CN105236798B - A kind of preparation method of naphthalene water reducer - Google Patents
A kind of preparation method of naphthalene water reducer Download PDFInfo
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- CN105236798B CN105236798B CN201410831025.6A CN201410831025A CN105236798B CN 105236798 B CN105236798 B CN 105236798B CN 201410831025 A CN201410831025 A CN 201410831025A CN 105236798 B CN105236798 B CN 105236798B
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- naphthalene
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- sulfuric acid
- water reducer
- methyl naphthalene
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 58
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000000463 material Substances 0.000 claims abstract description 83
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 77
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000009833 condensation Methods 0.000 claims abstract description 23
- 230000005494 condensation Effects 0.000 claims abstract description 23
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 21
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- 238000010792 warming Methods 0.000 claims description 22
- 229960003742 phenol Drugs 0.000 claims description 17
- 238000009413 insulation Methods 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000013517 stratification Methods 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 208000011580 syndromic disease Diseases 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims 2
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 15
- 239000004568 cement Substances 0.000 abstract description 9
- 238000006482 condensation reaction Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 230000003467 diminishing effect Effects 0.000 description 4
- 229940061610 sulfonated phenol Drugs 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920003266 Leaf® Polymers 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- FNBBNRGOHBQXCM-UHFFFAOYSA-N [S].OC1=CC=CC=C1 Chemical compound [S].OC1=CC=CC=C1 FNBBNRGOHBQXCM-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229960003666 liquefied phenol Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
A kind of preparation method of naphthalene water reducer, comprises the following steps：(1) methyl naphthalene and phenol are distinguished into sulfonation, obtains sulfonated methyl naphthalene material and p-hydroxybenzenyl sulfonate material；(2) reaction is hydrolyzed in sulfonated methyl naphthalene material, azeotropic deviates from unreacted methyl naphthalene or its homologue, and remaining sulfonated methyl naphthalene material enters in step (3) reaction；(3) formaldehyde for the p-hydroxybenzenyl sulfonate material concentrated sulfuric acid acidifying that step (2) is obtained sulfonated methyl naphthalene material, step (1) are obtained carries out condensation reaction, must be condensed material；(4) it is 7.5~9 that alkali lye is added in the condensation material that step (3) is obtained and carries out neutralization reaction to pH value, and reaction end obtains naphthalene water reducer.That the naphthalene water reducer of the present invention has is good to the adaptability of cement, concrete workability is good, protect plasticity can be compared with strong, the excellent performance such as concrete gradual loss is small, water-reducing rate is higher；And preparation method technique is simple, easily-controlled reaction conditions, and the production cost of naphthalene water reducer can also be reduced.
Description
(1) technical field
The present invention relates to the preparation method of concrete admixture, and in particular to a kind of preparation method of naphthalene water reducer.
(2) background technology
Naphthalene water reducer is domestic production amount maximum, using most wide water reducer, and occupation rate of market is about 70% or so.Naphthalene
It is the mature production technology of based water reducer, easy to use, small, preferable, concrete relative with cement adaptability is influenceed on setting time
Workability it is good, can be used with other various additive complexes, particularly for Use out of range, have than other class water reducers
More predictabilitys, there is extensive customer basis, are usually used in preparing large fluidity, high-strength, high performance concrete.However, naphthalene
Based water reducer is there is also certain defect, and the concrete slump gradual loss of simple admixture naphthalene water reducer is very fast.
Naphthalene series high-efficiency water-reducing agent is usually what raw material was produced with crude naphthalene.Due to the growth of concrete production amount, naphthalene system
Demand cumulative year after year of the water reducer to crude naphthalene.Crude naphthalene appearance in recent years is global in short supply, and the growth of consumption figure, causes in addition
The price of crude naphthalene constantly raises up.Patent CN CN102351458A, 101164955A, CN103864332A etc. are developed with valency
The relatively cheap washing oil of lattice, industrial acenaphthylene, methyl naphthalene are the high efficiency water reducing agent of raw material, and the raw materials for production for expanding high efficiency water reducing agent come
Source, and the production technology similar to naphthalene water reducer is used, synthesize polycyclic aromatic hydrocarbons (PAH) sulfonate and formaldehyde condensation product, make its performance
It is close with naphthalene water reducer.So being produced into for water reducer can be effectively reduced while crude naphthalene resource scarcity is alleviated
This, makes it have the stronger market competitiveness.
Water reducer with methyl naphthalene, industrial acenaphthylene, washing oil etc. for raw material and formaldehyde condensation belongs to the efficient diminishing of polycyclic aromatic hydrocarbon type
Agent, although its water-reducing rate is higher, air content is big and bubble is uneven so that concrete crushing strength does not reach requirement, and
Still the faster defect of concrete slump gradual loss can not be solved.Containing strong on the hydrophobic main chain of this kind of diminishing agent molecule
Hydrophilic radical sulfonic group, can play diminishing with the associated water molecules of polarity in cement particle surface one layer of solvation film of formation
Effect, but application after resistance to compression and protect modeling poor performance.If can be introduced different on the basis of original naphthalene water reducer technique
Organic radicals, can make naphthalene water reducer while with original water-reducing property, solve concrete slump gradual loss
Seriously, air content is higher causes the not high defect of concrete strength.
(3) content of the invention
An object of the present invention is to provide a kind of preparation method of new naphthalene water reducer, and the naphthalene water reducer not only has
The performance such as have, workability of concrete good to cement adaptability good, while overcoming prior art water reducer to Control Measures for Concrete Slump
Degree gradual loss is serious, air content is higher causes the problems such as concrete strength is not high；And its preparation method technique is simple, reaction
Condition is easy to control, and can also reduce the production cost of naphthalene water reducer.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of naphthalene water reducer, comprises the following steps：
(1) sulfonation
Methyl naphthalene under molten condition is placed in xanthator, 110~140 DEG C are warming up to, 98% dense sulphur is slowly added dropwise
Acid or oleum, the time control of dropwise addition carry out 2.5~3h of sulfonating reaction, instead in more than 30min in 140~170 DEG C of insulations
Answer terminal point control feed acidity 18~40%, preferably 25~32%, obtain sulfonated methyl naphthalene material；The methyl naphthalene and sulphur
The ratio between amount of material of acid is 1：1~2, preferably 1：1.1~1.5；
Will after Liquefaction Products in Phenol put into reactor in, be warming up to 60~70 DEG C, be slowly added dropwise in 30min 98% concentrated sulfuric acid or
Oleum, control temperature is no more than 80 DEG C, and 90~100 DEG C, 2~3h of insulation reaction, reaction end are warming up to after completion of dropping
Control feed acidity 22~40%, preferably 27~32%, obtain p-hydroxybenzenyl sulfonate material；The material of the phenol and sulfuric acid
The ratio between amount be 1：1~2, preferably 1：1~1.3；
(2) hydrolyze
The sulfonated methyl naphthalene material that step (1) is obtained is transferred in the de- naphthalene device of hydrolysis, reduces temperature to 100~130 DEG C,
Control feed acidity add water 10~32%, preferably 16~26%, 15~30min of reaction, unreacted methyl is hydrolyzed
Naphthalene or its homologue are deviate from vapor azeotropic, and remaining sulfonated methyl naphthalene material enters in step (3) reaction；Azeotropic abjection
Stratification when material is cooled to less than 100 DEG C, lower floor is that methyl naphthalene may be recovered reproduction；
(3) it is condensed
The sulfonated methyl naphthalene material that step (2) is obtained is cooled to 90~95 DEG C, the para hydroxybenzene sulphur obtained with step (1)
Sour material is mixed by a certain percentage to be transferred to after condensation device, and the regulation reaction system that adds water acidity is 20~25%, within 1~2h
It is slowly added dropwise after the formaldehyde being acidified with the concentrated sulfuric acid, completion of dropping and is warming up to 95~105 DEG C of insulation 3~4h of condensation, can optionally adds
Water adjusts material viscosity, must be condensed material；The ratio between amount of material of the sulfonated methyl naphthalene and p-hydroxybenzenyl sulfonate is 1.4~2：1,
Preferably 1.5~1.7：1；The ratio between amount of the formaldehyde and p-hydroxybenzenyl sulfonate material is 1.5~6：1, preferably 2.3~4.4：
1；The formaldehyde that is acidified with the concentrated sulfuric acid is that to adjust the pH of formalin with the concentrated sulfuric acid be 2~3 and gained after stirring；
In above formula：A, b, c are selected from 0~25 integer, and as a=0, b, c are not equal to 0；
(4) neutralize
The condensation material that step (3) is obtained is transferred in neutralization device, and alkali lye is added at 60~80 DEG C and carries out neutralization reaction extremely
PH value is 7.5~9, and reaction end produces liquid naphthalene water reducer, and solid naphthalene water reducer is obtained by the way that processing is further dried
Finished product；The alkali lye can use sodium hydroxide solution, sodium bicarbonate solution or sodium carbonate liquor.
Further, the preparation method is carried out in accordance with the following steps：
(1) sulfonation
Methyl naphthalene under molten condition is placed in xanthator, 110~140 DEG C are warming up to, 98% dense sulphur is slowly added dropwise
Acid or oleum, the time control of dropwise addition carry out 2.5~3h of sulfonating reaction, instead in more than 30min in 140~170 DEG C of insulations
Terminal point control feed acidity is answered 25~32%, sulfonated methyl naphthalene material is obtained；The amount of the material of the methyl naphthalene and sulfuric acid it
Than for 1：1.1~1.5；
Will after Liquefaction Products in Phenol put into reactor in, be warming up to 60~70 DEG C, be slowly added dropwise in 30min 98% concentrated sulfuric acid or
Oleum, control temperature is no more than 80 DEG C, and 90~100 DEG C, 2~3h of insulation reaction, reaction end are warming up to after completion of dropping
Control feed acidity 27~32%, obtain p-hydroxybenzenyl sulfonate material；The ratio between amount of material of the phenol and sulfuric acid is 1：1~
1.3；
(2) hydrolyze
The sulfonated methyl naphthalene material that step (1) is obtained is transferred in the de- naphthalene device of hydrolysis, reduces temperature to 100~130 DEG C,
Control feed acidity add water 16~26%, 15~30min of reaction is hydrolyzed, unreacted methyl naphthalene or its homologue are with water
Steam azeotropic is deviate from, and remaining sulfonated methyl naphthalene material enters in step (3) reaction；The material of azeotropic abjection is cooled to 100 DEG C
Stratification when following, lower floor is that methyl naphthalene carries out reclaiming production；
(3) it is condensed
The sulfonated methyl naphthalene material that step (2) is obtained is cooled to 90~95 DEG C, the para hydroxybenzene sulphur obtained with step (1)
Sour material is mixed by a certain percentage to be transferred to after condensation device, and the regulation reaction system that adds water acidity is 20~25%, within 1~2h
It is slowly added dropwise after the formaldehyde being acidified with the concentrated sulfuric acid, completion of dropping and is warming up to 95~105 DEG C of insulation 3~4h of condensation, can optionally adds
Water adjusts material viscosity, must be condensed material；The ratio between amount of material of the sulfonated methyl naphthalene and p-hydroxybenzenyl sulfonate is 1.5~1.7：
1；The ratio between amount of the formaldehyde and p-hydroxybenzenyl sulfonate material is 2.3~4.4：1；The formaldehyde being acidified with the concentrated sulfuric acid is with dense
The pH of sulfuric acid regulation formalin is 2~3 and gained after stirring；
(4) neutralize
The condensation material that step (3) is obtained is transferred in neutralization device, and alkali lye is added at 60~80 DEG C and carries out neutralization reaction extremely
PH value is 7.5~9, and reaction end produces liquid naphthalene water reducer, and solid naphthalene water reducer is obtained by the way that processing is further dried
Finished product；The alkali lye uses sodium hydroxide solution, sodium bicarbonate solution or sodium carbonate liquor.
In the present invention, acidity (AG) calculation formula is as follows：
[H in formula+] and [OH-] substance withdrawl syndrome of hydrogen ion and hydroxide ion in system is represented respectively.
The present invention introduces after formaldehyde condensation products the naphthalene water reducer obtained by preparing by the way that phenol is carried out into sulfonation, compared to normal
The water reducer that rule are produced with crude naphthalene, its advantage is mainly reflected in：
1. carrying out ternary polycondensation reaction by sulfonated methyl naphthalene, sulfonated phenol and formaldehyde, make in the formaldehyde condensation products of synthesis
Containing new organic radicals, solve traditional naphthalene system product and protect the defect of modeling poor performance, so that imparting product protects modeling characteristic；
2. sulfonic density on main chain is considered in raising product molecule on molecular structure so that the diminishing of water reducer
Rate and guarantor's plasticity can be improved；
3. the route of sulfonation is separated with phenol organic matter using naphthalene system's organic matter, it is ensured that reaction intermediate sulfonated methyl naphthalene
With the sulfonation effect of sulfonated phenol so that subsequently carry out the naphthalene system product water-reducing property and quality of condensation reaction generation not with formaldehyde
It is impacted.
4. naphthalene water reducer of the present invention, it is with the adaptability to cement is good, concrete workability is good, protect plasticity
Can be relatively strong, concrete gradual loss is small, the excellent performance such as water-reducing rate is higher.
(4) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This (following weight is percentage amount)：
Embodiment 1：
Methyl naphthalene sulfonation：
83% technical methylnaphthalene 2000kg, 98% concentrated sulfuric acid 1655kg is weighed respectively, and it is anti-that technical methylnaphthalene is put into sulfonation
Kettle is answered, 130 DEG C are to slowly warm up to, 40min is uniformly added dropwise into sulfonating reaction kettle in 98% concentrated sulfuric acid, control is warming up to 160 DEG C,
2.5h is continuously stirred, obtained sulfonated methyl naphthalene is reacted standby.
Phenol sulfonation：
The phenol 1325kg, 98% concentrated sulfuric acid 1550kg after liquefaction are weighed respectively.Liquefied phenol is put into sulphonation kettle,
60 DEG C are warming up to, concentrated sulfuric acid control is slowly added dropwise and is added in 30min, keeping temperature is no more than 80 DEG C, drips off and is risen after the concentrated sulfuric acid
High-temperature is to 90 DEG C, and sulfonating reaction 2h, obtained sulfonated phenol is standby.
The de- naphthalene of hydrolysis：
Above-mentioned sulfonated methyl naphthalene is transferred in hydrolytic reaction pot, reduction temperature to the regulation feed acidity that after 120 DEG C, adds water is
25%, reaction 20min is hydrolyzed.Unreacted free methyl naphthalene is deviate from vapor azeotropic, is cooled to 90 DEG C of upper lower leafs,
Lower floor's recovery.
Condensation reaction：
Material after above-mentioned hydrolysis is cooled to 95 DEG C, 1550kg sulfonated methyls naphthalene and 770kg sulfonated phenols are beaten simultaneously
Enter in condensation reaction kettle, the acidity 22% for the regulation reaction system that adds water, 515kg is slowly added dropwise in 2h is acidified to pH value with the concentrated sulfuric acid
In 2~3 37% formalin (it is 2~3 to adjust the pH of formalin that mass concentration is 37% with the concentrated sulfuric acid), then
105 DEG C of condensation insulation 3h are warming up to, obtained condensation material is standby.
Neutralization reaction：
Above-mentioned condensation material is transferred to neutralization kettle by transfering material pump, neutralization reaction is carried out at 80 DEG C, with 30% NaOH water
Solution regulation pH value is 7.5~9, produces liquid methyl naphthalene water reducer, by the way that processing is further dried, can obtain solid methyl naphthalene and subtract
Aqua finished product.
Embodiment 2
Naphthalene sulfonation：
83% technical methylnaphthalene 1600kg, 98% concentrated sulfuric acid 1545kg is weighed respectively, and crude naphthalene is put into sulfonating reaction kettle,
130 DEG C are to slowly warm up to, 98% concentrated sulfuric acid is uniformly added dropwise in sulfonating reaction kettle, 30min is dripped.Control is warming up to 165
DEG C, 3h is continuously stirred, obtained sulfonated methyl naphthalene is reacted standby.
Phenol sulfonation：
The phenol 1060kg, 98% concentrated sulfuric acid 1225kg after liquefaction are weighed respectively.Liquefaction methylphenol is put into sulfonation
In kettle, 70 DEG C are warming up to, concentrated sulfuric acid control is slowly added dropwise and is added in 30min, keeping temperature is no more than 80 DEG C, drips off the concentrated sulfuric acid
Rise temperature is to 100 DEG C afterwards, and sulfonating reaction 2.5h, obtained sulfonated phenol is standby.
The de- naphthalene of hydrolysis：
Above-mentioned sulfonated methyl naphthalene is transferred in hydrolytic reaction pot, reduction temperature to the regulation feed acidity that after 110 DEG C, adds water is
20%, reaction 20min is hydrolyzed.Unreacted free naphthalene is deviate from vapor azeotropic, is cooled to 95 DEG C of upper lower leafs, lower floor
Recovery.
Condensation reaction
Material after above-mentioned hydrolysis is cooled to 90 DEG C, 2000kg sulfonated methyls naphthalene and 1050kg sulfonated phenols are beaten simultaneously
Enter in condensation reaction kettle, the acidity 20% for the regulation reaction system that adds water, 550kg is slowly added dropwise in 1.5h is acidified to pH with the concentrated sulfuric acid
It is worth 37% formalin 2~3, then heats to 100 DEG C of condensation insulation 4h, obtained condensation material is standby.
Neutralization reaction：
Above-mentioned condensation material is transferred to neutralization kettle by transfering material pump, the 30% NaOH aqueous solution is added, in 70 DEG C are carried out
And reaction, adjustment pH value is 7.5~9, produces liquid methyl naphthalene water reducer, by the way that processing is further dried, can obtain solid methyl
Naphthalene water reducer finished product.
Comparative example 1~3
Respectively take embodiment 3 in CN103864332A, in CN103159425A and CN101723616A embodiment 1 as pair
Ratio 1~3.
(naphthalene, sulfuric acid, formaldehyde mass ratio are 240 to comparative example 4:260:145 (non-foldings hundred))
Sulfonating reaction：
Weigh in 95% crude naphthalene 1500kg, 98% concentrated sulfuric acid 1515kg, input sulfonating reaction kettle, be to slowly warm up to respectively
140 DEG C, 30min is interior to be uniformly added into the concentrated sulfuric acid to sulfonating reaction kettle, and charging terminates, and controls 170 DEG C of successive reaction 3h of temperature, obtains
Sulfonation material it is standby.
The de- naphthalene of hydrolysis：
Above-mentioned sulfonated naphthalene is transferred in hydrolytic reaction pot, compound reduces temperature to after 110 DEG C, and add water regulation feed acidity
For 22%, stirring, hydrolysis 30min.Unreacted free naphthalene is deviate from vapor azeotropic, is cooled to 95 DEG C of upper lower leafs,
Lower floor recycles.
Condensation reaction
Sulfonation material after above-mentioned hydrolysis is cooled into 95 DEG C to squeeze into condensation reaction kettle, the acidity for the regulation reaction system that adds water
It is slowly added dropwise within 22%, 2h after 37% formaldehyde 318kg, completion of dropping and is warming up to 105 DEG C of condensation insulation 4h, obtained condensation
Material is standby.
Neutralization reaction：
Above-mentioned condensation material is transferred to neutralization kettle by transfering material pump, the 30% NaOH aqueous solution is added, in 70 DEG C are carried out
And reaction, adjustment pH value is 7.5~9, produces liquid naphthalene water reducer, by the way that processing is further dried, can obtain solid naphthalene system and subtract
Aqua finished product.
Application Example：
By the water reducer prepared by embodiment 1,2, the water reducer prepared by comparative example 1~4, according to GB/T8077 to cement
Paste flowing degree and water reducing ratio of cement mortar test, test cement is local conch cement 42.5R, the ratio of mud 0.29, water reducer volume
It is 0.6%, testing result see the table below.
As seen from the above table, the properties of product of comparative example 1 and embodiment 1,2 are closest, but comparative example 1 makes in sulfonation process
With organic solvent, it can remain and pollute in the product, while also being had a certain impact to properties of product；From comparative example 2, right
The net slurry test result of ratio 3 is understood, when phenol and naphthalene mixing sulfonation, is protected plasticity and has been declined compared with embodiment 1,2, this is
Because the sulfonation effect of reaction intermediate sulfonated products can not be ensured in mixing sulfonation process；Comparative example 4 is current existing system
Preparation Method, does not add phenol, and cement guarantor's plasticity after its products application is poor, while water-reducing rate is also relatively lower slightly.In addition,
Sulfonated phenol-methyl naphthalene sulfonic acid the water reducer prepared using the production method of the present invention, obtained product color is shallow, effectively improves
The product color of traditional raw material mixing process for sulfonation.
Claims (10)
1. a kind of preparation method of naphthalene water reducer, comprises the following steps：
(1) sulfonation
Methyl naphthalene under molten condition is placed in xanthator, 110~140 DEG C are warming up to, be slowly added dropwise 98% concentrated sulfuric acid or
Oleum, the time control of dropwise addition carries out 2.5~3h of sulfonating reaction, reaction is eventually in more than 30min in 140~170 DEG C of insulations
Point control feed acidity obtains sulfonated methyl naphthalene material 18~40%；The ratio between amount of material of the methyl naphthalene and sulfuric acid is
1：1~2；
It will be put into after Liquefaction Products in Phenol in reactor, be warming up to 60~70 DEG C, 98% concentrated sulfuric acid or smoke are slowly added dropwise in 30min
Sulfuric acid, control temperature is no more than 80 DEG C, and 90~100 DEG C, 2~3h of insulation reaction, control of reaction end point are warming up to after completion of dropping
Feed acidity obtains p-hydroxybenzenyl sulfonate material 22~40%；The ratio between amount of material of the phenol and sulfuric acid is 1：1~2；
(2) hydrolyze
The sulfonated methyl naphthalene material that step (1) is obtained is transferred in the de- naphthalene device of hydrolysis, and reduction temperature adds water to 100~130 DEG C
Feed acidity is controlled 10~32%, 15~30min of reaction is hydrolyzed, unreacted methyl naphthalene is deviate from vapor azeotropic,
Remaining sulfonated methyl naphthalene material enters in step (3) reaction；The material of azeotropic abjection is stood when being cooled to less than 100 DEG C to be divided
Layer, lower floor is that methyl naphthalene carries out reclaiming production；
(3) it is condensed
The sulfonated methyl naphthalene material that step (2) is obtained is cooled to 90~95 DEG C, the p-hydroxybenzenyl sulfonate thing obtained with step (1)
Material mixing by a certain percentage is transferred to after condensation device, and the regulation reaction system that adds water acidity is 20~25%, slow within 1~2h
95~105 DEG C of insulation 3~4h of condensation are warming up to after the formaldehyde that dropwise addition is acidified with the concentrated sulfuric acid, completion of dropping, can optionally add water tune
Material viscosity is saved, material must be condensed；The ratio between amount of material of the sulfonated methyl naphthalene and p-hydroxybenzenyl sulfonate is 1.4~2：1；It is described
The ratio between amount of formaldehyde and p-hydroxybenzenyl sulfonate material is 1.5~6：1；The formaldehyde being acidified with the concentrated sulfuric acid is adjusted with the concentrated sulfuric acid
The pH of formalin is 2~3 and gained after stirring；
(4) neutralize
The condensation material that step (3) is obtained is transferred in neutralization device, and alkali lye is added at 60~80 DEG C and carries out neutralization reaction to pH value
For 7.5~9, reaction end produces liquid naphthalene water reducer, and solid naphthalene water reducer finished product is obtained by the way that processing is further dried；
Wherein, acidity is represented with AG, and calculation formula is as follows：
[H in formula+] and [OH-] substance withdrawl syndrome of hydrogen ion and hydroxide ion in system is represented respectively.
2. the preparation method of naphthalene water reducer as claimed in claim 1, it is characterised in that：The sulfonated methyl naphthalene thing of step (1)
Expect in preparation process, control of reaction end point feed acidity is 25~32%.
3. the preparation method of naphthalene water reducer as claimed in claim 1, it is characterised in that：The sulfonated methyl naphthalene thing of step (1)
Expect in preparation process, the ratio between amount of material of the methyl naphthalene and sulfuric acid is 1：1.1~1.5.
4. the preparation method of naphthalene water reducer as claimed in claim 1, it is characterised in that：The p-hydroxybenzenyl sulfonate of step (1)
In material preparation process, control of reaction end point feed acidity is 27~32%.
5. the preparation method of naphthalene water reducer as claimed in claim 1, it is characterised in that：The p-hydroxybenzenyl sulfonate of step (1)
In material preparation process, the ratio between amount of material of the phenol and sulfuric acid is 1：1~1.3.
6. the preparation method of naphthalene water reducer as claimed in claim 1, it is characterised in that：In step (2), add water control feed liquid
Acidity is 16~26%.
7. the preparation method of naphthalene water reducer as claimed in claim 1, it is characterised in that：In step (3), the sulfonated methyl
The ratio between amount of material of naphthalene and p-hydroxybenzenyl sulfonate is 1.5~1.7：1.
8. the preparation method of naphthalene water reducer as claimed in claim 1, it is characterised in that：In step (3), the formaldehyde with it is right
The ratio between amount of hydroxy benzene sulfonic acid material is 2.3~4.4：1.
9. the preparation method of naphthalene water reducer as claimed in claim 1, it is characterised in that：In step (4), the alkali lye is used
Sodium hydroxide solution, sodium bicarbonate solution or sodium carbonate liquor.
10. the preparation method of naphthalene water reducer as claimed in claim 1, it is characterised in that the preparation method is according to following step
It is rapid to carry out：
(1) sulfonation
Methyl naphthalene under molten condition is placed in xanthator, 110~140 DEG C are warming up to, be slowly added dropwise 98% concentrated sulfuric acid or
Oleum, the time control of dropwise addition carries out 2.5~3h of sulfonating reaction, reaction is eventually in more than 30min in 140~170 DEG C of insulations
Point control feed acidity obtains sulfonated methyl naphthalene material 25~32%；The ratio between amount of material of the methyl naphthalene and sulfuric acid is
1：1.1~1.5；
It will be put into after Liquefaction Products in Phenol in reactor, be warming up to 60~70 DEG C, 98% concentrated sulfuric acid or smoke are slowly added dropwise in 30min
Sulfuric acid, control temperature is no more than 80 DEG C, and 90~100 DEG C, 2~3h of insulation reaction, control of reaction end point are warming up to after completion of dropping
Feed acidity obtains p-hydroxybenzenyl sulfonate material 27~32%；The ratio between amount of material of the phenol and sulfuric acid is 1：1~1.3；
(2) hydrolyze
The sulfonated methyl naphthalene material that step (1) is obtained is transferred in the de- naphthalene device of hydrolysis, and reduction temperature adds water to 100~130 DEG C
Control feed acidity 16~26%, 15~30min of reaction is hydrolyzed, unreacted methyl naphthalene or its homologue are with vapor
Azeotropic is deviate from, and remaining sulfonated methyl naphthalene material enters in step (3) reaction；The material of azeotropic abjection is cooled to less than 100 DEG C
When stratification, lower floor be methyl naphthalene carry out reclaiming production；
(3) it is condensed
The sulfonated methyl naphthalene material that step (2) is obtained is cooled to 90~95 DEG C, the p-hydroxybenzenyl sulfonate thing obtained with step (1)
Material mixing by a certain percentage is transferred to after condensation device, and the regulation reaction system that adds water acidity is 20~25%, slow within 1~2h
95~105 DEG C of insulation 3~4h of condensation are warming up to after the formaldehyde that dropwise addition is acidified with the concentrated sulfuric acid, completion of dropping, can optionally add water tune
Material viscosity is saved, material must be condensed；The ratio between amount of material of the sulfonated methyl naphthalene and p-hydroxybenzenyl sulfonate is 1.5~1.7：1；Institute
It is 2.3~4.4 to state the ratio between amount of formaldehyde and p-hydroxybenzenyl sulfonate material：1；The formaldehyde being acidified with the concentrated sulfuric acid is to use the concentrated sulfuric acid
The pH of regulation formalin is 2~3 and gained after stirring；
(4) neutralize
The condensation material that step (3) is obtained is transferred in neutralization device, and alkali lye is added at 60~80 DEG C and carries out neutralization reaction to pH value
For 7.5~9, reaction end produces liquid naphthalene water reducer, by be further dried processing obtain solid naphthalene water reducer into
Product；The alkali lye uses sodium hydroxide solution, sodium bicarbonate solution or sodium carbonate liquor.
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| CN109810542A (en) * | 2019-01-19 | 2019-05-28 | 浙江吉盛化学建材有限公司 | A kind of naphthalene system dispersing agent and preparation method thereof |
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| 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 |
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| CN111689879A (en) * | 2020-06-03 | 2020-09-22 | 浙江五龙新材股份有限公司 | Clean production method of dispersing agent |
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| CN114669077B (en) * | 2022-04-15 | 2024-04-16 | 煤炭科学技术研究院有限公司 | Purification system and purification method of 2-methylnaphthalene |
| CN114890991A (en) * | 2022-05-20 | 2022-08-12 | 东南大学 | Preparation method and application of hyperbranched bifunctional polymerization ionic liquid catalyst |
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