CN117049987A - Beta-sodium naphthalene sulfonate formaldehyde condensate and preparation method thereof - Google Patents
Beta-sodium naphthalene sulfonate formaldehyde condensate and preparation method thereof Download PDFInfo
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- CN117049987A CN117049987A CN202311039518.1A CN202311039518A CN117049987A CN 117049987 A CN117049987 A CN 117049987A CN 202311039518 A CN202311039518 A CN 202311039518A CN 117049987 A CN117049987 A CN 117049987A
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- beta
- sulfonic acid
- naphthalene sulfonic
- naphthalene
- sodium
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims abstract description 93
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 60
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000002425 crystallisation Methods 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 92
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 82
- 238000001816 cooling Methods 0.000 claims description 54
- 239000000047 product Substances 0.000 claims description 48
- 230000008025 crystallization Effects 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000006482 condensation reaction Methods 0.000 claims description 29
- 238000006386 neutralization reaction Methods 0.000 claims description 26
- YWPOLRBWRRKLMW-UHFFFAOYSA-M sodium;naphthalene-2-sulfonate Chemical compound [Na+].C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 YWPOLRBWRRKLMW-UHFFFAOYSA-M 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 13
- IWQLXFICQJMUGN-UHFFFAOYSA-N C=O.[Na].C1=C(C=CC2=CC=CC=C12)S(=O)(=O)O Chemical compound C=O.[Na].C1=C(C=CC2=CC=CC=C12)S(=O)(=O)O IWQLXFICQJMUGN-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 230000035900 sweating Effects 0.000 claims description 12
- 238000010533 azeotropic distillation Methods 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000006277 sulfonation reaction Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 210000004243 sweat Anatomy 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000017105 transposition Effects 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 17
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 9
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 9
- 239000004571 lime Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 20
- 229910052938 sodium sulfate Inorganic materials 0.000 description 20
- 235000011152 sodium sulphate Nutrition 0.000 description 20
- 238000000034 method Methods 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 13
- 239000011575 calcium Substances 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- HLPHHOLZSKWDAK-UHFFFAOYSA-M sodium;formaldehyde;naphthalene-1-sulfonate Chemical compound [Na+].O=C.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HLPHHOLZSKWDAK-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 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
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- 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
-
- 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
- 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
- C07C303/22—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 from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- 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
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical industry, in particular to a beta-sodium naphthalene sulfonate formaldehyde condensate and a preparation method thereof. According to the invention, the beta-naphthalene sulfonic acid is extracted from the naphthalene sulfonic acid mixture by adopting a melt crystallization method, so that the purity is high, the yield is high, the alpha-naphthalene sulfonic acid is avoided being removed by hydrolysis reaction, the generated naphthalene is recovered, lime is not required to be used for removing impurities, and further the introduction of calcium ions, magnesium ions and other impurities can be avoided.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a beta-sodium naphthalene sulfonate formaldehyde condensate and a preparation method thereof.
Background
The sodium naphthalene sulfonate formaldehyde condensate is an anionic surfactant, is a powdery solid, has stable chemical property, is easy to dissolve in water, has good emulsifying, dispersing, wetting and penetrating performances, can be compounded with various dispersing agents for use, and is widely applied to the fields of water-soluble dyes, fiber softeners, water treatment agents and the like. As a water treatment agent, the sodium naphthalene sulfonate formaldehyde condensate can play a double role of a precipitator and a complexing agent, so that the transparency and the quality of water are improved; as a dye, it can enhance the hydrophilicity, dispersibility and dyeing effect of the dye, and make the dyeing fast, uniform and durable; as a fiber softener, it can enhance the hydrophilicity of the softener and improve the softness and gloss of the fiber material. In addition, the sodium naphthalene sulfonate formaldehyde condensate diluent is used for controlling the pulp of the paper industry, so that the two-sided property can be reduced, the retention rate of fine fibers can be adjusted, and the viscosity of the coating can be reduced.
Sodium naphthalene sulfonate formaldehyde condensate is also widely used in the fields of leather, pesticides, building concrete and the like, for example: the product can be used as tanning agent of leather, dispersing agent and filler of pesticide, cement concrete water reducer and oil well cement water reducer for building, etc. It can also be used as an efficient dispersant for water-based paint, pigment paste, and as an adhesive, as a filler powder for polymers, to improve the water resistance of the material in the sealing layer. Sodium naphthalene sulfonate formaldehyde condensate has various excellent properties and is an important component in the field of organic synthesis.
The beta-sodium naphthalene sulfonate formaldehyde condensate is a common sodium naphthalene sulfonate formaldehyde condensate, and the traditional preparation method is as follows: the method comprises the steps of using concentrated sulfuric acid and naphthalene as raw materials, sulfonating to obtain a mixture of alpha-naphthalene sulfonic acid and beta-naphthalene sulfonic acid, removing the alpha-naphthalene sulfonic acid through hydrolysis, condensing the beta-naphthalene sulfonic acid with formaldehyde, removing excessive sulfuric acid by lime, and neutralizing sodium hydroxide to obtain the beta-naphthalene sulfonic acid sodium formaldehyde condensate. The preparation method has the defects that when the intermediate product beta-naphthalene sulfonic acid is prepared, alpha-naphthalene sulfonic acid is required to be removed through hydrolysis reaction, and generated naphthalene is recovered, a large amount of sulfuric acid is generated, then low-cost lime is required to neutralize the sulfuric acid, excessive sulfuric acid is required to be removed in the form of calcium sulfate, the adsorption capacity of the calcium sulfate to the product is high, the product loss is caused, calcium and magnesium ions (impurities) are introduced in the neutralization process to reduce the quality of the final product, the preparation method is complex in operation, the product purity is low, and the yield is low.
In this regard, in the preparation method of the high-concentration naphthalene sulfonic acid formaldehyde condensate disclosed in the patent CN107674005a, the amount of alkali liquor and lime used in the neutralization process is reduced by adding a water-carrying agent to carry out acid water in the sulfonation reaction process, however, the water-carrying agent only forms azeotropy with water, a large amount of sulfuric acid cannot be carried out, lime is still used in the neutralization process, calcium and magnesium ions still can be introduced, and the purity of the naphthalene sulfonic acid formaldehyde condensate cannot be further improved. As another example, in the preparation method disclosed in patent CN102070495a, an attempt is made to neutralize naphthalene sulfonic acid selectively by utilizing the difference in acidity between naphthalene sulfonic acid and sulfuric acid so that it does not react with sulfuric acid, but the neutralization end point is ph=7 to 9, at which time sulfuric acid has reacted with sodium hydroxide, and the intended purpose cannot be achieved.
Therefore, a preparation method capable of avoiding introducing calcium and magnesium ions into products to improve the quality of the products and simultaneously producing the beta-sodium naphthalene sulfonate formaldehyde condensate with high efficiency is needed.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a β -naphthalene sulfonic acid sodium formaldehyde condensate and a preparation method thereof, so as to solve the technical problems of the prior art that calcium and magnesium ions are introduced during the production of the β -naphthalene sulfonic acid sodium formaldehyde condensate, the preparation method is complex to operate, the product quality is low, and the yield is low.
In order to achieve the above and other related objects, the present invention provides a method for preparing a sodium beta-naphthalene sulfonate formaldehyde condensate, which uses naphthalene and sulfuric acid as raw materials to prepare a naphthalene sulfonic acid mixture, extracts beta-naphthalene sulfonic acid in the naphthalene sulfonic acid mixture through melt crystallization, and sequentially performs condensation reaction, neutralization reaction and purification steps on the beta-naphthalene sulfonic acid to obtain the sodium beta-naphthalene sulfonate formaldehyde condensate.
The principle of the invention is as follows: by utilizing the fact that the melting points of the beta-naphthalene sulfonic acid and the alpha-naphthalene sulfonic acid have larger difference, and further adopting a melting crystallization mode to extract the beta-naphthalene sulfonic acid from the naphthalene sulfonic acid mixture, the purity of the beta-naphthalene sulfonic acid can be ensured, meanwhile, the alpha-naphthalene sulfonic acid obtained through separation can be continuously converted into the beta-naphthalene sulfonic acid, the conversion rate of naphthalene and the yield of the beta-naphthalene sulfonic acid are improved, and further, the alpha-naphthalene sulfonic acid is not required to be removed through hydrolysis reaction, and the produced naphthalene is recovered. The key point is that when the beta-naphthalene sulfonic acid is prepared, sulfuric acid is not additionally generated, lime is not needed to be adopted for neutralization reaction, namely calcium and magnesium ions are not introduced, and the prepared beta-naphthalene sulfonic acid can be directly used for condensation reaction. However, the condensation reaction needs to use a catalyst sulfuric acid, and when the subsequent neutralization reaction is carried out on the condensation product, the sulfuric acid is converted into sulfate by alkali, and finally, the sulfate is removed through a purification step, so that the purity of the subsequent preparation of the beta-sodium naphthalene sulfonate formaldehyde condensate is ensured, and the yield and quality of the product are improved.
Optionally, the melting crystallization sequentially comprises direct cooling, primary cooling, secondary cooling and heating and sweating.
Optionally, the naphthalene sulfonic acid mixture is directly cooled to 95-105 ℃.
Optionally, the primary cooling is carried out at a cooling rate of 0.5 ℃/3-5 min.
Optionally, the second-stage cooling is performed at a cooling rate of 0.1 ℃/1-2 min.
Optionally, the heating up and sweating are carried out at a heating up rate of 0.1 ℃/3-5 min.
The invention sequentially comprises four processes, namely direct cooling, primary cooling, secondary cooling and heating and sweating, wherein the direct cooling aims to cool the naphthalene sulfonic acid mixture in a high temperature state to a state to be crystallized, the primary cooling is carried out slowly until crystals are generated, namely, the beta-naphthalene sulfonic acid with higher melting point in the naphthalene sulfonic acid mixture starts to crystallize, the secondary cooling is carried out further slowly until the beta-naphthalene sulfonic acid is crystallized, then a crystallization mother liquor containing a large amount of alpha-naphthalene sulfonic acid is discharged, and then the alpha-naphthalene sulfonic acid remained in the beta-naphthalene sulfonic acid crystals is discharged through heating and sweating, so that the alpha-naphthalene sulfonic acid in the naphthalene sulfonic acid mixture is removed, and the beta-naphthalene sulfonic acid is obtained.
The preparation method of the invention comprises the following steps:
s1, preparing naphthalene sulfonic acid mixture: adding sulfuric acid into naphthalene to obtain a mixture, heating and preserving heat of the mixture for sulfonation reaction to obtain a sulfonated product, then carrying out azeotropic distillation and reduced pressure distillation on the sulfonated product in sequence, and then carrying out secondary heating and preserving heat of the sulfonated product for transposition reaction to obtain a naphthalene sulfonic acid mixture;
s2, extracting beta-naphthalene sulfonic acid: carrying out melt crystallization on the naphthalene sulfonic acid mixture, namely sequentially carrying out direct cooling, primary cooling and secondary cooling, removing crystallization mother liquor to obtain beta-naphthalene sulfonic acid crystals, then carrying out heating and sweating on the beta-naphthalene sulfonic acid crystals, and removing sweat to obtain beta-naphthalene sulfonic acid;
s3, preparing a sodium beta-naphthalene sulfonate formaldehyde condensate: adding formaldehyde, a catalyst and a solvent into the obtained beta-naphthalene sulfonic acid to perform condensation reaction, adding alkali after the condensation reaction is finished to perform neutralization reaction, sequentially concentrating, crystallizing and filtering to remove salt in a reaction liquid, continuously concentrating the filtered filtrate, and finally drying to obtain the product beta-naphthalene sulfonic acid sodium formaldehyde condensate.
In the invention, the alkali used in the neutralization reaction comprises, but is not limited to, sodium hydroxide, and the steps of condensation reaction, crystallization, filtration and subsequent concentration and drying after the neutralization reaction are sequentially carried out on the beta-naphthalene sulfonic acid, so that the byproduct salt generated in the neutralization reaction and the solvent in the reaction system are removed, and the purity of the product is further improved.
Optionally, in step S1, the molar ratio of sulfuric acid to naphthalene is 1:1.05 to 1.2.
In the invention, the raw material sulfuric acid is concentrated sulfuric acid or fuming sulfuric acid, the sulfuric acid is added dropwise, the dropwise adding rate is 54-108 mL/h, the sulfuric acid is added dropwise, and the dropwise adding rate is controlled, so that naphthalene sublimation caused by over-high temperature of the solution can be avoided.
Optionally, in the step S1, the temperature is heated to 110-120 ℃ once, and the time for heat preservation after the primary heating is 1.5-2 h.
Optionally, in the step S1, the temperature is heated to 150-165 ℃ for a second time, and the time for heat preservation after the second time is 2-2.5 h.
Optionally, in step S1, the entrainer used in the azeotropic distillation includes at least one of n-heptane, petroleum ether, dichloromethane and dichloroethane.
In the invention, the dosage of the entrainer is 160-200 g.
Optionally, in step S1, the reflux time of the azeotropic distillation is 5-6 h.
Optionally, in step S1, the temperature of the reduced pressure distillation is 70 to 100 ℃.
Optionally, in step S1, the pressure of the reduced pressure distillation is 0.085-0.095 MPa.
In the present invention, azeotropic distillation is aimed at bringing out moisture generated by sulfonation reaction; the purpose of the reduced pressure distillation is to remove unreacted refined naphthalene.
Optionally, in step S3, the molar ratio of β -naphthalene sulfonic acid to formaldehyde is 1:0.5 to 1, preferably 1:0.6 to 0.8.
Optionally, in step S3, the catalyst includes sulfuric acid.
Optionally, in step S3, the solvent includes water.
Optionally, in step S3, the formaldehyde is added dropwise.
In the invention, formaldehyde is added into beta-naphthalene sulfonic acid in a dropwise manner, so that the formaldehyde can be prevented from volatilizing due to high temperature.
Optionally, in step S3, the mass ratio of sulfuric acid to β -naphthalene sulfonic acid is 1:4 to 20, preferably 1:5 to 10.
Alternatively, in step S3, the temperature of the condensation reaction is 100 to 150 ℃, preferably 110 to 130 ℃.
Optionally, in step S3, the end point of the neutralization reaction is ph=9 to 10.
Optionally, in step S3, the temperature at the time of crystallization is 80 to 90 ℃, preferably 85 to 90 ℃.
The invention also provides a beta-sodium naphthalene sulfonate formaldehyde condensate prepared according to the preparation method.
The invention has the beneficial effects that:
according to the invention, the beta-naphthalene sulfonic acid is extracted from the naphthalene sulfonic acid mixture by utilizing the fact that the melting points of the beta-naphthalene sulfonic acid and the alpha-naphthalene sulfonic acid have larger difference, and further the beta-naphthalene sulfonic acid is extracted from the naphthalene sulfonic acid mixture in a melting crystallization mode, and the separated alpha-naphthalene sulfonic acid can be continuously converted into the beta-naphthalene sulfonic acid, so that the purity and the yield of the beta-naphthalene sulfonic acid can be ensured, and meanwhile, the alpha-naphthalene sulfonic acid is prevented from being removed through hydrolysis reaction and the generated naphthalene is recovered, namely, the impurity is not required to be removed by lime, and further the introduction of calcium-magnesium ions and other impurities can be avoided, and the beta-naphthalene sulfonic acid is subjected to condensation reaction, neutralization reaction and purification to prepare the beta-naphthalene sulfonic acid sodium formaldehyde condensate. Compared with the traditional method, the operation steps of the invention are simpler, and the prepared beta-sodium naphthalene sulfonate formaldehyde condensate product has high purity and high yield, and improves the quality and economy of the product.
Detailed Description
The following embodiments of the present invention will be described with reference to specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be understood that the preferred embodiments are presented by way of illustration only and not by way of limitation.
The invention provides a preparation method of a beta-sodium naphthalene sulfonate formaldehyde condensate, which is characterized in that naphthalene and sulfuric acid are used as raw materials to prepare a naphthalene sulfonic acid mixture, beta-naphthalene sulfonic acid in the naphthalene sulfonic acid mixture is extracted through melt crystallization, and the beta-naphthalene sulfonic acid is subjected to condensation reaction, neutralization reaction and purification steps in sequence to obtain the beta-sodium naphthalene sulfonate formaldehyde condensate.
Wherein, the melting crystallization comprises directly cooling naphthalene sulfonic acid mixture to 95-105 ℃, then carrying out primary cooling at a cooling rate of 0.5 ℃/3-5 min, then carrying out secondary cooling at a cooling rate of 0.1 ℃/1-2 min, and finally carrying out heating and sweating at a heating rate of 0.1 ℃/3-5 min.
In one embodiment of the invention, the method for preparing the sodium beta-naphthalenesulfonate formaldehyde condensate comprises the following steps:
s1, preparing naphthalene sulfonic acid mixture: the molar ratio of sulfuric acid to naphthalene is 1: adding sulfuric acid into naphthalene to obtain a mixture, heating the mixture to 110-120 ℃ for 1.5-2 h at one time to carry out sulfonation reaction to obtain a sulfonated product, carrying out azeotropic distillation on the sulfonated product by adopting an entrainer for 5-6 h, carrying out reduced pressure distillation on the sulfonated product under the conditions of 70-100 ℃ and 0.085-0.095 MPa, and carrying out secondary heating on the sulfonated product to 150-165 ℃ and heat preservation for 2-2.5 h to carry out transposition reaction to obtain a naphthalene sulfonic acid mixture;
s2, extracting beta-naphthalene sulfonic acid: carrying out melt crystallization on the prepared naphthalene sulfonic acid mixture, namely directly cooling the naphthalene sulfonic acid mixture to 95-105 ℃, then carrying out primary cooling at the cooling rate of 0.5 ℃/3-5 min until crystals are generated, then carrying out secondary cooling at the cooling rate of 0.1 ℃/1-2 min until crystallization is completed, removing crystallization mother liquor, then carrying out heating and sweating at the rate of 0.1 ℃/3-5 min, and removing sweat after heating and sweating are completed to obtain beta-naphthalene sulfonic acid;
s3, preparing a sodium beta-naphthalene sulfonate formaldehyde condensate: firstly, according to the mass ratio of sulfuric acid to beta-naphthalene sulfonic acid of 1: adding catalyst sulfuric acid and solvent water into the obtained beta-naphthalene sulfonic acid, and then according to the mole ratio of the beta-naphthalene sulfonic acid to formaldehyde of 1: dropwise adding formaldehyde into beta-naphthalene sulfonic acid at 0.5-1, performing condensation reaction at 100-150 ℃, adding alkali after the condensation reaction is finished to perform neutralization reaction, wherein the end point of the neutralization reaction is pH=9-10, sequentially concentrating, crystallizing and filtering to remove salt in reaction liquid, wherein the crystallization temperature is 80-90 ℃, continuously concentrating the filtered filtrate, and finally drying to obtain the product beta-sodium naphthalene sulfonate formaldehyde condensate.
In the step S1, sulfuric acid is added dropwise at the dropwise adding rate of 54-108 mL/h;
in the step S1, the entrainer comprises at least one of n-heptane, petroleum ether, methylene dichloride and dichloroethane, and the dosage of the entrainer is 160-200 g;
in the step S3, the alkali added after the condensation reaction is finished is sodium hydroxide, and the sodium salt removed in the purification step is sodium sulfate.
The invention also provides a beta-sodium naphthalene sulfonate formaldehyde condensate prepared according to the preparation method.
The present invention will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
In the present invention, the reaction equation of the chemical reaction involved is as follows:
sulfonation reaction:
the translocation reaction:
condensation reaction:
neutralization reaction:
in the invention, in the preparation process of naphthalene sulfonic acid mixture, concentrated sulfuric acid and refined naphthalene are adopted as raw materials naphthalene, and before the concentrated sulfuric acid and the refined naphthalene are mixed, the refined naphthalene is heated to be dissolved into liquid, wherein the heated target temperature is 80-90 ℃; in the preparation process of the beta-sodium naphthalene sulfonate formaldehyde condensate, after adding catalyst concentrated sulfuric acid and solvent water into beta-naphthalene sulfonic acid, and before adding formaldehyde, the solution needs to be heated.
Example 1
The embodiment provides a preparation method of a beta-sodium naphthalene sulfonate formaldehyde condensate, which comprises the following steps:
s1, preparing naphthalene sulfonic acid mixture: the molar ratio of the concentrated sulfuric acid to the refined naphthalene is 1:1.1, heating 142.2g of refined naphthalene to 85 ℃ to dissolve the refined naphthalene, dropwise adding 54mL (namely 100 g) of concentrated sulfuric acid with the concentration of 98wt% into the refined naphthalene at the dropwise adding rate of 80mL/h to obtain a mixture, heating the mixture to 115 ℃ for one time and preserving heat for 1.8 hours to carry out sulfonation reaction to obtain a sulfonated product, adding 180g of n-heptane into the sulfonated product to reflux for 5.5 hours for azeotropic distillation, then placing the sulfonated product under the conditions of 0.090MPa and 85 ℃ for reduced pressure distillation, and then carrying out secondary heating to 158 ℃ and preserving heat for 2.2 hours to carry out transposition reaction to obtain a naphthalene sulfonic acid mixture;
s2, extracting beta-naphthalene sulfonic acid: the prepared naphthalene sulfonic acid mixture is subjected to melt crystallization, namely the naphthalene sulfonic acid mixture is directly cooled to 100 ℃, then subjected to primary cooling at the cooling rate of 0.5 ℃/4min, crystals are observed to be generated when the temperature is reduced to 88.3 ℃, then subjected to secondary cooling at the cooling rate of 0.1 ℃/1.5min, after the temperature is reduced to 82.4 ℃, the crystallization is completed, the crystallization mother liquor is poured out, beta-naphthalene sulfonic acid crystals are obtained, then the temperature is raised to 88.5 ℃ again at the rate of 0.1 ℃/4min, the sweating is finished, and the sweats are poured out, so that the beta-naphthalene sulfonic acid is obtained;
the quality of the beta-naphthalene sulfonic acid is 145.5g, and the purity is 99.1 percent.
S3, preparing a sodium beta-naphthalene sulfonate formaldehyde condensate: firstly, according to the mass ratio of sulfuric acid to beta-naphthalene sulfonic acid of 1:9.7 adding 200g of water and 15g of concentrated sulfuric acid to the obtained beta-naphthalenesulfonic acid, heating the solution to 110 ℃, and then obtaining the beta-naphthalenesulfonic acid and formaldehyde in a molar ratio of 1: and (3) dropwise adding 46.5g of formaldehyde solution with the volume fraction of 37% into beta-naphthalene sulfonic acid at 0.76, carrying out condensation reaction for 4 hours at the temperature of 120 ℃, adding sodium hydroxide after the condensation reaction is finished to carry out neutralization reaction until the pH value is=9, concentrating, cooling to 85 ℃ for crystallization for 1 hour, filtering while the mixture is hot, washing a filter cake with a small amount of water, drying to obtain sodium sulfate, continuously concentrating the filtrate to remove a large amount of water, drying in an oven, and crushing to obtain light yellow powder, namely the product beta-naphthalene sulfonic acid sodium formaldehyde condensate.
The quality of the product beta-sodium naphthalene sulfonate formaldehyde condensate is 151.2g, the purity is 99.2%, wherein the content of sodium sulfate is 0.2%, the moisture content is 0.4%, the content of calcium and magnesium ions is 2PPM, and the quality of byproduct sodium sulfate is 18.7g.
Example 2
The embodiment provides a preparation method of a beta-sodium naphthalene sulfonate formaldehyde condensate, which comprises the following steps:
s1, preparing naphthalene sulfonic acid mixture: the molar ratio of the concentrated sulfuric acid to the refined naphthalene is 1:1.05 heating 135.8g of refined naphthalene to 90 ℃ to dissolve the refined naphthalene, dropwise adding 54mL (namely 100 g) of concentrated sulfuric acid with the concentration of 98wt% into the refined naphthalene at the dropwise adding rate of 54mL/h to obtain a mixture, heating the mixture to 120 ℃ for one time and preserving heat for 1.5 hours to carry out sulfonation reaction to obtain a sulfonated product, adding 160g of petroleum ether into the sulfonated product to reflux for 5 hours for azeotropic distillation, then placing the sulfonated product at the temperature of 0.085MPa and 100 ℃ for reduced pressure distillation, and then carrying out secondary heating to 165 ℃ and preserving heat for 2 hours to carry out transposition reaction to obtain a naphthalene sulfonic acid mixture;
s2, extracting beta-naphthalene sulfonic acid: the prepared naphthalene sulfonic acid mixture is subjected to melt crystallization, namely the naphthalene sulfonic acid mixture is directly cooled to 105 ℃, then subjected to primary cooling at the cooling rate of 0.5 ℃/3min, crystals are observed to be generated when the temperature is reduced to 88.7 ℃, then subjected to secondary cooling at the cooling rate of 0.1 ℃/1min, when the temperature is reduced to 82.9 ℃, crystallization is completed, a crystallization mother liquor is poured out, beta-naphthalene sulfonic acid crystals are obtained, then the temperature is raised to sweat at the rate of 0.1 ℃/3min, the temperature is raised to 88.6 ℃, and the sweat is poured out, so that the beta-naphthalene sulfonic acid is obtained;
the quality of the beta-naphthalene sulfonic acid is 143.6g, and the purity is 98.9 percent.
S3, preparing a sodium beta-naphthalene sulfonate formaldehyde condensate: firstly, according to the mass ratio of sulfuric acid to beta-naphthalene sulfonic acid of 1:4 to the beta-naphthalenesulfonic acid obtained, 200g of water and 35.9g of concentrated sulfuric acid were added, and the solution was heated to 110℃and then a molar ratio of beta-naphthalenesulfonic acid to formaldehyde was 1:1, 60.4g of formaldehyde solution with the volume fraction of 37% is dropwise added into beta-naphthalene sulfonic acid, the temperature is maintained at 150 ℃ for condensation reaction for 4 hours, sodium hydroxide is added after the condensation reaction is finished to perform neutralization reaction until the pH value is=9.2, then concentration is performed, cooling is performed to 80 ℃ for crystallization for 1 hour, filtering is performed while the mixture is hot, filter cakes are washed with a small amount of water and dried to obtain sodium sulfate, meanwhile, the filtrate is continuously concentrated to remove a large amount of water, and the mixture is placed into an oven for drying treatment and crushed to obtain light yellow powder, namely the product beta-naphthalene sulfonic acid sodium formaldehyde condensate.
The quality of the product beta-sodium naphthalene sulfonate formaldehyde condensate is 151.9g, the purity is 98.3%, wherein the content of sodium sulfate is 0.8%, the moisture content is 0.4%, the content of calcium and magnesium ions is 5PPM, and the quality of byproduct sodium sulfate is 49.4g.
Example 3
The embodiment provides a preparation method of a beta-sodium naphthalene sulfonate formaldehyde condensate, which comprises the following steps:
s1, preparing naphthalene sulfonic acid mixture: the molar ratio of the concentrated sulfuric acid to the refined naphthalene is 1:1.2 heating 155.2g of refined naphthalene to 80 ℃ to dissolve the refined naphthalene, dropwise adding 54mL (namely 100 g) of concentrated sulfuric acid with the concentration of 98wt% into the refined naphthalene at the dropwise adding rate of 108mL/h to obtain a mixture, heating the mixture to 110 ℃ for one time and preserving heat for 2 hours to carry out sulfonation reaction to obtain a sulfonated product, adding 200g of methylene dichloride into the sulfonated product to reflux for 6 hours for azeotropic distillation, then placing the sulfonated product at the temperature of 0.095MPa and 70 ℃ for reduced pressure distillation, and then heating the sulfonated product to 150 ℃ for the second time and preserving heat for 2.5 hours for transposition reaction to obtain a naphthalene sulfonic acid mixture;
s2, extracting beta-naphthalene sulfonic acid: the prepared naphthalene sulfonic acid mixture is subjected to melt crystallization, namely the naphthalene sulfonic acid mixture is directly cooled to 95 ℃, then subjected to primary cooling at the cooling rate of 0.5 ℃/5min, crystals are observed to be generated when the temperature is reduced to 88.4 ℃, then subjected to secondary cooling at the cooling rate of 0.1 ℃/2min, when the temperature is reduced to 82.3 ℃, crystallization is completed, a crystallization mother liquor is poured out, beta-naphthalene sulfonic acid crystals are obtained, then the temperature is raised to sweat at the rate of 0.1 ℃/5min, the temperature is raised to 88.5 ℃, and the sweat is poured out, so that beta-naphthalene sulfonic acid is obtained;
the quality of the beta-naphthalene sulfonic acid is 143.1g, and the purity is 99.05 percent.
S3, preparing a sodium beta-naphthalene sulfonate formaldehyde condensate: firstly, according to the mass ratio of sulfuric acid to beta-naphthalene sulfonic acid of 1:20 to the beta-naphthalenesulfonic acid obtained, 200g of water and 7.2g of concentrated sulfuric acid were added, and the solution was heated to 100℃and then a molar ratio of beta-naphthalenesulfonic acid to formaldehyde was 1:0.5, dropwise adding 30.1g of formaldehyde solution with the volume fraction of 37% into beta-naphthalene sulfonic acid, carrying out condensation reaction for 4 hours at the temperature of 100 ℃, adding sodium hydroxide after the condensation reaction is finished to carry out neutralization reaction until the pH value is=10, concentrating, cooling to 90 ℃ for crystallization for 1 hour, filtering while hot, washing a filter cake with a small amount of water, drying to obtain sodium sulfate, simultaneously continuously concentrating the filtrate to remove a large amount of water, drying in an oven, and crushing to obtain light yellow powder, namely the product beta-naphthalene sulfonic acid sodium formaldehyde condensate.
The quality of the product beta-sodium naphthalene sulfonate formaldehyde condensate is 146.7g, the purity is 98.8%, wherein the content of sodium sulfate is 0.1%, the moisture content is 0.5%, the content of calcium and magnesium ions is 4PPM, and the quality of byproduct sodium sulfate is 10.2g.
Example 4
This example provides a process for the preparation of a sodium beta-naphthalenesulfonate formaldehyde condensate, carried out according to the process of example 1, which differs from example 1 in that:
s3, preparing a sodium beta-naphthalene sulfonate formaldehyde condensate: firstly, according to the mass ratio of sulfuric acid to beta-naphthalene sulfonic acid of 1:5 to the beta-naphthalenesulfonic acid obtained, 200g of water and 29.1g of concentrated sulfuric acid were added, and the solution was heated to 110℃and then a molar ratio of beta-naphthalenesulfonic acid to formaldehyde was 1: and 0.6 g of formaldehyde solution with the volume fraction of 37% is dropwise added into beta-naphthalene sulfonic acid, the temperature is maintained at 120 ℃ for condensation reaction for 4 hours, sodium hydroxide is added after the condensation reaction is finished to perform neutralization reaction until the pH value is=9.5, then concentration is performed, cooling is performed to 87 ℃ for crystallization for 1 hour, filtering is performed while the mixture is hot, filter cakes are washed with a small amount of water and dried to obtain sodium sulfate, meanwhile, the filtrate is continuously concentrated to remove a large amount of water, and the mixture is placed in an oven for drying treatment and crushed to obtain light yellow powder, namely the product beta-naphthalene sulfonic acid sodium formaldehyde condensate.
The remaining steps were the same as in example 1.
The quality of the product beta-sodium naphthalene sulfonate formaldehyde condensate is 149.8g, the purity is 99.0%, the content of sodium sulfate is 0.3%, the moisture content is 0.5%, the content of calcium and magnesium ions is 4PPM, and in addition, the quality of byproduct sodium sulfate is 34.3g.
Example 5
This example provides a process for the preparation of a sodium beta-naphthalenesulfonate formaldehyde condensate, carried out according to the process of example 1, which differs from example 1 in that:
s3, preparing a sodium beta-naphthalene sulfonate formaldehyde condensate: firstly, according to the mass ratio of sulfuric acid to beta-naphthalene sulfonic acid of 1:10 to the beta-naphthalenesulfonic acid obtained, 200g of water and 14.55g of concentrated sulfuric acid were added, and the solution was heated to 110℃and then a molar ratio of beta-naphthalenesulfonic acid to formaldehyde was 1:0.8, dropwise adding 49.0g of formaldehyde solution with the volume fraction of 37% into beta-naphthalene sulfonic acid, preserving heat at 130 ℃ for condensation reaction for 4 hours, adding sodium hydroxide after the condensation reaction is finished to perform neutralization reaction until the pH value is=9.5, concentrating, cooling to 88 ℃ for crystallization for 1 hour, filtering while hot, washing a filter cake with a small amount of water, drying to obtain sodium sulfate, continuously concentrating the filtrate to remove a large amount of water, drying in an oven, and crushing to obtain light yellow powder, namely the product beta-naphthalene sulfonic acid sodium formaldehyde condensate.
The remaining steps were the same as in example 1.
The quality of the product beta-sodium naphthalene sulfonate formaldehyde condensate is 151.7g, the purity is 99.1%, wherein the content of sodium sulfate is 0.2%, the moisture content is 0.3%, the content of calcium and magnesium ions is 3PPM, and the quality of byproduct sodium sulfate is 18.5g.
Comparative example 1
This comparative example differs from example 1 in that: removing alpha-naphthalene sulfonic acid in the naphthalene sulfonic acid mixture through hydrolysis to obtain beta-naphthalene sulfonic acid (sulfuric acid containing impurities), and removing excessive sulfuric acid by lime after condensation reaction of the beta-naphthalene sulfonic acid and formaldehyde, wherein the specific steps are as follows:
s2, extracting beta-naphthalene sulfonic acid: placing the obtained naphthalene sulfonic acid mixture into an acidic water system for hydrolysis reaction, and introducing steam into the obtained hydrolysis reaction liquid after the hydrolysis reaction is finished to remove unreacted refined naphthalene and naphthalene generated by the hydrolysis reaction to obtain 2-naphthalene sulfonic acid;
the quality of the beta-naphthalene sulfonic acid is 164.7g, and the purity is 92.5 percent.
In step S3, after the condensation reaction is completed, a proper amount of lime is added to the reaction system before the neutralization reaction is performed, and the excess sulfuric acid is removed in the form of calcium sulfate.
The other preparation conditions and steps were the same as in example 1, and it was examined that the product sodium beta-naphthalenesulfonate formaldehyde condensate had a mass of 147.8g and a purity of 91.3%, wherein the content of sodium sulfate was 1.8%, the content of moisture was 0.5%, the content of calcium and magnesium ions was 137PPM, and further that the mass of by-product sodium sulfate was 10.1g.
As is clear from examples 1 to 5, the purity of the beta-naphthalenesulfonic acid obtained in examples 1 to 3 was 98.9% or more, the purity of the sodium beta-naphthalenesulfonate formaldehyde condensate obtained in examples 1 to 5 was 98.3% or more, the purity of the sodium beta-naphthalenesulfonate formaldehyde condensate obtained in examples 1 and 4 to 5 was 99.0% or more, and the sodium sulfate content in the sodium beta-naphthalenesulfonate formaldehyde condensate was less than 1%, the moisture content was 5% or less, and the calcium magnesium ion content was 5PPM or less. The result shows that the beta-naphthalene sulfonic acid prepared by the preparation method has high purity and high yield, the beta-sodium naphthalene sulfonate formaldehyde condensate prepared by the beta-naphthalene sulfonic acid has high purity, the content of calcium and magnesium ions is extremely low, and the product quality is excellent.
From comparative example 1 and example 1, it was found that the purity of the β -naphthalenesulfonic acid obtained in comparative example 1 was 92.5%, the purity of the sodium β -naphthalenesulfonate formaldehyde condensate obtained from the β -naphthalenesulfonic acid was 91.3%, both of which were significantly lower than in example 1, while the content of sodium sulfate by-product in comparative example 1 was 1.8%, which was higher than in example 1, and the calcium-magnesium ion content thereof was 137PPM, which was far higher than in example 1. The result shows that the beta-naphthalene sulfonic acid is extracted from the naphthalene sulfonic acid mixture by a melt crystallization mode, so that a large amount of impurity calcium and magnesium ions can be prevented from being introduced into the product, and the product quality of the beta-naphthalene sulfonic acid sodium formaldehyde condensate is improved.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. A preparation method of a beta-sodium naphthalene sulfonate formaldehyde condensate is characterized by comprising the following steps of: naphthalene and sulfuric acid are used as raw materials to prepare naphthalene sulfonic acid mixture, beta-naphthalene sulfonic acid in the naphthalene sulfonic acid mixture is extracted through melt crystallization, and condensation reaction, neutralization reaction and purification steps are sequentially carried out on the beta-naphthalene sulfonic acid to obtain beta-sodium naphthalene sulfonate formaldehyde condensate.
2. The method of manufacturing according to claim 1, characterized in that: the melting crystallization sequentially comprises direct cooling, primary cooling, secondary cooling and heating and sweating.
3. The preparation method according to claim 2, characterized in that: directly cooling the naphthalene sulfonic acid mixture to 95-105 ℃;
and/or, performing primary cooling at a cooling rate of 0.5 ℃/3-5 min;
and/or, carrying out secondary cooling at a cooling rate of 0.1 ℃/1-2 min;
and/or heating up and sweating at a heating up rate of 0.1 ℃/3-5 min.
4. The preparation method according to claim 1 or 2, characterized in that the preparation method comprises the steps of:
s1, preparing naphthalene sulfonic acid mixture: adding sulfuric acid into naphthalene to obtain a mixture, heating and preserving heat of the mixture for sulfonation reaction to obtain a sulfonated product, then carrying out azeotropic distillation and reduced pressure distillation on the sulfonated product in sequence, and then carrying out secondary heating and preserving heat of the sulfonated product for transposition reaction to obtain a naphthalene sulfonic acid mixture;
s2, extracting beta-naphthalene sulfonic acid: carrying out melt crystallization on the naphthalene sulfonic acid mixture, namely sequentially carrying out direct cooling, primary cooling and secondary cooling, removing crystallization mother liquor to obtain beta-naphthalene sulfonic acid crystals, then carrying out heating and sweating on the beta-naphthalene sulfonic acid crystals, and removing sweat to obtain beta-naphthalene sulfonic acid;
s3, preparing a sodium beta-naphthalene sulfonate formaldehyde condensate: adding formaldehyde, a catalyst and a solvent into the obtained beta-naphthalene sulfonic acid to perform condensation reaction, adding alkali after the condensation reaction is finished to perform neutralization reaction, sequentially concentrating, crystallizing and filtering to remove salt in a reaction liquid, continuously concentrating the filtered filtrate, and finally drying to obtain the product beta-naphthalene sulfonic acid sodium formaldehyde condensate.
5. The method of manufacturing according to claim 4, wherein: in the step S1, the molar ratio of sulfuric acid to naphthalene is 1:1.05 to 1.2;
and/or in the step S1, heating to 110-120 ℃ for one time, wherein the time for heat preservation after one time heating is 1.5-2 hours;
and/or in the step S1, the secondary heating is carried out to 150-165 ℃, and the heat preservation time after the secondary heating is 2-2.5 h.
6. The method of manufacturing according to claim 4, wherein: in the step S1, the entrainer used in the azeotropic distillation comprises at least one of n-heptane, petroleum ether, methylene dichloride and dichloroethane;
and/or, in the step S1, the reflux time of the azeotropic distillation is 5-6 h;
and/or, in the step S1, the temperature of the reduced pressure distillation is 70-100 ℃;
and/or, in the step S1, the pressure of the reduced pressure distillation is 0.085-0.095 MPa.
7. The method of manufacturing according to claim 4, wherein: in the step S3, the mol ratio of the beta-naphthalene sulfonic acid to formaldehyde is 1:0.5 to 1;
and/or, in step S3, the catalyst comprises sulfuric acid;
and/or, in step S3, the solvent comprises water.
8. The method of manufacturing according to claim 7, wherein: in the step S3, the formaldehyde is added dropwise;
and/or, in the step S3, the mass ratio of the sulfuric acid to the beta-naphthalene sulfonic acid is 1:4 to 20.
9. The method of manufacturing according to claim 4, wherein: in the step S3, the temperature of the condensation reaction is 100-150 ℃;
and/or, in the step S3, the end point of the neutralization reaction is ph=9 to 10;
and/or, in the step S3, the temperature at the time of crystallization is 80-90 ℃.
10. A sodium beta-naphthalenesulfonate formaldehyde condensate produced by the production process according to any one of claims 1 to 9.
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