CN106117481A - A kind of solvent method concentrates the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer - Google Patents
A kind of solvent method concentrates the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer Download PDFInfo
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- CN106117481A CN106117481A CN201610467983.9A CN201610467983A CN106117481A CN 106117481 A CN106117481 A CN 106117481A CN 201610467983 A CN201610467983 A CN 201610467983A CN 106117481 A CN106117481 A CN 106117481A
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- 239000002904 solvent Substances 0.000 title claims abstract description 131
- 238000009833 condensation Methods 0.000 title claims abstract description 87
- 230000005494 condensation Effects 0.000 title claims abstract description 87
- 238000006277 sulfonation reaction Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000012141 concentrate Substances 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 124
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 230000018044 dehydration Effects 0.000 claims abstract description 23
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 23
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims description 46
- 238000005086 pumping Methods 0.000 claims description 35
- 230000007062 hydrolysis Effects 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 19
- 230000003301 hydrolyzing effect Effects 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 11
- 235000021050 feed intake Nutrition 0.000 claims description 10
- 238000009834 vaporization Methods 0.000 claims description 10
- 230000008016 vaporization Effects 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 16
- 230000007423 decrease Effects 0.000 abstract description 12
- 238000006482 condensation reaction Methods 0.000 abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 4
- 239000010802 sludge Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 86
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 39
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000003756 stirring Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 17
- 238000010792 warming Methods 0.000 description 17
- 239000001117 sulphuric acid Substances 0.000 description 16
- 235000011149 sulphuric acid Nutrition 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 pottery Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0237—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
- C04B24/226—Sulfonated naphtalene-formaldehyde condensation products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of solvent method to concentrate the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, including feeding intake, sulfonation, be dehydrated, hydrolyze, be condensed, the step such as neutralization, use low complex acid amount sulfonation, do not produce disulfonic acid or many sulfonic acid, improve the selectivity of β～LOMAR PWA EINECS 246-676-2, improve the quality of water reducer, decrease waste sludge discharge；Using solvent during sulfonation, using water yield as reaction end desired value, dehydration uses quantity of solvent gradually to reduce every time, reduces solvent usage amount to greatest extent, thus reduces thermal loss；Use large-volume reaction kettle to concentrate sulfonation, take full advantage of exothermic heat of reaction, keep temperature of reaction kettle, decrease steam usage amount；Decrease waste gas discharge；Condensation reaction is the most with pressure, and safety is high.
Description
Technical field
The present invention relates to concrete admixture production technical field, particularly relate to a kind of solvent method and concentrate the contracting of sulfonation separate mealing type
The production method of naphthalene water reducer is produced in symphysis.
Background technology
Water reducer is a kind of under conditions of maintaining concrete slump constant, can reduce outside the concrete of mixing water amount
Add agent.Mostly belong to anion surfactant, have lignosulfonates, naphthalene sulphonate formaldehyde polymer etc..Add concrete
After mixture, cement granules there is is peptizaiton, its workability can be improved, reduce unit consumption of water, improve concrete mix
Mobility；Or minimizing unit cement consumption, save cement.
Naphthalene water reducer is widely used high efficiency water reducing agent, is a kind of super plasticizer, has good diminishing and early pretends
With, it is applied in Concrete Industry more, is also applied to the industries such as plasterboard, water-coal-slurry, pottery, oil well.Its production technology is main
It is that crude naphthalene is put in reactor, is warmed up to uniform temperature, stir and drip concentrated sulphuric acid and carry out sulfonation, insulation, water
Solving, add formaldehyde condensation, neutralize, be dried and obtain, at present, general production method is to carry out sulfonation in 5 cubes of reactors, sulphur
After having changed, dripping formaldehyde condensation in same reactor, such operation has following four problem: (1) gives birth on a large scale
During product, owing to coolant and heating agent are used alternatingly, thermal loss is big；(2) single batch operation heat scatters and disappears serious, does not make full use of
Exothermic heat of reaction；(3) during reaction, area is big, and waste gas volatile quantity is big；(4) production efficiency is low, it is impossible to realize continuous prodution；(5) work
When industry naphthalene and sulfuric acid sulfonation, especially with the sulphuric acid of high concentration, during the high concentration concentrated sulphuric acid such as such as 100%, 105%, 120%, dense
Sulphuric acid can not get disperseing in time, contacts with naphthalene, easily produces disulfonic acid or many sulfonic acid, makes the selectivity of β～LOMAR PWA EINECS 246-676-2 reduce, shadow
Ring next step formaldehyde condensation, affect the quality of water reducer.
If there being a kind of heat utilization rate high, and the method that serialization large-scale production can be realized, above depositing can be avoided
Problem, it is possible to be greatly improved production efficiency.The present invention, based on problem above, has invented a kind of solvent method and has concentrated sulfonation to divide
The condensation of meal formula produces the production method of naphthalene water reducer, and heat utilization rate is high, and quality is good, can realize serialization large-scale production
Requirement, improves production efficiency.
Summary of the invention
It is an object of the invention to, overcome the deficiencies in the prior art, it is provided that a kind of solvent method concentrates the contracting of sulfonation separate mealing type
The production method of naphthalene water reducer is produced in symphysis, can meet rapid dispersion mixing sulfonating agent, it is to avoid many sulfonation, and energy-conservation, minimizing is given up
Gas, can realize again serialization and improve the requirement of production efficiency.
For solving above-mentioned technical problem, the technical scheme is that a kind of solvent method of offer concentrates the contracting of sulfonation separate mealing type
The production method of naphthalene water reducer is produced in symphysis, and described production method comprises the following steps: to feed intake, sulfonation, be dehydrated, hydrolyze, be condensed
And neutralization, wherein, described dehydration is: being continuously pumped into solvent in the reactor equipped with sulfonating reaction liquid, solvent is at high temperature
Taking the water that sulfonating reaction produces during volatilization out of, separated with solvent by water after condensation, isolated solvent pumps in reactor again, when
Water yield stops pumping into solvent after reaching the setting percentage ratio of sulfonating reaction water yield, in question response still temperature be increased to 140～
Start again at when 170 DEG C and pump into solvent, start to circulate next time, last after temperature is increased to 160～165 DEG C of insulations 1～6h.
Preferably, described sulfonating reaction water yield set percentage ratio as: 40～70%, 15～45%, 10～30%, 5～
20%。
Preferably, described sulfonating reaction water yield set percentage ratio as: 40～70%, 10～30%, 10～15%, 5～
12%, 3～5%.
Solvent dehydration is used, using water yield as reaction end desired value, the setting hundred of sulfonating reaction water yield after sulfonation
Proportion by subtraction reduces successively, and dehydration uses quantity of solvent gradually to reduce every time, decreases solvent usage amount to greatest extent, thus decreases heat
Amount loss.
Preferably, sub-material is also included between described dehydration and hydrolysing step: the reaction being dehydrated in reactor
Liquid is transferred at least one condensation kettle the most successively, and described hydrolysis, condensation and neutralization procedure are all carried out in described condensation kettle.
Preferably, sub-material step is also included between described hydrolysing step and condensation step: by what reactor had been dehydrated
Reactant liquor is transferred at least one condensation kettle the most successively, and described condensation and neutralization procedure are all carried out in described condensation kettle,
Described hydrolysing step is carried out in a kettle..
Reactant liquor hydrolysis completed is transferred in condensation kettle carry out follow-up condensation and neutralization procedure, sulfonation in reactor
The temperature requirement of reaction and hydrolysis is of a relatively high, and condensation reaction requires that temperature is relatively low, by sulfonation with condensation respectively
Different containers carries out, it is to avoid cold and heat succeed each other, decrease thermal losses.
Preferably, sub-material step is also included between described dehydration and hydrolysing step: by what reactor had been dehydrated
Reactant liquor is transferred at least one condensation kettle the most successively, and described hydrolysis, condensation and neutralization procedure are all in described condensation kettle
Carry out.
Reactant liquor dehydration completed is transferred in condensation kettle carry out follow-up hydrolysis, condensation and neutralization procedure, reactor
Middle sulfonating reaction temperature is high, and hydrolyze, setting-up point low, sulfonation and hydrolysis, condensation are separately carried out, it is to avoid cold and hot friendship
Replace, decrease thermal losses.
Preferably, the capacity of described condensation kettle is 2m3～20m3。
Preferably, the capacity of described reactor is at least 3m3。
Use large-volume reaction kettle to concentrate sulfonation, take full advantage of exothermic heat of reaction, keep temperature of reaction kettle, decrease heat energy
Usage amount.
Preferably, described material addition step is: put into the naphthalene through metering in reactor.
Preferably, described sulfonation procedure is: the reactor that will be equipped with naphthalene heats up, when in reactor, the temperature of naphthalene rises to
When 140～145 DEG C, add concentrated sulphuric acid, preferably use 98% concentrated sulphuric acid, the follow-up temperature of continuing rising of acid adding, carry out under the conditions of 160～165 DEG C
Sulfonating reaction, wherein, the described concentrated sulphuric acid of addition and the weight ratio of naphthalene are 0.65～0.88:1, for low complex acid amount sulfonation, do not give birth to
Produce disulfonic acid or many sulfonic acid, improve the selectivity of beta-naphthalenesulfonic-acid, improve the quality of water reducer, reduce waste sludge discharge.
The reaction equation of described sulfonating reaction is:
As shown in above formula, having water to generate in sulfonating reaction, described dehydration is that the water produced in sulfonating reaction step is gone
Removing, be continuously pumped into solvent in the reactor equipped with sulfonating reaction liquid, solvent takes what sulfonating reaction produced out of when vaporization at high temperature
Water, separates water with solvent after condensation, and isolated solvent continues to pump in reactor, and solvent is recycled, and isolates
Water reach certain percentage ratio of sulfonating reaction theory water yield after stop pumping into solvent, now sulfonating reaction generate water is molten
A part is taken in agent out of, makes the concentration of residual sulfuric acid be further enhanced, and promotes that reaction is carried out to the right, improves turning of LOMAR PWA EINECS 246-676-2
Rate, sulfonating reaction is released heat, is made temperature in reactor raise, start again at when temperature rises to 140～170 DEG C and pump into
Solvent, starts second time circulation；The percentage ratio of sulfonating reaction theory water yield sets and reduces successively, such as, when the naphthalene of 100mol
When carrying out sulfonating reaction with the concentrated sulphuric acid of 100mol, produce the water of 100mol in theory, when in dehydration, cycle-index is four
Time secondary, the percentage ratio setting water yield successively is followed successively by 40%, 30%, 20%, 10%, i.e. after starting to pump into solvent for the first time, when cold
The water separated after Ning reaches the 40% of 100mol, i.e. (can be converted into weight) during 40mol, stops pumping into solvent, when temperature rises
Starting again at second time during to 160 DEG C and pump into solvent, when the water separated after condensation reaches the 30% of 100mol, stopping pumps into molten
Agent, the like.
After the dehydration is completed, take the reactant liquor in reactor survey its acidity should be between 20～25%.
Preferably, described hydrolysing step is: add water in the reactant liquor in described condensation kettle, at 110 DEG C of Water Unders
Solving 30min, stir while hydrolysis, hydrolytic acidity controls 17～22%, and wherein, the water yield of addition is 100～800L.
Preferably, described condensation step is: add in the reactant liquor in described hydrolysing step under the conditions of 95～100 DEG C
Formaldehyde, adding the formaldehyde time is 2～5h, is warming up to 100～115 DEG C of condensations 2～20h after adding formaldehyde.
The reaction equation of condensation reaction is:
Preferably, in described condensation reaction, when the clean rising value of electric current reaches 5～20A, terminate condensation, add immediately
Water, stirs 1～5 hour, will not be the highest with the degree of polymerization (molecular weight) and material viscosity controlling naphthalene sulfonic acid-formaldehyde condensation product, and contracting
Close course of reaction the most with pressure, safety.
Preferably, described neutralization procedure is: add alkali in the reactant liquor in described condensation step being neutralized to PH is 7～9,
Obtain naphthalene water reducer.
Preferably, described solvent be Carbon bisulfide, pyridine, dimethylbenzene, toluene, benzene, dichloroethanes, carbon tetrachloride, chloroform,
One or more kinds of mixture in dioxane, ethyl acetate, acrylonitrile and tetrachloromethane.
The beneficial effect of the technical scheme that the present invention provides:
1, in common process, naphthalene and sulfuric acid dosage ratio is for 1:1.3～1.5, and in the technique that the present invention provides, naphthalene with sulfuric acid dosage ratio is
1:0.65～0.88, this technique uses low complex acid amount sulfonation, does not produce disulfonic acid or many sulfonic acid, improves β～LOMAR PWA EINECS 246-676-2
Selectivity, improves the quality of water reducer, decreases waste sludge discharge；
2, energy-conservation, use solvent during sulfonation, using water yield as reaction end desired value, dehydration uses quantity of solvent gradually to subtract every time
Few, reduce solvent usage amount to greatest extent, thus reduce thermal loss；
3, use large-volume reaction kettle to concentrate sulfonation, take full advantage of exothermic heat of reaction, keep temperature of reaction kettle, decrease steam and make
Consumption；Decrease waste gas discharge；
4, sub-material step is increased, by follow-up hydrolysis relatively low with demand temperature for sulfonating reaction step higher for demand temperature, contracting
Close reactions steps to divide and carry out to different containers, it is to avoid cold and heat succeed each other, save thermal losses.
5, condensation reaction is the most with pressure, safety.
6, this method energy multiscale water reducer product simultaneously, produces sodium sulphate content 0.1～20%, alkali content 0.01～18%
Naphthalene water reducer.
7, decrease containing sulfur dioxide, sulfuric acid mist and the discharge of naphthalene waste gas.
Accompanying drawing explanation
Fig. 1 is that a kind of solvent method that the embodiment of the present invention provides concentrates the condensation of sulfonation separate mealing type to produce the life of naphthalene water reducer
The schematic flow sheet of product method.
Fig. 2 is that the another kind of solvent method that the embodiment of the present invention provides concentrates the condensation of sulfonation separate mealing type to produce naphthalene water reducer
The schematic flow sheet of production method.
Fig. 3 is that the third solvent method that the embodiment of the present invention provides concentrates the condensation of sulfonation separate mealing type to produce naphthalene water reducer
The schematic flow sheet of production method.
Detailed description of the invention
For the technical scheme making those skilled in the art be more fully understood that in the present invention, real below in conjunction with the present invention
Execute the accompanying drawing in example, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under not making creative work premise, all should belong to present invention protection
Scope.
Embodiment 1
Disclosure embodiment provides a kind solvent method to concentrate the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, as
Shown in Fig. 1, comprise the following steps:
S101: feed intake: add 5000kg liquid naphthalene in the reactor of 12.5m, and carry out steam intensification；
S102: sulfonation: start addition 98% concentrated sulphuric acid 4250kg slowly, at the uniform velocity when the temperature of liquid naphthalene rises to 140 DEG C,
60min adds, and continues steam and heat up after acid adding, is incubated 4h, carries out sulfonating reaction after being warming up to 160 DEG C；
S103: dehydration: being continuously pumped into ethyl acetate solvent in the reactant liquor of described step S102, solvent carries when vaporization at high temperature
Going out the water that sulfonating reaction produces, separated with ethyl acetate solvent by water after condensation, isolated solvent continues to pump in reactor,
Stop pumping into ethyl acetate solvent, when temperature is increased to 140 DEG C in question response still again after the isolated water yield reaches 281kg
Starting to pump into ethyl acetate solvent, start second time circulation, water yield stops pumping into solvent when reaching 317kg for the second time, and the 3rd
Stop when secondary water yield reaches 70kg pumping into solvent, stop when the 4th time water yield reaches 35kg pumping into solvent, so circulation 4 times
After temperature is increased to 160 DEG C of insulation 6h.
S104: hydrolysis: add water in the reactant liquor in described step S103, stirs 30min at 110 DEG C and carries out water
Solving, it is 17% that hydrolytic acidity controls；
S105: condensation: adding 300kg concentration in thread mode in the reactant liquor in described step S104 under the conditions of 95 DEG C is
The formaldehyde of 37%, 5h adds, and is warming up to 100 DEG C of condensation 3h, adds water immediately, stir 1h after being condensed after being added dropwise to complete；
S106: neutralize: add Caustic soda in the reactant liquor in described step S105 and neutralize, be 7 to pH value, obtain naphthalene system of naphthalene system and subtract
Water preparation.
Embodiment 2
Disclosure embodiment provides a kind solvent method to concentrate the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, as
Shown in Fig. 1, comprise the following steps:
S101: feed intake: add 5200kg liquid naphthalene in 20m reactor, and carry out steam intensification；
S102: sulfonation: start addition 98% concentrated sulphuric acid 3380kg slowly, at the uniform velocity when the temperature of liquid naphthalene rises to 145 DEG C,
70min adds, and continues steam and heat up after acid adding, is incubated 2.5h, carries out sulfonating reaction after being warming up to 165 DEG C；
S103: dehydration: being continuously pumped into xylene solvent in the reactant liquor of described step S102, solvent is taken out of when vaporization at high temperature
The water that sulfonating reaction produces, separates water with xylene solvent after condensation, and isolated solvent continues to pump in reactor, when dividing
The water yield separated out stops pumping into solvent after reaching 434kg, and in question response still, temperature is increased to when 170 DEG C start again at pump into diformazan
Benzene solvent, starts second time circulation, and water yield stops pumping into solvent when reaching 74kg for the second time, and water yield reaches 62kg for the third time
Time stop pumping into solvent, stop when the 4th time water yield reaches 31kg pumping into solvent, stop when the 5th water yield reaches 19kg
Pump into solvent, after so circulating 5 times, temperature is increased to 165 DEG C of insulation 1h.
S104: hydrolysis: add water in the reactant liquor in described step S103, stirs 30min at 110 DEG C and carries out water
Solving, hydrolytic acidity is 22%；
S105: condensation: add 3120kg concentration in thread mode in the reactant liquor in described step S104 under the conditions of 98 DEG C
Being the formaldehyde of 37%, 3h adds, and is warming up to 115 DEG C of condensation 2h, adds water immediately, stir 5h after being condensed after being added dropwise to complete；
S106: neutralize: add Caustic soda in the reactant liquor in described step S105 and neutralize, be 9 to pH value, obtain naphthalene system of naphthalene system and subtract
Water preparation.
Embodiment 3
Disclosure embodiment provides a kind solvent method to concentrate the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, as
Shown in Fig. 1, comprise the following steps:
S101: feed intake: add 5200kg liquid naphthalene in 20m reactor, and carry out steam intensification；
S102: sulfonation: start addition 98% concentrated sulphuric acid 3380kg slowly, at the uniform velocity when the temperature of liquid naphthalene rises to 145 DEG C,
70min adds, and continues steam and heat up after acid adding, is incubated 2.5h, carries out sulfonating reaction after being warming up to 165 DEG C；
S103: dehydration: being continuously pumped into xylene solvent in the reactant liquor of described step S102, solvent is taken out of when vaporization at high temperature
The water that sulfonating reaction produces, separates water with xylene solvent after condensation, and isolated solvent continues to pump in reactor, when dividing
The water yield separated out stops pumping into solvent after reaching 248kg, and in question response still, temperature is increased to when 170 DEG C start again at pump into diformazan
Benzene solvent, starts second time circulation, and water yield stops pumping into solvent when reaching 93kg for the second time, and water yield reaches for the third time
Stop during 186kg pumping into solvent, stop when the 4th time water yield reaches 93kg pumping into solvent, by temperature liter after so circulating 4 times
Up to 165 DEG C insulation 1h.
S104: hydrolysis: add water in the reactant liquor in described step S103, stirs 30min at 110 DEG C and carries out water
Solving, hydrolytic acidity is 22%；
S105: condensation: add 3120kg concentration in thread mode in the reactant liquor in described step S104 under the conditions of 98 DEG C
Being the formaldehyde of 37%, 3h adds, and is warming up to 115 DEG C of condensation 2h, adds water immediately, stir 5h after being condensed after being added dropwise to complete；
S106: neutralize: add Caustic soda in the reactant liquor in described step S105 and neutralize, be 9 to pH value, obtain naphthalene system of naphthalene system and subtract
Water preparation.
Embodiment 4
Disclosure embodiment provides a kind solvent method to concentrate the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, as
Shown in Fig. 1, comprise the following steps:
S101: feed intake: add 5000kg liquid naphthalene in the reactor of 12.5m, and carry out steam intensification；
S102: sulfonation: start addition 98% concentrated sulphuric acid 4250kg slowly, at the uniform velocity when the temperature of liquid naphthalene rises to 140 DEG C,
60min adds, and continues steam and heat up after acid adding, is incubated 4h, carries out sulfonating reaction after being warming up to 160 DEG C；
S103: dehydration: being continuously pumped into ethyl acetate solvent in the reactant liquor of described step S102, solvent carries when vaporization at high temperature
Going out the water that sulfonating reaction produces, separated with ethyl acetate solvent by water after condensation, isolated solvent continues to pump in reactor,
Stop pumping into ethyl acetate solvent, when temperature is increased to 140 DEG C in question response still again after the isolated water yield reaches 281kg
Starting to pump into ethyl acetate solvent, start second time circulation, water yield stops pumping into solvent when reaching 211kg for the second time, and the 3rd
Stop when secondary water yield reaches 106kg pumping into solvent, stop when the 4th time water yield reaches 70kg pumping into solvent, the 5th water outlet
Stop when amount reaches 35kg pumping into solvent, after so circulating 5 times, temperature is increased to 160 DEG C of insulation 6h.
S104: hydrolysis: add water in the reactant liquor in described step S103, stirs 30min at 110 DEG C and carries out water
Solving, it is 17% that hydrolytic acidity controls；
S105: condensation: adding 300kg concentration in thread mode in the reactant liquor in described step S104 under the conditions of 95 DEG C is
The formaldehyde of 37%, 5h adds, and is warming up to 100 DEG C of condensation 3h, adds water immediately, stir 1h after being condensed after being added dropwise to complete；
S106: neutralize: add Caustic soda in the reactant liquor in described step S105 and neutralize, be 7 to pH value, obtain naphthalene system of naphthalene system and subtract
Water preparation.
Embodiment 5
Disclosure embodiment provides a kind solvent method to concentrate the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, as
Shown in Fig. 2, comprise the following steps:
S101: feed intake: add 5000kg liquid naphthalene in the reactor of 12.5m, and carry out steam intensification；
S102: sulfonation: start addition 98% concentrated sulphuric acid 4400kg slowly, at the uniform velocity when the temperature of liquid naphthalene rises to 142 DEG C,
50min adds, and continues steam and heat up after acid adding, is incubated 2.5h, carries out sulfonating reaction after being warming up to 162 DEG C；
S103: dehydration: being continuously pumped into benzene solvent in the reactant liquor of described step S102, solvent takes sulfonation out of when vaporization at high temperature
The water that reaction produces, separates water with benzene solvent after condensation, and isolated solvent continues to pump in reactor, when isolated water
Amount stops pumping into benzene solvent after reaching 492kg, and in question response still, temperature is increased to when 160 DEG C start again at pump into benzene solvent, opens
The second time that begins circulation, water yield stops pumping into solvent when reaching 106kg for the second time, and water yield reaches to stop pump during 70kg for the third time
Enter solvent, stop when the 4th time water yield reaches 35kg pumping into solvent, after so circulating 4 times, temperature is increased to 160 DEG C of insulations
2h。
S104: sub-material: the reactant liquor in described step S103 is transferred in the condensation kettle of 5 3m respectively, successively；
S105: hydrolysis: add 100L water in the reactant liquor in described step S104, stirs 30min at 110 DEG C and carries out water
Solving, it is 18% that hydrolytic acidity controls；
S106: condensation: under the conditions of 100 DEG C, add 3500kg in thread mode in the reactant liquor in described step S105 dense
Degree is the formaldehyde of 37%, and 2h adds, and is warming up to 115 DEG C of condensation 20h, adds 200L water immediately, stir after being condensed after being added dropwise to complete
Mix 1h；
S107: neutralize: add Caustic soda in the reactant liquor in described step S106 and neutralize, be 8 to pH value, obtain naphthalene system of naphthalene system and subtract
Water preparation.
Embodiment 6
Disclosure embodiment provides a kind solvent method to concentrate the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, as
Shown in Fig. 3, comprise the following steps:
S101: feed intake: add 5200kg liquid naphthalene in the reactor of 15m, and carry out steam intensification；
S102: sulfonation: start addition 98% concentrated sulphuric acid 4500kg slowly, at the uniform velocity when the temperature of liquid naphthalene rises to 145 DEG C,
60min adds, and continues steam and heat up after acid adding, is incubated 2.5h, carries out sulfonating reaction after being warming up to 163 DEG C；
S103: dehydration: being continuously pumped into chloroform solvent in the reactant liquor of described step S102, solvent takes sulphur out of when vaporization at high temperature
Changing the water that reaction produces, separated with chloroform solvent by water after condensation, isolated solvent continues to pump in reactor, when isolating
The water yield reach 278kg after stop pumping into solvent, in question response still, temperature is increased to when 150 DEG C start again at that to pump into chloroform molten
Agent, starts second time circulation, and water yield stops pumping into solvent, when water yield reaches 110kg for the third time when reaching 219kg for the second time
Stopping pumping into solvent, stop pumping into solvent when the 4th time water yield reaches 88kg, the 5th water yield reaches to stop pump during 36kg
Enter solvent, after so circulating 5 times, temperature is increased to 165 DEG C of insulation 2h.
S104: hydrolysis: add 800L water in the reactant liquor in described step S103, stirs 30min at 110 DEG C and carries out
Hydrolysis, it is 19% that hydrolytic acidity controls；
S105: sub-material: the reactant liquor in described step S104 is transferred in the condensation kettle of 8 6m respectively, successively；
S106: condensation: add 3600kg concentration in thread mode in the reactant liquor in described step S105 under the conditions of 100 DEG C
Being the formaldehyde of 37%, 2h adds, and is warming up to 110 DEG C of condensation 5h, adds 200L water immediately, stirring after being condensed after being added dropwise to complete
2h；
S107: neutralize: add Caustic soda in the reactant liquor in described step S106 and neutralize, be 9 to pH value, obtain naphthalene system of naphthalene system and subtract
Water preparation.
Embodiment 7
Disclosure embodiment provides a kind solvent method to concentrate the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, as
Shown in Fig. 2, comprise the following steps:
S101: feed intake: add 5000kg liquid naphthalene in the reactor of 12.5m, and carry out steam intensification；
S102: sulfonation: start addition 98% concentrated sulphuric acid 4400kg slowly, at the uniform velocity when the temperature of liquid naphthalene rises to 142 DEG C,
50min adds, and continues steam and heat up after acid adding, is incubated 2.5h, carries out sulfonating reaction after being warming up to 162 DEG C；
S103: dehydration: being continuously pumped into benzene solvent in the reactant liquor of described step S102, solvent takes sulfonation out of when vaporization at high temperature
The water that reaction produces, separates water with benzene solvent after condensation, and isolated solvent continues to pump in reactor, when isolated water
Amount stops pumping into benzene solvent after reaching 351kg, and in question response still, temperature is increased to when 160 DEG C start again at pump into benzene solvent, opens
The second time that begins circulation, water yield stops pumping into solvent when reaching 141kg for the second time, and water yield reaches to stop pump during 70kg for the third time
Enter solvent, stop when the 4th time water yield reaches 141kg pumping into solvent, after so circulating 4 times, temperature is increased to 160 DEG C of insulations
2h。
S104: sub-material: the reactant liquor in described step S103 is transferred in the condensation kettle of 5 3m respectively, successively；
S105: hydrolysis: add 100L water in the reactant liquor in described step S104, stirs 30min at 110 DEG C and carries out water
Solving, it is 18% that hydrolytic acidity controls；
S106: condensation: under the conditions of 100 DEG C, add 3500kg in thread mode in the reactant liquor in described step S105 dense
Degree is the formaldehyde of 37%, and 2h adds, and is warming up to 115 DEG C of condensation 20h, adds 200L water immediately, stir after being condensed after being added dropwise to complete
Mix 1h；
S107: neutralize: add Caustic soda in the reactant liquor in described step S106 and neutralize, be 8 to pH value, obtain naphthalene system of naphthalene system and subtract
Water preparation.
Embodiment 8
Disclosure embodiment provides a kind solvent method to concentrate the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, as
Shown in Fig. 3, comprise the following steps:
S101: feed intake: add 5200kg liquid naphthalene in the reactor of 15m, and carry out steam intensification；
S102: sulfonation: start addition 98% concentrated sulphuric acid 4500kg slowly, at the uniform velocity when the temperature of liquid naphthalene rises to 145 DEG C,
60min adds, and continues steam and heat up after acid adding, is incubated 2.5h, carries out sulfonating reaction after being warming up to 163 DEG C；
S103: dehydration: being continuously pumped into chloroform solvent in the reactant liquor of described step S102, solvent takes sulphur out of when vaporization at high temperature
Changing the water that reaction produces, separated with chloroform solvent by water after condensation, isolated solvent continues to pump in reactor, when isolating
The water yield reach 372kg after stop pumping into solvent, in question response still, temperature is increased to when 150 DEG C start again at that to pump into chloroform molten
Agent, starts second time circulation, and water yield stops pumping into solvent when reaching 62kg for the second time, and water yield reaches to stop during 93kg for the third time
Only pump into solvent, stop when the 4th time water yield reaches 74kg pumping into solvent, stop when the 5th time water yield reaches 19kg pumping into
Solvent, is increased to 165 DEG C of insulation 2h by temperature after so circulating 5 times.
S104: hydrolysis: add 800L water in the reactant liquor in described step S103, stirs 30min at 110 DEG C and carries out
Hydrolysis, it is 19% that hydrolytic acidity controls；
S105: sub-material: the reactant liquor in described step S104 is transferred in the condensation kettle of 8 6m respectively, successively；
S106: condensation: add 3600kg concentration in thread mode in the reactant liquor in described step S105 under the conditions of 100 DEG C
Being the formaldehyde of 37%, 2h adds, and is warming up to 110 DEG C of condensation 5h, adds 200L water immediately, stirring after being condensed after being added dropwise to complete
2h；
S107: neutralize: add Caustic soda in the reactant liquor in described step S106 and neutralize, be 9 to pH value, obtain naphthalene system of naphthalene system and subtract
Water preparation.
The above is only the detailed description of the invention of the present invention, makes to skilled artisans appreciate that or realize this
Bright.Multiple amendment to these embodiments will be apparent to one skilled in the art, as defined herein
General Principle can realize without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and principles disclosed herein and features of novelty phase one
The widest scope caused.
Claims (7)
1. the production method that a solvent method concentrates the condensation of sulfonation separate mealing type to produce naphthalene water reducer, it is characterised in that described life
Product method comprises the following steps: to feed intake, sulfonation, be dehydrated, hydrolyze, be condensed and neutralize, and wherein, described dehydration is: to equipped with
Being continuously pumped into solvent in the reactor of sulfonating reaction liquid, the water that sulfonating reaction produces taken out of by solvent when vaporization at high temperature, after condensation
Being separated with solvent by water, isolated solvent pumps in reactor again, when water yield reaches the setting hundred of sulfonating reaction water yield
Stopping after proportion by subtraction pumping into solvent, in question response still, temperature is increased to when 140～170 DEG C start again at pump into solvent, starts next
Secondary circulation, is finally increased to 160～165 DEG C of insulations 1～6h by temperature.
Solvent method the most according to claim 1 concentrates the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, its
Being characterised by, the cycle-index in described dehydration is 4 times, described sulfonating reaction water yield set percentage ratio as: 40～
70%, 15～45%, 10～30%, 5～20%.
Solvent method the most according to claim 1 concentrates the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, its
Being characterised by, the cycle-index in described dehydration is 5 times, described sulfonating reaction water yield set percentage ratio as: 40～
70%, 10～30%, 10～15%, 5～12%, 3～5%.
4. concentrate the condensation of sulfonation separate mealing type to produce the production of naphthalene water reducer according to the solvent method described in any one of claim 1-3
Method, it is characterised in that also include sub-material step between described hydrolysing step and condensation step: by be dehydrated in reactor
Reactant liquor is transferred at least one condensation kettle the most successively, and described condensation and neutralization procedure are all carried out in described condensation kettle.
5. concentrate the condensation of sulfonation separate mealing type to produce the production of naphthalene water reducer according to the solvent method described in any one of claim 1-3
Method, it is characterised in that also include sub-material step between described dehydration and hydrolysing step: by be dehydrated in reactor
Reactant liquor is transferred at least one condensation kettle the most successively, and described hydrolysis, condensation and neutralization procedure are all in described condensation kettle
Carry out.
Solvent method the most according to claim 5 concentrates the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, its
Being characterised by, the capacity of described condensation kettle is 2m3～20m3。
Solvent method the most according to claim 6 concentrates the condensation of sulfonation separate mealing type to produce the production method of naphthalene water reducer, its
Being characterised by, the capacity of described reactor is at least 3m3。
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| CN107619693A (en) * | 2017-10-10 | 2018-01-23 | 陕西立雅能源科技有限公司 | A kind of slurries additive agent and its preparation method and application |
| 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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