CN106117481B - A kind of solvent method concentrates the production method of sulfonation separate mealing type condensation production naphthalene water reducer - Google Patents
A kind of solvent method concentrates the production method of sulfonation separate mealing type condensation production naphthalene water reducer Download PDFInfo
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- CN106117481B CN106117481B CN201610467983.9A CN201610467983A CN106117481B CN 106117481 B CN106117481 B CN 106117481B CN 201610467983 A CN201610467983 A CN 201610467983A CN 106117481 B CN106117481 B CN 106117481B
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- 239000002904 solvent Substances 0.000 title claims abstract description 130
- 238000009833 condensation Methods 0.000 title claims abstract description 100
- 230000005494 condensation Effects 0.000 title claims abstract description 100
- 238000006277 sulfonation reaction Methods 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 43
- 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 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 152
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 117
- 230000018044 dehydration Effects 0.000 claims abstract description 29
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 29
- 230000007062 hydrolysis Effects 0.000 claims abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 22
- 230000003301 hydrolyzing effect Effects 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 11
- 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
- 235000021050 feed intake Nutrition 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 74
- 239000002253 acid Substances 0.000 abstract description 17
- 238000006482 condensation reaction Methods 0.000 abstract description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000010802 sludge Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- -1 naphthalene sulfonic acids Chemical class 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000010792 warming Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 150000002790 naphthalenes Chemical class 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000630 rising effect Effects 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 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
- 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
- 230000009467 reduction 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
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010924 continuous production Methods 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
- 230000000694 effects Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 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
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010025 steaming Methods 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)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides the production method that a kind of solvent method concentrates sulfonation separate mealing type condensation production naphthalene water reducer, including feeding intake, sulfonation, dehydration, hydrolysis, condensation, neutralize and etc., using low complex acid amount sulfonation, disulfonic acid or more sulfonic acid are not generated, improve the selectivity of β~naphthalene sulfonic acids, the quality of water-reducing agent is improved, reduces waste sludge discharge；Using solvent during sulfonation, using water yield as reaction end desired value, dehydration every time is gradually reduced using quantity of solvent, solvent usage amount is reduced to greatest extent, so as to reduce thermal loss；Sulfonation is concentrated using large-volume reaction kettle, takes full advantage of exothermic heat of reaction, temperature of reaction kettle is kept, reduces steam usage amount；Reduce exhaust gas discharge；Condensation reaction is not with pressure, safe.
Description
Technical field
The present invention relates to concrete admixture production technical fields more particularly to a kind of solvent method to concentrate the contracting of sulfonation separate mealing type
The production method of naphthalene water reducer is produced in symphysis.
Background technology
Water-reducing agent is outside a kind of concrete that under conditions of maintaining concrete slump constant, can reduce mixing water amount
Add agent.Belong to anion surfactant mostly, there is lignosulfonates, naphthalene sulphonate formaldehyde polymer etc..Add in concrete
There is peptizaiton to cement granules after mixture, its workability can be improved, reduce unit consumption of water, improve concrete mix
Mobility；Or unit cement consumption is reduced, save cement.
Naphthalene water reducer is widely used high efficiency water reducing agent, is a kind of super plasticizer, and there is good diminishing early to pretend
With mostly applied in Concrete Industry, being also applied to the industries such as plasterboard, water-coal-slurry, ceramics, oil well.Its production technology is main
It is to put into crude naphthalene in reaction kettle, is warming up to certain temperature, the concentrated sulfuric acid is added dropwise while stirring and carries out sulfonation, heat preservation, water
Solution, adds formaldehyde condensation, neutralizes, and dries and obtains, at present, general production method is that sulfonation is carried out in 5 cubes of reaction kettles, sulphur
After the completion of change, formaldehyde condensation is added dropwise in same reaction kettle, such operation has following four problem：（1）It is extensive raw
During production, since refrigerant and heating agent are used alternatingly, thermal loss is big；（2）Single batch operation heat scatters and disappears seriously, does not make full use of
Exothermic heat of reaction；（3）Area is big during reaction, and exhaust gas volatile quantity is big；（4）Low production efficiency, it is impossible to realize continuous production；（5）Work
When industry naphthalene is with sulfuric acid sulfonation, especially with the sulfuric acid of high concentration, such as 100%, 105%, 120% when the high concentrations concentrated sulfuric acid, dense
Sulfuric acid cannot disperse in time, be contacted with naphthalene, easily produce disulfonic acid or more sulfonic acid, make the selectivity of β~naphthalene sulfonic acids reduce, shadow
Next step formaldehyde condensation is rung, influences the quality of water-reducing agent.
It, can be to avoid depositing above if there is a kind of heat utilization rate method that is high, and can realizing serialization large-scale production
The problem of, it is possible to greatly improve production efficiency.The present invention is based on problem above, have invented a kind of solvent method and have concentrated sulfonation point
The production method of meal formula condensation production naphthalene water reducer, heat utilization rate is high, high-quality, can realize serialization large-scale production
It is required that improve production efficiency.
Invention content
It is an object of the present invention to having overcome the deficiencies of the prior art and provide 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, avoids more sulfonation, and energy saving, reduction is given up
Gas, and can realize that serialization improves the requirement of production efficiency.
In order to solve the above technical problems, the technical scheme is that：A kind of solvent method is provided and concentrates the contracting of sulfonation separate mealing type
The production method of naphthalene water reducer is produced in symphysis, and the production method includes the following steps：Feed intake, sulfonation, dehydration, hydrolysis, condensation
And neutralization, wherein, the dehydration is：Solvent is continuously pumped into the reaction kettle equipped with sulfonating reaction liquid, solvent is in high temperature
It takes the water of sulfonating reaction generation during volatilization out of, detaches water and solvent after condensation, the solvent isolated is pumped into reaction kettle again, when
Water yield stops being pumped into solvent after reaching the setting percentage of sulfonating reaction water yield, treat in reaction kettle temperature be increased to 140~
It is started again at 170 DEG C and is pumped into solvent, start to recycle next time, 160~165 DEG C of 1~6h of heat preservation are raised the temperature to after last.
Preferably, the sulfonating reaction water yield set percentage as：40~70%, 15~45%, 10~30%, 5~
20%。
Preferably, the sulfonating reaction water yield set percentage as：40~70%, 10~30%, 10~15%, 5~
12%th, 3~5%.
Solvent dehydration, using water yield as reaction end desired value, the setting hundred of sulfonating reaction water yield are used after sulfonation
Divide and reduced than successively, dehydration every time is gradually reduced using quantity of solvent, reduces solvent usage amount to greatest extent, so as to reduce heat
Amount loss.
Preferably, sub-material is further included between the dehydration and hydrolysing step：The reaction of completion will be dehydrated in reaction kettle
Liquid is transferred at least one condensation kettle successively respectively, and the hydrolysis, condensation and neutralization procedure carry out in the condensation kettle.
Preferably, sub-material step is further included between the hydrolysing step and condensation step：Dehydration in reaction kettle is completed
Reaction solution is transferred at least one condensation kettle successively respectively, and the condensation and neutralization procedure carry out in the condensation kettle,
The hydrolysing step carries out in a kettle.
The reaction solution for hydrolyzing completion is transferred in condensation kettle and carries out subsequent condensation and neutralization procedure, sulfonation in reaction kettle
The temperature requirement of reaction and hydrolysis is relatively high, and condensation reaction requirement temperature is relatively low, and sulfonation and condensation are distinguished
It is carried out in different containers, avoids hot and cold alternation, reduce thermal losses.
Preferably, sub-material step is further included between the dehydration and hydrolysing step：Dehydration in reaction kettle is completed
Reaction solution is transferred at least one condensation kettle successively respectively, and the hydrolysis, condensation and neutralization procedure are in the condensation kettle
It carries out.
The reaction solution for being dehydrated completion is transferred in condensation kettle and carries out subsequent hydrolysis, condensation and neutralization procedure, reaction kettle
Middle sulfonating reaction temperature is high, and hydrolyze, setting-up point it is low, by sulfonation and hydrolysis, condensation separately progress, avoid cold and hot friendship
It replaces, reduces thermal losses.
Preferably, the capacity of the condensation kettle is 2m3~20m3。
Preferably, the capacity of the reaction kettle is at least 3m3。
Sulfonation is concentrated using large-volume reaction kettle, takes full advantage of exothermic heat of reaction, temperature of reaction kettle is kept, reduces thermal energy
Usage amount.
Preferably, the material addition step is：The naphthalene through metering is put into reaction kettle.
Preferably, the sulfonation procedure is：By equipped with naphthalene reaction kettle heat up, when naphthalene in reaction kettle temperature rise extremely
At 140~145 DEG C, the concentrated sulfuric acid is added in, preferably with 98% concentrated sulfuric acid, the subsequent temperature of continuing rising of acid adding carries out under the conditions of 160~165 DEG C
Sulfonating reaction, wherein, the concentrated sulfuric acid of addition and the weight ratio of naphthalene are 0.65~0.88:1, it is low complex acid amount sulfonation, does not give birth to
Disulfonic acid or more sulfonic acid are produced, improves the selectivity of beta-naphthalenesulfonic-acid, improves the quality of water-reducing agent, reduces waste sludge discharge.
The reaction equation of the sulfonating reaction is：
There is water generation as shown in above formula, in sulfonating reaction, the dehydration in sulfonating reaction step generating
Water removes, and solvent is continuously pumped into the reaction kettle equipped with sulfonating reaction liquid, and solvent takes sulfonating reaction production out of in vaporization at high temperature
Raw water detaches water and solvent after condensation, and the solvent isolated continues to be pumped into reaction kettle, and solvent is recycled, point
The water separated out stops being pumped into solvent after reaching some percentage of sulfonating reaction theory water yield, and sulfonating reaction generates to obtain water at this time
A part is taken out of by solvent, the concentration of residual sulfuric acid is made to be further enhanced, reaction is promoted to carry out to the right, improves naphthalene sulfonic acids
Conversion ratio, sulfonating reaction releases heat, increases in reaction kettle temperature, started again at when temperature rise is to 140~170 DEG C
Solvent is pumped into, starts second and recycles；The percentage setting of sulfonating reaction theory water yield is reduced successively, for example, working as 100mol
Naphthalene and 100mol the concentrated sulfuric acid carry out sulfonating reaction when, theoretically generate 100mol water, when cycle-index in dehydration
When being four times, the percentage for setting water yield successively is followed successively by 40%, 30%, 20%, 10%, that is, start for the first time after being pumped into solvent,
The water detached after condensation reaches the 40% of 100mol, i.e. during 40mol（Weight can be converted into）, stop being pumped into solvent, work as temperature
It is started again at when rising to 160 DEG C and is pumped into solvent for the second time, when the water detached after condensation reaches the 30% of 100mol, stop pump
Enter solvent, and so on.
After the dehydration is completed, the reaction solution in reaction kettle is taken to survey its acidity should be between 20~25%.
Preferably, the hydrolysing step is：Water is added in reaction solution into the condensation kettle, the water under the conditions of 110 DEG C
30min is solved, hydrolysis while, stirs, and hydrolytic acidity is controlled 17~22%, wherein, the water of addition is 100~800L.
Preferably, the condensation step is：It is added in reaction solution under the conditions of 95~100 DEG C into the hydrolysing step
Formaldehyde adds the formaldehyde time for 2~5h, and 100~115 DEG C of 2~20h of condensation are warming up to after adding formaldehyde.
The reaction equation of condensation reaction is：
Preferably, in the condensation reaction, when the net rising value of electric current reaches 5~20A, condensation is terminated, immediately
Water is added in, is stirred 1~5 hour, to control the degree of polymerization of naphthalene sulfonic acid-formaldehyde condensation product（Molecular weight）Will not be too high with material viscosity,
And condensation reaction is not with pressure, safety.
Preferably, the neutralization procedure is：In reaction solution into the condensation step add in alkali neutralization to PH be 7~9,
Obtain naphthalene water reducer.
Preferably, the solvent for carbon disulfide, pyridine, dimethylbenzene, toluene, benzene, dichloroethanes, carbon tetrachloride, chloroform,
One or more kinds of mixtures in dioxane, ethyl acetate, acrylonitrile and tetrachloromethane.
The advantageous effect of technical solution provided by the invention：
1st, naphthalene and sulfuric acid dosage ratio are 1 in common process：1.3~1.5, naphthalene and sulfuric acid dosage in technique provided by the invention
Than being 1:0.65~0.88, this technique uses low complex acid amount sulfonation, does not produce disulfonic acid or more sulfonic acid, improves β~naphthalene sulphur
The selectivity of acid, improves the quality of water-reducing agent, reduces waste sludge discharge；
2nd, it is energy saving, using solvent during sulfonation, using water yield as reaction end desired value, every time dehydration use quantity of solvent by
Secondary reduction, reduces solvent usage amount to greatest extent, so as to reduce thermal loss；
3rd, sulfonation is concentrated using large-volume reaction kettle, takes full advantage of exothermic heat of reaction, kept temperature of reaction kettle, reduce steaming
Vapour usage amount；Reduce exhaust gas discharge；
4th, increase sub-material step, by the higher sulfonating reaction step of demand temperature and the relatively low subsequent water of demand temperature
Solution, step of condensation, which are divided into different containers, to be carried out, and is avoided hot and cold alternation, is saved thermal losses.
5th, condensation reaction is not with pressure, safety.
6th, this method energy while multiscale water-reducing agent product, produce sodium sulphate content 0.1~20%, alkali content 0.01~18%
Naphthalene water reducer.
7th, reduce the discharge containing sulfur dioxide, sulfuric acid mist and naphthalene exhaust gas.
Description of the drawings
Fig. 1 is the life that a kind of solvent method provided in an embodiment of the present invention concentrates sulfonation separate mealing type condensation production naphthalene water reducer
The flow diagram of production method.
Fig. 2 is that another solvent method provided in an embodiment of the present invention concentrates sulfonation separate mealing type condensation production naphthalene water reducer
The flow diagram of production method.
Fig. 3 is that the third solvent method provided in an embodiment of the present invention concentrates sulfonation separate mealing type condensation production naphthalene water reducer
The flow diagram of production method.
Specific embodiment
In order to which those skilled in the art is made to more fully understand the technical solution in the present invention, below in conjunction with of the invention real
The attached drawing in example is applied, the technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described implementation
Example is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiments obtained without making creative work, should all belong to protection of the present invention
Range.
Embodiment 1
The embodiment of the present disclosure provides the producer that a kind solvent method concentrates sulfonation separate mealing type condensation production naphthalene water reducer
Method, as shown in Figure 1, including the following steps：
S101：It feeds intake：5000kg liquid naphthalenes are added in into the reaction kettle of 12.5m3, and carry out steam heating；
S102：Sulfonation：Start slow, 98% concentrated sulfuric acid of addition at the uniform velocity when the temperature of liquid naphthalene rises to 140 DEG C
4250kg, 60min are added, and continue steam heating after acid adding, 4h is kept the temperature after being warming up to 160 DEG C, carry out sulfonating reaction；
S103：Dehydration：Ethyl acetate solvent is continuously pumped into the reaction solution of the step S102, solvent is in vaporization at high temperature
When take the water of sulfonating reaction generation out of, water and ethyl acetate solvent are detached after condensation, the solvent isolated continues to be pumped into reaction
In kettle, stop being pumped into ethyl acetate solvent after the water isolated reaches 281kg, treat that temperature is increased to 140 DEG C in reaction kettle
When start again at and be pumped into ethyl acetate solvent, start second and recycle, stop being pumped into when second of water yield reaches 317kg molten
Agent stops being pumped into solvent when third time water yield reaches 70kg, stops being pumped into solvent when water yield reaches 35kg for the 4th time, so
160 DEG C of heat preservation 6h are raised the temperature to after recycling 4 times.
S104：Hydrolysis：Water is added in reaction solution into the step S103,30min is stirred at 110 DEG C and carries out water
Solution, hydrolytic acidity control are 17%；
S105：Condensation：It is dense that 300kg is added in a manner of thread in reaction solution under the conditions of 95 DEG C into the step S104
The formaldehyde for 37% is spent, 5h is added, and 100 DEG C of condensation 3h are warming up to after being added dropwise to complete, water is added in after the completion of condensation immediately, stirs 1h；
S106：It neutralizes：Caustic soda is added in reaction solution into the step S105 to neutralize, until pH value is 7, obtains naphthalene system naphthalene
Based water reducer.
Embodiment 2
The embodiment of the present disclosure provides the producer that a kind solvent method concentrates sulfonation separate mealing type condensation production naphthalene water reducer
Method, as shown in Figure 1, including the following steps：
S101：It feeds intake：5200kg liquid naphthalenes are added in into 20m3 reaction kettles, and carry out steam heating；
S102：Sulfonation：Start slow, 98% concentrated sulfuric acid of addition at the uniform velocity when the temperature of liquid naphthalene rises to 145 DEG C
3380kg, 70min are added, and continue steam heating after acid adding, 2.5h is kept the temperature after being warming up to 165 DEG C, carry out sulfonating reaction；
S103：Dehydration：Xylene solvent is continuously pumped into the reaction solution of the step S102, solvent is in vaporization at high temperature
It takes the water of sulfonating reaction generation out of, detaches water and xylene solvent after condensation, the solvent isolated continues to be pumped into reaction kettle,
Stop being pumped into solvent after the water isolated reaches 434kg, start again at and be pumped into when temperature in reaction kettle is increased to 170 DEG C
Xylene solvent, starts second and recycles, and stops being pumped into solvent when second of water yield reaches 74kg, third time water yield reaches
Stop being pumped into solvent during 62kg, stop being pumped into solvent for the 4th time when water yield reaches 31kg, when the 5th time water yield reaches 19kg
Stopping is pumped into solvent, and 165 DEG C of heat preservation 1h are raised the temperature to after so recycling 5 times.
S104：Hydrolysis：Water is added in reaction solution into the step S103,30min is stirred at 110 DEG C and carries out water
Solution, hydrolytic acidity 22%；
S105：Condensation：3120kg is added in a manner of thread in reaction solution under the conditions of 98 DEG C into the step S104
A concentration of 37% formaldehyde, 3h are added, and 115 DEG C of condensation 2h are warming up to after being added dropwise to complete, water is added in immediately after the completion of condensation, stirs
5h；
S106：It neutralizes：Caustic soda is added in reaction solution into the step S105 to neutralize, until pH value is 9, obtains naphthalene system naphthalene
Based water reducer.
Embodiment 3
The embodiment of the present disclosure provides the producer that a kind solvent method concentrates sulfonation separate mealing type condensation production naphthalene water reducer
Method, as shown in Figure 1, including the following steps：
S101：It feeds intake：5200kg liquid naphthalenes are added in into 20m3 reaction kettles, and carry out steam heating；
S102：Sulfonation：Start slow, 98% concentrated sulfuric acid of addition at the uniform velocity when the temperature of liquid naphthalene rises to 145 DEG C
3380kg, 70min are added, and continue steam heating after acid adding, 2.5h is kept the temperature after being warming up to 165 DEG C, carry out sulfonating reaction；
S103：Dehydration：Xylene solvent is continuously pumped into the reaction solution of the step S102, solvent is in vaporization at high temperature
It takes the water of sulfonating reaction generation out of, detaches water and xylene solvent after condensation, the solvent isolated continues to be pumped into reaction kettle,
Stop being pumped into solvent after the water isolated reaches 248kg, start again at and be pumped into when temperature in reaction kettle is increased to 170 DEG C
Xylene solvent, starts second and recycles, and stops being pumped into solvent when second of water yield reaches 93kg, third time water yield reaches
Stop being pumped into solvent during 186kg, stop being pumped into solvent when water yield reaches 93kg for the 4th time, so by temperature liter after cycle 4 times
Up to 165 DEG C heat preservation 1h.
S104：Hydrolysis：Water is added in reaction solution into the step S103,30min is stirred at 110 DEG C and carries out water
Solution, hydrolytic acidity 22%；
S105：Condensation：3120kg is added in a manner of thread in reaction solution under the conditions of 98 DEG C into the step S104
A concentration of 37% formaldehyde, 3h are added, and 115 DEG C of condensation 2h are warming up to after being added dropwise to complete, water is added in immediately after the completion of condensation, stirs
5h；
S106：It neutralizes：Caustic soda is added in reaction solution into the step S105 to neutralize, until pH value is 9, obtains naphthalene system naphthalene
Based water reducer.
Embodiment 4
The embodiment of the present disclosure provides the producer that a kind solvent method concentrates sulfonation separate mealing type condensation production naphthalene water reducer
Method, as shown in Figure 1, including the following steps：
S101：It feeds intake：5000kg liquid naphthalenes are added in into the reaction kettle of 12.5m3, and carry out steam heating；
S102：Sulfonation：Start slow, 98% concentrated sulfuric acid of addition at the uniform velocity when the temperature of liquid naphthalene rises to 140 DEG C
4250kg, 60min are added, and continue steam heating after acid adding, 4h is kept the temperature after being warming up to 160 DEG C, carry out sulfonating reaction；
S103：Dehydration：Ethyl acetate solvent is continuously pumped into the reaction solution of the step S102, solvent is in vaporization at high temperature
When take the water of sulfonating reaction generation out of, water and ethyl acetate solvent are detached after condensation, the solvent isolated continues to be pumped into reaction
In kettle, stop being pumped into ethyl acetate solvent after the water isolated reaches 281kg, treat that temperature is increased to 140 DEG C in reaction kettle
When start again at and be pumped into ethyl acetate solvent, start second and recycle, stop being pumped into when second of water yield reaches 211kg molten
Agent stops being pumped into solvent when third time water yield reaches 106kg, stops being pumped into solvent when water yield reaches 70kg for the 4th time, the
Stop being pumped into solvent when five times water yield reaches 35kg, so raise the temperature to 160 DEG C of heat preservation 6h after cycle 5 times.
S104：Hydrolysis：Water is added in reaction solution into the step S103,30min is stirred at 110 DEG C and carries out water
Solution, hydrolytic acidity control are 17%；
S105：Condensation：It is dense that 300kg is added in a manner of thread in reaction solution under the conditions of 95 DEG C into the step S104
The formaldehyde for 37% is spent, 5h is added, and 100 DEG C of condensation 3h are warming up to after being added dropwise to complete, water is added in after the completion of condensation immediately, stirs 1h；
S106：It neutralizes：Caustic soda is added in reaction solution into the step S105 to neutralize, until pH value is 7, obtains naphthalene system naphthalene
Based water reducer.
Embodiment 5
The embodiment of the present disclosure provides the producer that a kind solvent method concentrates sulfonation separate mealing type condensation production naphthalene water reducer
Method, as shown in Fig. 2, including the following steps：
S101：It feeds intake：5000kg liquid naphthalenes are added in into the reaction kettle of 12.5m3, and carry out steam heating；
S102：Sulfonation：Start slow, 98% concentrated sulfuric acid of addition at the uniform velocity when the temperature of liquid naphthalene rises to 142 DEG C
4400kg, 50min are added, and continue steam heating after acid adding, 2.5h is kept the temperature after being warming up to 162 DEG C, carry out sulfonating reaction；
S103：Dehydration：Benzene solvent is continuously pumped into the reaction solution of the step S102, solvent is taken out of in vaporization at high temperature
The water that sulfonating reaction generates detaches water and benzene solvent after condensation, and the solvent isolated continues to be pumped into reaction kettle, when isolating
Water reach and stop after 492kg being pumped into benzene solvent, start again at that be pumped into benzene molten when temperature in reaction kettle is increased to 160 DEG C
Agent, starts second and recycles, and stops being pumped into solvent when second of water yield reaches 106kg, when third time water yield reaches 70kg
Stopping is pumped into solvent, stops being pumped into solvent when water yield reaches 35kg for the 4th time, so raises the temperature to 160 after cycle 4 times
DEG C heat preservation 2h.
S104：Sub-material：Reaction solution in the step S103 is transferred in the condensation kettle of 5 3m3 respectively, successively；
S105：Hydrolysis：100L water is added in reaction solution into the step S104,30min is stirred at 110 DEG C and is carried out
Hydrolysis, hydrolytic acidity control are 18%；
S106：Condensation：Under the conditions of 100 DEG C, added in a manner of thread in the reaction solution into the step S105
The formaldehyde of 3500kg a concentration of 37%, 2h are added, and 115 DEG C of condensation 20h are warming up to after being added dropwise to complete, are added in immediately after the completion of condensation
200L water stirs 1h；
S107：It neutralizes：Caustic soda is added in reaction solution into the step S106 to neutralize, until pH value is 8, obtains naphthalene system naphthalene
Based water reducer.
Embodiment 6
The embodiment of the present disclosure provides the producer that a kind solvent method concentrates sulfonation separate mealing type condensation production naphthalene water reducer
Method, as shown in figure 3, including the following steps：
S101：It feeds intake：5200kg liquid naphthalenes are added in into the reaction kettle of 15m3, and carry out steam heating；
S102：Sulfonation：Start slow, 98% concentrated sulfuric acid of addition at the uniform velocity when the temperature of liquid naphthalene rises to 145 DEG C
4500kg, 60min are added, and continue steam heating after acid adding, 2.5h is kept the temperature after being warming up to 163 DEG C, carry out sulfonating reaction；
S103：Dehydration：Chloroform solvent, solvent band in vaporization at high temperature are continuously pumped into the reaction solution of the step S102
Go out the water of sulfonating reaction generation, detach water and chloroform solvent after condensation, the solvent isolated continues to be pumped into reaction kettle, when point
The water separated out stops being pumped into solvent after reaching 278kg, is started again at when temperature in reaction kettle is increased to 150 DEG C and is pumped into chloroform
Solvent, starts second and recycles, and stops being pumped into solvent when second of water yield reaches 219kg, third time water yield reaches 110kg
When stop being pumped into solvent, stop being pumped into solvent when water yield reaches 88kg for the 4th time, stop when water yield reaches 36kg for the 5th time
Solvent is pumped into, 165 DEG C of heat preservation 2h are raised the temperature to after so recycling 5 times.
S104：Hydrolysis：800L water is added in reaction solution into the step S103,30min is stirred at 110 DEG C and is carried out
Hydrolysis, hydrolytic acidity control are 19%；
S105：Sub-material：Reaction solution in the step S104 is transferred in the condensation kettle of 8 6m3 respectively, successively；
S106：Condensation：3600kg is added in a manner of thread in reaction solution under the conditions of 100 DEG C into the step S105
A concentration of 37% formaldehyde, 2h are added, and 110 DEG C of condensation 5h are warming up to after being added dropwise to complete, add in 200L water after the completion of condensation immediately,
Stir 2h；
S107：It neutralizes：Caustic soda is added in reaction solution into the step S106 to neutralize, until pH value is 9, obtains naphthalene system naphthalene
Based water reducer.
Embodiment 7
The embodiment of the present disclosure provides the producer that a kind solvent method concentrates sulfonation separate mealing type condensation production naphthalene water reducer
Method, as shown in Fig. 2, including the following steps：
S101：It feeds intake：5000kg liquid naphthalenes are added in into the reaction kettle of 12.5m3, and carry out steam heating；
S102：Sulfonation：Start slow, 98% concentrated sulfuric acid of addition at the uniform velocity when the temperature of liquid naphthalene rises to 142 DEG C
4400kg, 50min are added, and continue steam heating after acid adding, 2.5h is kept the temperature after being warming up to 162 DEG C, carry out sulfonating reaction；
S103：Dehydration：Benzene solvent is continuously pumped into the reaction solution of the step S102, solvent is taken out of in vaporization at high temperature
The water that sulfonating reaction generates detaches water and benzene solvent after condensation, and the solvent isolated continues to be pumped into reaction kettle, when isolating
Water reach and stop after 351kg being pumped into benzene solvent, start again at that be pumped into benzene molten when temperature in reaction kettle is increased to 160 DEG C
Agent, starts second and recycles, and stops being pumped into solvent when second of water yield reaches 141kg, when third time water yield reaches 70kg
Stopping is pumped into solvent, stops being pumped into solvent when water yield reaches 141kg for the 4th time, so raises the temperature to 160 after cycle 4 times
DEG C heat preservation 2h.
S104：Sub-material：Reaction solution in the step S103 is transferred in the condensation kettle of 5 3m3 respectively, successively；
S105：Hydrolysis：100L water is added in reaction solution into the step S104,30min is stirred at 110 DEG C and is carried out
Hydrolysis, hydrolytic acidity control are 18%；
S106：Condensation：Under the conditions of 100 DEG C, added in a manner of thread in the reaction solution into the step S105
The formaldehyde of 3500kg a concentration of 37%, 2h are added, and 115 DEG C of condensation 20h are warming up to after being added dropwise to complete, are added in immediately after the completion of condensation
200L water stirs 1h；
S107：It neutralizes：Caustic soda is added in reaction solution into the step S106 to neutralize, until pH value is 8, obtains naphthalene system naphthalene
Based water reducer.
Embodiment 8
The embodiment of the present disclosure provides the producer that a kind solvent method concentrates sulfonation separate mealing type condensation production naphthalene water reducer
Method, as shown in figure 3, including the following steps：
S101：It feeds intake：5200kg liquid naphthalenes are added in into the reaction kettle of 15m3, and carry out steam heating；
S102：Sulfonation：Start slow, 98% concentrated sulfuric acid of addition at the uniform velocity when the temperature of liquid naphthalene rises to 145 DEG C
4500kg, 60min are added, and continue steam heating after acid adding, 2.5h is kept the temperature after being warming up to 163 DEG C, carry out sulfonating reaction；
S103：Dehydration：Chloroform solvent, solvent band in vaporization at high temperature are continuously pumped into the reaction solution of the step S102
Go out the water of sulfonating reaction generation, detach water and chloroform solvent after condensation, the solvent isolated continues to be pumped into reaction kettle, when point
The water separated out stops being pumped into solvent after reaching 372kg, is started again at when temperature in reaction kettle is increased to 150 DEG C and is pumped into chloroform
Solvent, starts second and recycles, and stops being pumped into solvent when second of water yield reaches 62kg, when third time water yield reaches 93kg
Stopping is pumped into solvent, stops being pumped into solvent when water yield reaches 74kg for the 4th time, and the 5th water yield stops pump when reaching 19kg
Enter solvent, 165 DEG C of heat preservation 2h are raised the temperature to after so recycling 5 times.
S104：Hydrolysis：800L water is added in reaction solution into the step S103,30min is stirred at 110 DEG C and is carried out
Hydrolysis, hydrolytic acidity control are 19%；
S105：Sub-material：Reaction solution in the step S104 is transferred in the condensation kettle of 8 6m3 respectively, successively；
S106：Condensation：3600kg is added in a manner of thread in reaction solution under the conditions of 100 DEG C into the step S105
A concentration of 37% formaldehyde, 2h are added, and 110 DEG C of condensation 5h are warming up to after being added dropwise to complete, add in 200L water after the completion of condensation immediately,
Stir 2h；
S107：It neutralizes：Caustic soda is added in reaction solution into the step S106 to neutralize, until pH value is 9, obtains naphthalene system naphthalene
Based water reducer.
The above is only the specific embodiment of the present invention, is made skilled artisans appreciate that or realizing this hair
It is bright.A variety of modifications of these embodiments will be apparent to one skilled in the art, it is as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide range caused.
Claims (7)
1. a kind of solvent method concentrates the production method of sulfonation separate mealing type condensation production naphthalene water reducer, which is characterized in that the life
Production method includes the following steps：Feed intake, sulfonation, dehydration, hydrolysis, condensation and neutralization, wherein, the dehydration is：To equipped with
Solvent is continuously pumped into the reaction kettle of sulfonating reaction liquid, solvent takes the water of sulfonating reaction generation out of in vaporization at high temperature, after condensation
Water and solvent are detached, the solvent isolated is pumped into reaction kettle again, when water yield reaches the setting hundred of sulfonating reaction water yield
Stop being pumped into solvent after dividing ratio, started again at when temperature in reaction kettle is increased to 140~170 DEG C and be pumped into solvent, started next
Secondary cycle finally raises the temperature to 160~165 DEG C of 1~6h of heat preservation.
2. solvent method according to claim 1 concentrates the production method of sulfonation separate mealing type condensation production naphthalene water reducer,
Be characterized in that, the cycle-index in the dehydration be 4 times, the sulfonating reaction water yield set percentage as：40~
70%th, 15~45%, 10~30%, 5~20%.
3. solvent method according to claim 1 concentrates the production method of sulfonation separate mealing type condensation production naphthalene water reducer,
Be characterized in that, the cycle-index in the dehydration be 5 times, the sulfonating reaction water yield set percentage as：40~
70%th, 10~30%, 10~15%, 5~12%, 3~5%.
4. the production of sulfonation separate mealing type condensation production naphthalene water reducer is concentrated according to claim 1-3 any one of them solvent method
Method, which is characterized in that sub-material step is further included between the hydrolysing step and condensation step：Dehydration in reaction kettle is completed
Reaction solution is transferred at least one condensation kettle successively respectively, and the condensation and neutralization procedure carry out in the condensation kettle.
5. the production of sulfonation separate mealing type condensation production naphthalene water reducer is concentrated according to claim 1-3 any one of them solvent method
Method, which is characterized in that sub-material step is further included between the dehydration and hydrolysing step：Dehydration in reaction kettle is completed
Reaction solution is transferred at least one condensation kettle successively respectively, and the hydrolysis, condensation and neutralization procedure are in the condensation kettle
It carries out.
6. solvent method according to claim 5 concentrates the production method of sulfonation separate mealing type condensation production naphthalene water reducer,
It is characterized in that, the capacity of the condensation kettle is 2m3~20m3。
7. solvent method according to claim 6 concentrates the production method of sulfonation separate mealing type condensation production naphthalene water reducer,
It is characterized in that, the capacity of the reaction kettle is at least 3m3。
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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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585675A (en) * | 2009-06-22 | 2009-11-25 | 江苏特密斯混凝土外加剂有限公司 | Sulphonation method for naphthalene series water reducing agent without naphthalene discharging |
| CN103864332A (en) * | 2014-02-26 | 2014-06-18 | 科之杰新材料集团有限公司 | Preparation method of slump loss resistant naphthalene water reducer |
| CN104176968A (en) * | 2014-08-21 | 2014-12-03 | 广东瑞安科技实业有限公司 | Production method for naphthalene high-concentration water reducer |
| CN105236798A (en) * | 2014-12-26 | 2016-01-13 | 上虞吉龙化学建材有限公司 | Preparation method of naphthalene-series water reducing agent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585675A (en) * | 2009-06-22 | 2009-11-25 | 江苏特密斯混凝土外加剂有限公司 | Sulphonation method for naphthalene series water reducing agent without naphthalene discharging |
| CN103864332A (en) * | 2014-02-26 | 2014-06-18 | 科之杰新材料集团有限公司 | Preparation method of slump loss resistant naphthalene water reducer |
| CN104176968A (en) * | 2014-08-21 | 2014-12-03 | 广东瑞安科技实业有限公司 | Production method for naphthalene high-concentration water reducer |
| CN105236798A (en) * | 2014-12-26 | 2016-01-13 | 上虞吉龙化学建材有限公司 | Preparation method of naphthalene-series water reducing agent |
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