CN100355719C - Salicylic acid preparing process - Google Patents
Salicylic acid preparing process Download PDFInfo
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- CN100355719C CN100355719C CNB2004100460764A CN200410046076A CN100355719C CN 100355719 C CN100355719 C CN 100355719C CN B2004100460764 A CNB2004100460764 A CN B2004100460764A CN 200410046076 A CN200410046076 A CN 200410046076A CN 100355719 C CN100355719 C CN 100355719C
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- Prior art keywords
- sodium
- reaction
- phenol
- solution
- obtains
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- 238000000034 method Methods 0.000 title claims abstract description 22
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 title abstract 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title abstract 3
- 229960004889 salicylic acid Drugs 0.000 title abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims abstract description 17
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 17
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229960004025 sodium salicylate Drugs 0.000 claims abstract description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 12
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 9
- 230000021523 carboxylation Effects 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 15
- 235000011089 carbon dioxide Nutrition 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000001175 calcium sulphate Substances 0.000 abstract 2
- 235000011132 calcium sulphate Nutrition 0.000 abstract 2
- 239000001569 carbon dioxide Substances 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 2
- -1 simultaneously Chemical compound 0.000 abstract 2
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 abstract 1
- 229950001102 salicylsulfuric acid Drugs 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing salicylic acid by phenol, calcium hydroxide, carbon dioxide and sulfuric acid which are used as raw materials. The method comprises the following steps: I) sodium sulfate solution is added to phenol, which reacts with calcium hydroxide, simultaneously, calcium phenoxide or calcium sulphate is generated, and finally, sodium phenolate solution and calcium sulphate can be obtained; II) after the obtained filter liquid, namely sodium phenolate, is dewatered, carbon dioxide is introduced, and sodium salicylate is generated through carboxylation; III) the obtained sodium salicylate reacts with sulfuric acid so as to obtain salicylic acid and sodium sulfate, and the obtained sodium sulfate solution is used for the reaction in step I).
Description
Invention field
The present invention relates to phenol, calcium hydroxide, carbonic acid gas and sulfuric acid is the salicylic method of feedstock production.
Background of invention
Whitfield's ointment is important Organic Chemicals, is widely used in fields such as synthetic perfume, synthetic medicine, synthetic pesticide, synthetic fine-chemical intermediate
At present, known is that the production method of raw material is to make sodium phenylate with phenol and sodium hydroxide reaction with phenol, again normal pressure or in depress and feed carbonic acid gas and carry out carboxylation reaction, make Whitfield's ointment with sulfuric acid acidation at last.
Yet these methods need consume a large amount of sodium hydroxide; In whole process of production, the consumption of water resources is big; And with acid-bearing wastewater that generates behind the sulfuric acid acidation and the aftertreatment complexity that contains a large amount of sodium sulfate byproduct, directly biochemical treatment, biochemical treatment again after needing to extract, diluting, big water gaging and sodium sulfate are discharged the general severe overweight of inorganic salt content in the waste water.
Higher in order to overcome existing method production cost, water resources consumption is big, waste water is difficult to biochemical treatment, has aftertreatment cost height, complex process, be difficult to shortcomings such as compliance with environmental protection requirements, we are by rational path combination and adopted cheap calcium hydroxide (or calcium oxide) to replace sodium hydroxide, by ingenious improvement, the sodium sulfate recirculation that produces in the technological process is used, thereby simplified phenol, Whitfield's ointment acidifying Wastewater Recovery treatment scheme, obtained versatile gypsum product simultaneously, eliminate the processing difficult problem of phenolic wastewater, realized successfully applying mechanically cleaner production.Both reached and reduced cost, protected the dual purpose of environment again.This invention provides a kind of easy, pollution-free, high produced in yields salicylic novel process.
Summary of the invention
The purpose of this invention is to provide the salicylic novel method of preparation.
Specifically, the invention provides a kind of is the salicylic method of feedstock production with phenol, calcium hydroxide, carbonic acid gas and sulfuric acid.
The invention provides the salicylic method of preparation, this method comprises the steps:
I) add metabisulfite solution in the phenol,, produce sodium phenylate and calcium sulfate, add sodium hydroxide again and continue to promote reaction, obtain sodium phenylate solution and calcium sulfate at last with calcium hydroxide reaction;
II) be that sodium phenylate dehydration back feeds carbonic acid gas the filtrate that obtains, carboxylation generates sodium salicylate;
III), obtain Whitfield's ointment and sodium sulfate with the sodium salicylate and the sulfuric acid reaction that obtain;
IV) metabisulfite solution that obtains is used for step I) reaction.
The specific embodiments that the present invention prepares salicylic method is as follows:
Step I): in a reaction vessel, phenol is mixed with sodium sulfate waste water; Under heating (for example, 50-80 ℃) stirring condition, slowly add calcium hydroxide powder or lime white reaction 40-100 minute, obtain sodium phenylate solution.By-product calcium sulfate is by filtering or centrifugation.
Step II): with step I the sodium phenylate solution dehydrates that obtains) feeds carbonic acid gas and carries out carboxylation reaction under normal pressure, produce sodium salicylate.
Step II I): to Step II add sulfuric acid in the sodium salicylate that obtains), obtain Whitfield's ointment and metabisulfite solution.Centrifugation.
Step IV): with Step II I isolated mother liquor is directly used in step I)).Main component is a sodium sulfate in the described mother liquor, has a considerable amount of phenol, Whitfield's ointment, sulfuric acid existence simultaneously, and this mother liquor need not to handle, and can be directly used in step I).
In the methods of the invention, generally speaking the reaction raw materials consumption of employing is the stoichiometric ratio according to reaction, difference according to circumstances, and a kind of or two kinds of raw materials wherein can increase or reduce.The choosing amount of reaction auxiliary can be selected by the general knowledge of this area.
The Whitfield's ointment that the inventive method is prepared can adopt conventional method to carry out aftertreatment, for example adopts methods such as washing, decolouring, recrystallization.
Compared with prior art, the present invention has following advantage:
One, cheap calcium hydroxide (or calcium oxide) the replacement sodium hydroxide of use, and by-product calcium sulfate can be used as the starting material of cement, plasterboard etc., thereby greatly reduces production cost;
Two, make full use of the sodium sulfate in the mother liquor, turned waste into wealth, reduced post-processing step, reduced processing costs, obtained new benefit;
Three, residual phenol, Whitfield's ointment is able to reuse in the mother liquor, and the total recovery of technological process obviously improves;
Four, the equipment of former technology is only changed slightly, increases filtration unit and can use the present invention.
Embodiment
In order to be illustrated more clearly in the present invention, hereinafter adopt indefiniteness embodiment to be described further.
Embodiment 1
Sodium sulfate 443kg and water 1343kg are dropped in the reactor, add phenol 610kg, heated and stirred slowly drops into 316kg calcium hydroxide (95%) under 60 ℃, reacts 60 minutes, drop into 25kg sodium hydroxide, reacted filtered while hot, small amount of thermal water washing solid 3 times (50kg hot water altogether) again 30 minutes, merge wash water in solution, obtain sodium phenylate solution 2057kg.
Sodium phenylate solution is dropped into reactor, add phenol 600kg, thermal dehydration 2 hours reclaims phenol 450kg, water 1377kg; Feeding 220kg (annotate: the practical situation of plant produced) carbonic acid gas, carried out carboxylation reaction 2 hours, reclaim phenol 190kg simultaneously; Obtain sodium salicylate 878kg.
Sodium salicylate through obtaining adds the 600kg hot water dissolving, transfers in the acidifying still.The sulfuric acid 1143kg acid out of adding 35% obtains Whitfield's ointment 687kg (content 99%), total recovery 91.7% behind filtration, washing, decolouring, the recrystallization under 80 ℃.
Also obtain 1940kg technology mother liquor simultaneously, but wherein contain sodium sulfate 443kg, Whitfield's ointment 10kg, phenol 50kg, sulfuric acid 94kg and water 1343kg direct reuse, do next pot raw material.
Embodiment 2
Get the technology mother liquor 1940kg of embodiment 1, wherein contain sodium sulfate 443kg, Whitfield's ointment 10kg, phenol 50kg, sulfuric acid 94kg and water 1343kg, drop in the reactor, add phenol 550kg, heated and stirred slowly drops into 316kg calcium hydroxide (95%) under 60 ℃, reacts 60 minutes, drop into 25kg sodium hydroxide, reacted filtered while hot, small amount of thermal water washing solid 3 times (50kg hot water altogether) again 30 minutes, merge wash water in solution, obtain sodium phenylate solution 2057kg.
Sodium phenylate solution is dropped into reactor, add phenol 600kg, thermal dehydration 2 hours reclaims phenol 450kg, water 1377kg; Feeding 220kg (annotate: the practical situation of plant produced) carbonic acid gas, carried out carboxylation reaction 2 hours, reclaim phenol 190kg simultaneously; Obtain sodium salicylate 878kg.
Sodium salicylate through obtaining adds the 600kg hot water dissolving, transfers in the acidifying still.The sulfuric acid 1143kg acid out of adding 35% obtains Whitfield's ointment 687kg (content 99%), total recovery 91.7% behind filtration, washing, decolouring, the recrystallization under 80 ℃.But the mother liquor direct reuse of compositions such as the contains sodium sulfate that obtains is done next pot raw material.
Comparative examples
Drop into phenol 560kg in reactor, add water 734kg, heating for dissolving adds 32% liquid caustic soda 781kg, and normal-temperature reaction 60 minutes adds solvent bank water phenol 600kg, and thermal dehydration 2 hours reclaims phenol; Feed the 220kg carbonic acid gas, carboxylation 5 hours adds the 4000kg water dissolution, adds 35% sulfuric acid 1186kg pickling, obtains Whitfield's ointment 679kg (content 99%) behind filtration, washing, decolouring, the recrystallization, total recovery 89%.The method of extraction, absorption and biochemical treatment is generally adopted in the aftertreatment of sodium sulfate byproduct, and inorganic salt content can't reduce in the waste water.
Claims (2)
1, the salicylic method of a kind of preparation, this method comprises the steps:
I) add metabisulfite solution in the phenol,, produce sodium phenylate and calcium sulfate, add sodium hydroxide again and continue to promote reaction, obtain sodium phenylate solution and calcium sulfate at last with calcium hydroxide reaction;
II) be that sodium phenylate dehydration back feeds carbonic acid gas the filtrate that obtains, carboxylation generates sodium salicylate;
III), obtain Whitfield's ointment and sodium sulfate with the sodium salicylate and the sulfuric acid reaction that obtain;
IV) metabisulfite solution that obtains is used for step I) reaction.
2, according to the process of claim 1 wherein:
I) in a reaction vessel, controlled temperature 50-80 ℃, under stirring condition, lentamente the calcium hydroxide powder is joined in phenol and the sodium sulfate mixing solutions and react, obtain sodium phenylate solution and calcium sulfate precipitation;
II) with step I) under normal pressure, feed carbonic acid gas after the sodium phenylate solution dehydrates that obtains and carry out carboxylation reaction, produce sodium salicylate;
III) in Step II) in add the sulfuric acid acid out in the sodium salicylate that obtains, obtain Whitfield's ointment;
IV) isolated mother liquor need not to handle Step II I), is directly used in step I).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100460764A CN100355719C (en) | 2004-06-04 | 2004-06-04 | Salicylic acid preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100460764A CN100355719C (en) | 2004-06-04 | 2004-06-04 | Salicylic acid preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1706791A CN1706791A (en) | 2005-12-14 |
| CN100355719C true CN100355719C (en) | 2007-12-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100460764A Expired - Fee Related CN100355719C (en) | 2004-06-04 | 2004-06-04 | Salicylic acid preparing process |
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| Country | Link |
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| CN (1) | CN100355719C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086562B (en) * | 2011-11-01 | 2015-02-18 | 上海博丹环境工程技术有限公司 | Phenolic resin wastewater processing method and special-purposed device |
| CN111170351A (en) * | 2018-11-13 | 2020-05-19 | 湖南省金翼有色金属综合回收有限公司 | Lead sulfate waste material desulfurization device and process thereof |
| CN115433074A (en) * | 2021-06-01 | 2022-12-06 | 广州市奥颜化妆品有限公司 | A kind of dissolving method and preparation technology of salicylic acid acne gel |
| CN116267989B (en) * | 2022-09-09 | 2024-05-07 | 兰州大学 | Nanometer iron antibacterial agent for fusarium trilineum |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6210043A (en) * | 1985-07-04 | 1987-01-19 | Mitsui Petrochem Ind Ltd | Method for producing salicylic acid derivatives |
| CN1289760A (en) * | 2000-09-25 | 2001-04-04 | 谢虎 | Process for preparing salicylic acid by solvent method |
-
2004
- 2004-06-04 CN CNB2004100460764A patent/CN100355719C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6210043A (en) * | 1985-07-04 | 1987-01-19 | Mitsui Petrochem Ind Ltd | Method for producing salicylic acid derivatives |
| CN1289760A (en) * | 2000-09-25 | 2001-04-04 | 谢虎 | Process for preparing salicylic acid by solvent method |
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| Publication number | Publication date |
|---|---|
| CN1706791A (en) | 2005-12-14 |
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Granted publication date: 20071219 Termination date: 20100604 |