CN1036000C - Method for producing condensation compound of methyl naphthalene sulfonic acid and formaldehyde - Google Patents
Method for producing condensation compound of methyl naphthalene sulfonic acid and formaldehyde Download PDFInfo
- Publication number
- CN1036000C CN1036000C CN92105199A CN92105199A CN1036000C CN 1036000 C CN1036000 C CN 1036000C CN 92105199 A CN92105199 A CN 92105199A CN 92105199 A CN92105199 A CN 92105199A CN 1036000 C CN1036000 C CN 1036000C
- Authority
- CN
- China
- Prior art keywords
- condensation
- formaldehyde
- sulfonation
- sulfonic acid
- naphthalene sulfonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000009833 condensation Methods 0.000 title claims abstract description 18
- 230000005494 condensation Effects 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 36
- WODGMMJHSAKKNF-UHFFFAOYSA-N 2-methylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WODGMMJHSAKKNF-UHFFFAOYSA-N 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 title claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 22
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 238000006277 sulfonation reaction Methods 0.000 claims description 18
- 238000006482 condensation reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000007859 condensation product Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- WQHQCQSAAOGHQP-UHFFFAOYSA-N formaldehyde;2-methylnaphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WQHQCQSAAOGHQP-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention belongs to a method for producing a dye dispersing agent, particularly to a method for producing a methylnaphthalene sulfonic acid formaldehyde condensation product. The present invention has a technological process comprising: methylnaphthalene fractions are boiled and sulfonated; total acidity is regulated by the circulation of condensation material; neutralization is implemented by wholly using sodium hydroxide. The method has the advantages of low consumption of sulfuric acid, short technological process, low equipment investment, low labor intensity and no waste slag of calcium sulfate. The calcium content of the product is no greater than 200 ppm.
Description
The invention belongs to a kind of production method of dye dispersant.A kind of production method of condensation compound of methyl naphthalene sulfonic acid and formaldehyde of low calcium content particularly.
Prior art be by the methylnaphthalene fraction (through or without pre-treatment) for main raw material, through conventional method of sulfonating, adopt high mixture ratio sulfuric acid (methylnaphthalene fraction and sulfuric acid are 1: 1.25～1: 1.4 in molar ratio), and high total acidity (27%～32%) down and formaldehyde condensation produce.So the sulfuric acid consumption quota is high, condenses contains more excess sulfuric acid.Thereby must be provided with the N-process of removing excess sulfuric acid with the oxygen hydrolith; And the filtration operation of calcium sulfate waste residue; And the operation that removes the excessive calcium ion that is difficult for Ex-all.Thereby the common flow process of prior art is as follows:
Sulfonation → condensation → calcium hydroxide and sodium hydroxide neutralization → filtration calcium sulfate
→ again in and decalcification → refilter → drying
Above-mentioned technology has sulfuric acid consumption quota height; Waste residues calcium sulfate is arranged; Technical process is long; The facility investment height; Labour intensity is big; The shortcoming of the impure calcium ion height of product (being higher than 1000ppm).
The purpose of this invention is to provide a kind of is core with the azeotropic sulfonation; Cooperate with circulation of part condensation product and water and regulate the condensation reaction total acidity; And the method for all coming the condensation compound of methyl naphthalene sulfonic acid and formaldehyde of the low calcium content of neutral production with sodium hydroxide.Its technical process is as follows:
This method can overcome whole shortcomings of above-mentioned technology, and quality can reach Chinese quality standard GB9294-88.
Realize that concrete grammar of the present invention is:
The present invention adopts the azeotropic sulfonation, promptly utilizes entrainer to remove generation water in the sulfonation reaction process, makes sulfonation reaction have higher sulfuric acid concentration all the time, thereby sulfonation reaction is finished under lower proportioning.
Its primary condition be the methylnaphthalene fraction (through or without pre-treatment) and the vitriolic mol ratio be generally 1: 1.02～1: 1.1, sulfuric acid concentration is 94%～105%, with 96%～100% serves as better, the temperature of sulfonation reaction is 130～170 ℃, with 145～160 ℃ serves as better, the entrainer consumption is generally 1 gram～50 gram/moles (methylnaphthalene fraction), the sulfonation time is 2～8 hours, with 4～8 hours served as better, the used entrainer that dewaters can be a paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbons, and their substituent, as pentane, hexane, heptane, gasoline, hexanaphthene, benzene, toluene, dimethylbenzene etc., with the total acidity of this method gained sulfonated bodies between 20～24%.
Condensation reaction is the reaction of above-mentioned sulfonated bodies and formaldehyde, concentration of formaldehyde is generally 30%～38%, with 35%～37% for well, the mole proportioning of sulfonated bodies and formaldehyde is 1: 0.5～1: 1.1, serves as better with 1: 0.6～1: 0.8, setting-up point is generally at 100～145 ℃, condensation reaction time was generally 2～8 hours, and for the total acidity of condensation reaction, available partial condensate material circulation and water are adjusted, its value is 14%～24%, and recycle stock accounts for 0～1/2 of condensation material.
Because the total acidity of sulfonation reaction is lower, condensation reaction then utilizes recycle stock to adjust its acidity, thereby the neutralization of condenses can all directly neutralize with sodium hydroxide, naoh concentration is generally 30%～40%, and it is 7～8 that neutralization requires pH value, available then spray-dryer (or rotating drum dryer) drying, get product, in the finished product sodium sulphate content can≤5%, the content of calcium is very low, generally below 200ppm.
The sulfuric acid proportioning that the present invention has sulfonation reaction is low, and the sulfuric acid consumption quota is low; Technical process is short; Facility investment is low; Labour intensity is low; No waste residues calcium sulfate; The impurity calcium contents is lower than the advantage of 200ppm in the product.
Embodiments of the invention:
In the enamel reaction still that whipping appts, thermometer, water trap are housed, add 213 kilograms the methylnaphthalene fraction (through or without pre-treatment), be warming up to 130 ℃, 166 kilograms of the vitriol oils of adding 96%, and be warming up to 160 ℃, adding 30 kilograms of hexanes then is entrainer, azeotropic sulfonation 8 hours, azeotropic is taken 30 kilograms in water out of, steams entrainer then, promptly gets the sulfonation material.
In the sulfonation material, add 50 kilograms of condensation recycle stocks, add concentration then and be 110 kilograms in 37% formaldehyde, remaining on 135 ℃ reacted 5 hours down, be cooled to 80 ℃ immediately, the flushing discharging, except that reserving 50 kilograms as the next batch condensation recycle stock, it is 7～8 that all the other condensation materials are neutralized to PH with 40% sodium hydroxide, can carry out drying.Sodium sulphate content in the product≤5%, calcium ion content≤200ppm.
Claims (4)
1. the production method of the condensation compound of methyl naphthalene sulfonic acid and formaldehyde of a low calcium content is characterized in that the azeotropic sulfonation by the methylnaphthalene fraction, partial condensate material round-robin condensation course, and all with the sodium hydroxide neutralization, and the flow process of dry combination.
2. press the production method of the condensation compound of methyl naphthalene sulfonic acid and formaldehyde of the described low calcium content of claim 1, the sulfonation that it is characterized by the methylnaphthalene fraction is the azeotropic sulfonation process, methylnaphthalene fraction and vitriolic mol ratio are 1: 1.02～1: 1.1, sulfuric acid concentration is 96～100%, sulfonation temperature is 130～170 ℃, the entrainer consumption is at 1 gram～50 gram/moles, and the sulfonation time is 2～8 hours, and entrainer can be paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbons and their substituent.
3. press the production method of the condensation compound of methyl naphthalene sulfonic acid and formaldehyde of the described low calcium content of claim 1, the total acidity that it is characterized by condensation reaction is 14～24%, the total acidity of condensation reaction is adjusted by condensation recycle stock and water, its amount is 0～1/2 of condensation material, the mol ratio of sulfonated bodies and formaldehyde is 1: 0.6～1: 0.8, setting-up point is 100～145 ℃, and the time is 2～8 hours.
4. press the production method of the condensation compound of methyl naphthalene sulfonic acid and formaldehyde of the described low calcium content of claim 1, the neutralization that it is characterized by the condensation reaction thing is without calcium hydroxide, only use sodium hydroxide separately, and sulfuric acid content is≤5% in the finished product, calcium ion content≤200ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92105199A CN1036000C (en) | 1992-07-14 | 1992-07-14 | Method for producing condensation compound of methyl naphthalene sulfonic acid and formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92105199A CN1036000C (en) | 1992-07-14 | 1992-07-14 | Method for producing condensation compound of methyl naphthalene sulfonic acid and formaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1081451A CN1081451A (en) | 1994-02-02 |
| CN1036000C true CN1036000C (en) | 1997-10-01 |
Family
ID=4941221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92105199A Expired - Fee Related CN1036000C (en) | 1992-07-14 | 1992-07-14 | Method for producing condensation compound of methyl naphthalene sulfonic acid and formaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1036000C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070495A (en) * | 2010-11-11 | 2011-05-25 | 吉化集团吉林市星云工贸有限公司 | Method for preparing naphthalene sulfonic acid-formaldehyde condensate |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10246209A1 (en) * | 2002-10-04 | 2004-04-15 | Basf Ag | Non-ionic anthraquinone, quinophthalone or azo dye composition, e.g. as inkjet or sublimation transfer printing ink, comprises naphthalene sulfonic acid/formaldehyde condensate of high molecular weight as dispersant |
| CN101386587B (en) * | 2007-09-13 | 2012-02-01 | 浙江龙盛集团股份有限公司 | A kind of production technology of methylnaphthalenesulfonic acid formaldehyde condensate |
| CN101474543B (en) * | 2008-12-30 | 2011-04-20 | 浙江龙盛染料化工有限公司 | Method for preparing composite dispersing agent |
| CN101880247A (en) * | 2010-05-31 | 2010-11-10 | 杭州吉华江东化工有限公司 | Method for producing naphthalene sulfonic formaldehyde condensation compound |
| CN102114396A (en) * | 2010-12-10 | 2011-07-06 | 江阴市盛通化工有限公司 | Non-quinoline dispersant MF and production process |
| CN105175289A (en) * | 2015-10-09 | 2015-12-23 | 江苏瑞燕橡塑助剂有限公司 | Aromatic hydrocarbon sulfonation method |
| CN106866467B (en) * | 2017-03-31 | 2018-07-31 | 九江善水科技股份有限公司 | A kind of production method of K acid |
| CN111689879A (en) * | 2020-06-03 | 2020-09-22 | 浙江五龙新材股份有限公司 | Clean production method of dispersing agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5874713A (en) * | 1981-10-27 | 1983-05-06 | Sanyo Chem Ind Ltd | Production of naphthalenesulfonic acid/formalin condensate |
| CN1030574A (en) * | 1987-06-25 | 1989-01-25 | 清华大学 | High-efficient water reducer made of alkyl aryl sulfonate and aldehyde naphthalene sulfonate condensate |
-
1992
- 1992-07-14 CN CN92105199A patent/CN1036000C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5874713A (en) * | 1981-10-27 | 1983-05-06 | Sanyo Chem Ind Ltd | Production of naphthalenesulfonic acid/formalin condensate |
| CN1030574A (en) * | 1987-06-25 | 1989-01-25 | 清华大学 | High-efficient water reducer made of alkyl aryl sulfonate and aldehyde naphthalene sulfonate condensate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070495A (en) * | 2010-11-11 | 2011-05-25 | 吉化集团吉林市星云工贸有限公司 | Method for preparing naphthalene sulfonic acid-formaldehyde condensate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1081451A (en) | 1994-02-02 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |