NAPTHALENE FLAKES. (INDUSTRIAL GRADE） (comparative example 2) to obtain for raw material, and products obtained therefrom look shallow, effectively improved and take NAPTHALENE FLAKES. (INDUSTRIAL GRADE） as raw material or take the product color that NAPTHALENE FLAKES. (INDUSTRIAL GRADE） and homologue thereof be raw material mixing process for sulfonation.
Claims (1)
1. a preparation method for naphthalene water reducer, described method comprises:
(1) naphthalene of molten state and naphthalene homologue are placed in respectively to different xanthators, add respectively the vitriol oil or oleum, in 150～165 ℃ of insulations, carry out sulfonation reaction 1～2 hour, obtain sulfonation material; The mass ratio of described naphthalene and naphthalene homologue is 2～5:1; The mass ratio of described naphthalene or its homologue and the vitriol oil is independent is respectively 1:1～1.5; Described naphthalene homologue is from one of following: naphtalene oil, carbolineum, washing oil, acenaphthene, methylnaphthalene;
(2) step (1) sulfonation material is mixed, proceed in the de-naphthalene device of hydrolysis, be cooled to 120～160 ℃, pass into 120～160 ℃ of water vapour and be hydrolyzed, unreacted naphthalene and naphthalene homologue are deviate from water vapour azeotropic, and residual sulfonated bodies carries out next step reaction;
(3) step (2) sulfonated bodies proceeds to condensation device, and adding water regulation system acidity is 18～24%, is cooled to 80～120 ℃ of formaldehyde that drip metering, is warming up at 90～135 ℃ and carries out condensation reaction after dropwising, and obtains condensation material; Described sulfonated bodies is 1:0.9～1.1 with the ratio of formaldehyde amount of substance;
(4) step (3) condensation material proceeds to neutralising arrangement, at 60～100 ℃, adding alkali lye to carry out neutralization reaction to pH value is 7.5～9.0, reaction finishes and obtains described liquid naphthalene water reducer, by further drying treatment, obtains the high dense type naphthalene series high-efficiency water-reducing agent finished product of solid; Described alkali lye is sodium hydroxide solution, sodium hydrogen carbonate solution or sodium carbonate solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010537832.9A CN102464464B (en) | 2010-11-09 | 2010-11-09 | Preparation method of naphthalene series water reducer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010537832.9A CN102464464B (en) | 2010-11-09 | 2010-11-09 | Preparation method of naphthalene series water reducer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102464464A CN102464464A (en) | 2012-05-23 |
| CN102464464B true CN102464464B (en) | 2014-03-12 |
Family
ID=46068631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010537832.9A Active CN102464464B (en) | 2010-11-09 | 2010-11-09 | Preparation method of naphthalene series water reducer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102464464B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951310A (en) * | 2013-12-28 | 2014-07-30 | 福清市永春混凝土外加剂有限公司 | Modified naphthalene-series water reducer and preparation method thereof |
| CN104497250A (en) * | 2014-12-19 | 2015-04-08 | 河南奥思达新材料有限公司 | Method for producing high-concentration efficient naphthalene water reducer by virtue of binary azeotropic method |
| CN105801786B (en) * | 2016-03-10 | 2019-03-01 | 安徽鑫固环保股份有限公司 | A kind of low cost is high to protect the modified naphthalene superplasticizer and preparation method thereof to collapse |
| CN106082756B (en) * | 2016-06-24 | 2018-01-09 | 山东省莱芜市汶河化工有限公司 | A kind of solvent method concentrates the production system of sulfonation separate mealing type condensation production naphthalene water reducer |
| CN106632938B (en) * | 2016-09-20 | 2019-01-01 | 江苏苏博特新材料股份有限公司 | A kind of energy saving preparation method and its special equipment of naphthalene water reducer |
| CN107522637A (en) * | 2017-08-31 | 2017-12-29 | 浙江吉盛化学建材有限公司 | A kind of production technology of Dispersant MF |
| CN108084383A (en) * | 2017-12-19 | 2018-05-29 | 萧县沃德化工科技有限公司 | A kind of high efficiency water reducing agent and preparation method thereof |
| CN111423551A (en) * | 2020-04-01 | 2020-07-17 | 山东汶河新材料有限公司 | System for producing high-concentration naphthalene water reducer by naphthalene excess method and production method thereof |
| CN112125564B (en) * | 2020-06-15 | 2022-10-04 | 安徽鑫固环保股份有限公司 | Naphthalene water reducer |
| CN113041820A (en) * | 2021-03-12 | 2021-06-29 | 广东科隆智谷新材料股份有限公司 | Method for treating sulfonated tail gas generated in production of water reducing agent from naphthalene |
| CN114106893A (en) * | 2021-12-24 | 2022-03-01 | 莱芜市兆信新材料股份有限公司 | Preparation method of naphthalene water reducer for coal water slurry |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355148A (en) * | 2000-11-24 | 2002-06-26 | 周效懿 | Naphthalene-series water-reducing strengthening agent for concrete and its preparing process |
| CN101863635A (en) * | 2010-04-13 | 2010-10-20 | 宫振鑫 | New process formula for producing naphthalene series water reducer of concrete admixture |
-
2010
- 2010-11-09 CN CN201010537832.9A patent/CN102464464B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102464464A (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102464464B (en) | Preparation method of naphthalene series water reducer | |
| CN101723860B (en) | Method for preparing naphthalene series water reducing agent | |
| CN101386587B (en) | Production technology of methyl naphthalenesulfonic acid-methyl aldehyde condensation compound | |
| CN105236798B (en) | A kind of preparation method of naphthalene water reducer | |
| CN101956030B (en) | Method for preparing succinic acid sulphonated fat-liquoring agent | |
| CN103964731B (en) | A kind of polycarboxylate water-reducer and preparation method thereof | |
| CN101376639A (en) | Method for coproduction of dispersants MF and sodium sulphite | |
| CN103242205B (en) | Tri-monomer preparation method capable of reducing waste water production | |
| CN105712906A (en) | Method for preparing high-quality dispersing agent MF with reactive distillation method | |
| CN100497304C (en) | Method of synthesizing sulfonation paraposition ester | |
| CN101898926A (en) | Sulfonation process for producing dye dispersant and concrete water reducing agent | |
| CN102114396A (en) | Non-quinoline dispersant MF and production process | |
| CN101125867A (en) | Method for preparing lignin sodium sulfonate by using sulphonation waste gas | |
| CN109942396A (en) | The Preparation Method of lanthanum acetylacetone | |
| CN106810412B (en) | Method for improving sulfonation reaction efficiency and production method of dispersing agent MF | |
| CN105669926A (en) | Preparation method of high-content naphthalene water reducer | |
| CN102372620B (en) | Magnesium Stearate improves the preparation method of its specific volume and whiteness | |
| CN102372456A (en) | Method for preparing naphthalene series additive from low-acidity process waste water | |
| CN105541672B (en) | A kind of process for cleanly preparing of dye dispersant MF | |
| CN100494138C (en) | Industrialized method for preparing resorcin | |
| CN111004362B (en) | Preparation method of naphthalene-based superplasticizer | |
| CN103011665A (en) | Aliphat water reducer and naphthalene water reducer chemical compound process | |
| CN109534712B (en) | Light yellow naphthalene water reducing agent and preparation method thereof | |
| CN104327535A (en) | Preparation method of acid black 172 | |
| CN108003070B (en) | Sulfonation method in H acid production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160811 Address after: 312368 Zhejiang city of Shaoxing province Shangyu City Road Town Patentee after: Zhejiang Longsheng Group Co., Ltd. Patentee after: Zhejiang Jisheng Chemical Building Materials Co.,Ltd. Address before: 312368 Zhejiang city of Shaoxing province Shangyu City Road Town Patentee before: Zhejiang Longsheng Group Co., Ltd. Patentee before: Shangyu Jilong Chemical Building Materials Co.,Ltd. Patentee before: Zhejiang Jisheng Chemical Building Materials Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201104 Address after: 321369 Weisan Road, Shangyu economic and Technological Development Zone, Hangzhou Bay, Shaoxing City, Zhejiang Province Patentee after: ZHEJIANG JISHENG CHEMICAL BUILDING MATERIALS Co.,Ltd. Address before: 312368 Zhejiang city of Shaoxing province Shangyu City Road Town Patentee before: ZHEJIANG LONGSHENG GROUP Co.,Ltd. Patentee before: ZHEJIANG JISHENG CHEMICAL BUILDING MATERIALS Co.,Ltd. |