CN104086400A - Production process of sodium naphthalene acetate - Google Patents
Production process of sodium naphthalene acetate Download PDFInfo
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- CN104086400A CN104086400A CN201410336395.2A CN201410336395A CN104086400A CN 104086400 A CN104086400 A CN 104086400A CN 201410336395 A CN201410336395 A CN 201410336395A CN 104086400 A CN104086400 A CN 104086400A
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- nafusaku
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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Abstract
The invention relates to the field of synthesis of plant growth regulators and particularly relates to a production process of sodium naphthalene acetate. The production process comprises the following steps of in the presence of a catalyst, reacting naphthalene with chloroacetic acid to obtain a naphthylacetic acid synthetic solution; reacting the naphthylacetic acid synthetic solution with sodium hydroxide to obtain an aqueous solution of sodium naphthalene acetate; acidifying the aqueous solution of sodium naphthalene acetate to remove impurities to obtain a filtrate, adding sodium chloride to the filtrate, and carrying out salting out and centrifuging to obtain sodium naphthalene acetate. By virtue of the production process, the usage amount of hydrochloric acid and sodium hydroxide as raw materials can be reduced, and the production cost of sodium naphthalene acetate is reduced; the acidic wastewater discharge in the industrial production can be decreased to solve the environmental pressure, and the clean production requirements are achieved; by virtue of the production process, the operation steps are simplified.
Description
Technical field
The present invention relates to plant-growth regulator synthetic field, particularly a kind of production technique of Nafusaku.
Background technology
Nafusaku is a kind of wide spectrum, efficient, low toxicity plant-growth regulator, and molecular formula is C
12h
9o
2na, structural formula is suc as formula shown in I.Nafusaku can promote rapidly cell fission and expansion, induction forms adventive root, there is growth regulation, hestening rooting, sprout, bloom, prevent fruit drop, form seedless fruit, promote the effects such as precocity, volume increase, also can strengthen simultaneously plant drought resisting, cold-resistant, disease-resistant, resist ability saline and alkaline, hot-dry wind tolerance.Nafusaku has remarkable solvability, and high purity α-naphthaleneacidsodium has water, oily two dissolubilities, therefore can make separately the formulations such as aqua, pulvis, missible oil, granula, and very easy to use, effect is very good.It is that unit molecule exists in solution, is uniformly dispersed, and is easily absorbed by plants.Meanwhile, Nafusaku has good mixture, high purity α-naphthaleneacidsodium can with the composite use of a lot of plant-growth regulator, as growth hormone, sodium nitrophenolate, the class of taking root material, sterilant, fertilizer etc.Because the effect of Nafusaku is better, have good mixture, can with the composite use of various plants growth regulator, so range of application is wider in real life.
Formula I
At present, in actual production, the method for synthetic Nafusaku is: add in still with naphthalene and Mono Chloro Acetic Acid, add iron powder and Potassium Bromide, after temperature reaction, the naphthylacetic acid that adds liquid caustic soda that reaction is generated changes Nafusaku into, use again steam distillation, steam the naphthalene not reacted, the Nafusaku solution that has distilled naphthalene is added to hydrochloric acid, condition pH value 5～7, except the superpolymer of dereaction generation, adding salt acid for adjusting pH value is 2 again, in reactor, boil the centrifugal solid obtaining dry moisture, add liquid caustic soda, regulating pH value is 10, boil dry after moisture, shatter to obtain product Nafusaku.The concrete technological process of production as shown in Figure 1.In the production process of this technique, on the one hand, can produce the acid waste water that a large amount of pH values is 2, bring very large pressure to environmental protection; On the other hand, need to consume a large amount of hydrochloric acid and sodium hydroxide and just can obtain the finished product, and produce a large amount of by product sodium-chlor, not only increased the cost of product, the by product sodium-chlor of generation has also increased aftertreatment cost.Therefore, provide a kind of and can reduce the discharge of acid waste water and the consumption of raw material, Nafusaku production technique that by product is few has important practical significance.
Summary of the invention
In view of this, the invention provides a kind of production technique of Nafusaku.This production technique directly adds sodium-chlor after carrying out acidifying removal of impurities at Nafusaku water liquid, adopt salting-out process to obtain Nafusaku, thereby can reduce the consumption of raw material hydrochloric acid and sodium hydroxide, solve reusing of former technique soda acid, reduce the production cost of Nafusaku; Can reduce industrial acid waste water discharge, solve the pressure of environmental protection, reach the requirement of cleaner production.
In order to realize foregoing invention object, the invention provides following technical scheme:
The production technique that the invention provides a kind of Nafusaku, comprises the steps:
Under the condition existing at catalyzer, naphthalene and chloroacetate reaction, obtain the synthetic liquid of naphthylacetic acid;
Get the synthetic liquid of naphthylacetic acid and sodium hydroxide reaction, obtain Nafusaku water liquid;
Get Nafusaku water liquid acidifying removal of impurities, obtain filtrate, in filtrate, add sodium-chlor, through saltouing, centrifugal, obtain Nafusaku.
Production principle of the present invention: steaming after naphthalene finishes, the product obtaining is approximately 12% Nafusaku and the water liquid of a large amount of impurity.Nafusaku water-soluble extremely strong, Nafusaku ionizes completely, when adding after the strong electrolyte sodium-chlor containing same ion in Nafusaku water liquid, in solution, [Na+] increases suddenly, and [Na+] is greater than Nafusaku and is dissolved in the Na ion concentration in water, due to common-ion effcet, balance is originally destroyed, the solubleness of Nafusaku in NaCl solution is reduced, and balance is moved to the left, thereby separates out Nafusaku crystal.
Filtrate being obtaining through saltouing, after centrifugal contained 4% Nafusaku and impurity, and this filtrate is added to acidification pool, and adding salt acid for adjusting pH value is 5～6, removes the impurity of separating out, and recycles for the synthetic recovery naphthalene operation stage of lower batch.
In order fully to separate out Nafusaku solid, in embodiment more provided by the invention, the mass ratio of sodium-chlor and filtrate is (18～25): (75～82).
As preferably, the mass ratio of sodium-chlor and filtrate is 20:80.
In the present invention, adopt the method for naturally cooling crystallization to separate out Nafusaku solid.In embodiment more provided by the invention, saltout and be specially: be naturally down to 15 DEG C～30 DEG C, stir.
As preferably, the temperature of saltouing is down to 15 DEG C～20 DEG C naturally.
In order fully to separate out Nafusaku solid, as preferably, the time of saltouing is 8～10h.
The time of preferably, saltouing is 8h.
In order fully to separate out Nafusaku solid, as preferably, the time of stirring is 2～4h.
Preferably, the time of stirring is 3h.
In embodiment more provided by the invention, centrifugal and obtain and also comprise step dry, that pulverize between Nafusaku.
In embodiment more provided by the invention, catalyzer is a kind of in iron powder or Potassium Bromide or both mixtures.
As preferably, catalyzer is the mixture of iron powder and Potassium Bromide.
Nafusaku water liquid contains impurity, and these impurity can generate superpolymer under acidic conditions, thereby can realize the object by removing by filter these impurity.In embodiment more provided by the invention, acidifying removal of impurities is specially: regulate pH value to 5～6, filter.
As preferably, regulating the reagent of pH value employing is hydrochloric acid.
As preferably, the mass percentage concentration of hydrochloric acid is 10%～25%.
As preferably, the temperature of acidifying removal of impurities is 35 DEG C～45 DEG C.
Preferably, the temperature of acidifying removal of impurities is 40 DEG C.
In embodiment more provided by the invention, the pH value of the synthetic liquid of naphthylacetic acid and sodium hydroxide reaction is 10～11.
In embodiment more provided by the invention, the temperature of the synthetic liquid of naphthylacetic acid and sodium hydroxide reaction is 40～80 DEG C.
In embodiment more provided by the invention, the mass percentage concentration of sodium hydroxide is 40%～50%.
As preferably, the mass percentage concentration of sodium hydroxide is 46%.
In the Nafusaku water liquid obtaining, contain unreacted naphthalene, in order to reclaim unreacted naphthalene, in embodiment more provided by the invention, obtaining Nafusaku water liquid and getting the step that also comprises distillation between Nafusaku water liquid acidifying removal of impurities.
The invention provides a kind of production technique of Nafusaku.This production technique comprises: under the condition existing at catalyzer, naphthalene and chloroacetate reaction, obtain the synthetic liquid of naphthylacetic acid; Get the synthetic liquid of naphthylacetic acid and sodium hydroxide reaction, obtain Nafusaku water liquid; Get Nafusaku water liquid acidifying removal of impurities, obtain filtrate, in filtrate, add sodium-chlor, through saltouing, centrifugal, obtain Nafusaku.This production technique directly adds sodium-chlor after carrying out acidifying removal of impurities at Nafusaku water liquid, adopt salting-out process to obtain Nafusaku, thereby can reduce the consumption of raw material hydrochloric acid and sodium hydroxide, solve reusing of former technique soda acid, reduce the production cost of Nafusaku; Can reduce industrial acid waste water discharge, solve the pressure of environmental protection, reach the requirement of cleaner production; This production technique has been simplified operation steps, after acidifying removal of impurities, add sodium-chlor can directly generate Nafusaku solid, avoid after acidifying removal of impurities, adding in former technique salt acid for adjusting pH value to 2 generation naphthylacetic acid, add again the loaded down with trivial details step that alkali generates Nafusaku, also avoid the post-processing step of the by product sodium-chlor producing in original production process simultaneously, saved cost.
Brief description of the drawings
Fig. 1 shows the production technological process of prior art production Nafusaku;
Fig. 2 shows the production technological process of production Nafusaku provided by the invention;
Fig. 3 shows the HPLC collection of illustrative plates of Nafusaku in embodiment 1.
Embodiment
The invention discloses a kind of production technique of Nafusaku, those skilled in the art can use for reference content herein, suitably improve processing parameter and realize.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are all deemed to be included in the present invention.Method of the present invention and application are described by preferred embodiment, related personnel obviously can change methods and applications as herein described in content of the present invention, spirit and scope or suitably change and combination not departing from, and realizes and apply the technology of the present invention.
In the production technique of Nafusaku provided by the invention, raw materials used or reagent all can be buied by market.
Below in conjunction with embodiment, further set forth the present invention:
Synthesizing of embodiment 1 Nafusaku
The production technique of Nafusaku is shown in Fig. 2.Concrete operations are as follows:
In reactor, add 300Kg naphthalene and 100Kg Mono Chloro Acetic Acid, add iron powder 2.5Kg and Sodium Bromide 12Kg at 210 DEG C, to carry out building-up reactions, after reaction finishes, to the liquid sodium hydroxide 85Kg that adds water 600L and 46% in reactor, at 40 DEG C, react, after regulating pH value to be 10～11, start to reclaim unreacted naphthalene with steam distillation, after naphthalene Distillation recovery is most, to contain in the water liquid suction acidification pool of Nafusaku, cool to 40 DEG C, adding mass percentage concentration is 25% hydrochloric acid, regulate pH value 5～6, remove the impurity generating in building-up reactions, after filtration, in filtrate, add sodium-chlor 180Kg, the content that makes sodium-chlor in filtrate is 20% (mass ratio of sodium-chlor and filtrate is 20:80).Be down to after 15 DEG C～20 DEG C in 5 hours, then stir after 3 hours, separate out solid, centrifugal.Collect the filtrate of centrifugal gained, for adding and recycle next time after naphthalene and Mono Chloro Acetic Acid building-up reactions finish.Get the solid obtaining after centrifugal and identify, as shown in Figure 3, spectrum data is in table 1 for qualification collection of illustrative plates, and result shows that solid is Nafusaku.Get solid in evaporating kettle by moisture evaporate to dryness, through pulverizing, obtain Nafusaku crude product 150Kg, content is 75%.
The spectrum data of table 1 Nafusaku
Synthesizing of embodiment 2 Nafusakus
The production technique of Nafusaku is shown in Fig. 2.Concrete operations are as follows:
In reactor, add 300Kg naphthalene and 100Kg Mono Chloro Acetic Acid, add iron powder 2.0Kg and Sodium Bromide 8.5Kg, at 210 DEG C, carry out building-up reactions, after reaction finishes, to the liquid sodium hydroxide 85Kg that adds water 600L and 40% in reactor, at 60 DEG C, react, after regulating pH value to be 10～11, start to reclaim unreacted naphthalene with steam distillation, after naphthalene Distillation recovery is most, to contain in the water liquid suction acidification pool of Nafusaku, cool to 35 DEG C, adding mass percentage concentration is 20% hydrochloric acid, regulate pH value 5～6, remove the impurity generating in building-up reactions, after filtration, in filtrate, add sodium-chlor 156Kg, the content that makes sodium-chlor in filtrate is 18% (mass ratio of sodium-chlor and filtrate is 18:82).Be down to after 15 DEG C～20 DEG C in 7 hours, then stir after 2 hours, separate out solid, centrifugal.Collect the filtrate of centrifugal gained, for adding and recycle next time after naphthalene and Mono Chloro Acetic Acid building-up reactions finish.Get the solid obtaining after centrifugal and identify, result shows that solid is Nafusaku.Get solid in evaporating kettle by moisture evaporate to dryness, through pulverizing, obtain Nafusaku crude product 145Kg, content is 76%.
Synthesizing of embodiment 3 Nafusakus
The production technique of Nafusaku is shown in Fig. 2.Concrete operations are as follows:
In reactor, add 300Kg naphthalene and 100Kg Mono Chloro Acetic Acid, add iron powder 2.5Kg and Sodium Bromide 12Kg, at 210 DEG C, carry out building-up reactions, after reaction finishes, to the liquid sodium hydroxide 85Kg that adds water 600L and 50% in reactor, at 80 DEG C, react, after regulating pH value to be 10～11, start to reclaim unreacted naphthalene with steam distillation, after naphthalene Distillation recovery is most, to contain in the water liquid suction acidification pool of Nafusaku, cool to 45 DEG C, adding mass percentage concentration is 10% hydrochloric acid, regulate pH value 5～6, remove the impurity generating in building-up reactions, after filtration, in filtrate, add sodium-chlor 220Kg, the content that makes sodium-chlor in filtrate is 25% (mass ratio of sodium-chlor and filtrate is 25:75).Be down to after 20 DEG C～30 DEG C in 6 hours, then stir after 4 hours, separate out solid, centrifugal.Collect the filtrate of centrifugal gained, for adding and recycle next time after naphthalene and Mono Chloro Acetic Acid building-up reactions finish.Get the solid obtaining after centrifugal and identify, result shows that solid is Nafusaku.Get solid in evaporating kettle by moisture evaporate to dryness, through pulverizing, obtain Nafusaku crude product 162Kg, content is 73.5%.
Synthesizing of comparative example 1 Nafusaku
The production technique of Nafusaku is shown in Fig. 1, and concrete operations are as follows:
300Kg naphthalene and 100Kg Mono Chloro Acetic Acid are added in still, add iron powder 2.5Kg and Potassium Bromide 12.0Kg, after temperature reaction, the naphthylacetic acid that adds 85Kg liquid caustic soda that reaction is generated changes Nafusaku into, use again steam distillation, steam the naphthalene not reacted, the Nafusaku solution that has distilled naphthalene is added to hydrochloric acid, condition pH value 5～7, except the superpolymer of dereaction generation, adding salt acid for adjusting pH value is 2 again, in reactor, boil the centrifugal solid obtaining dry moisture, add the liquid caustic soda of 75Kg (46%), regulating pH value is 10, boil dry after moisture, shatter to obtain product Nafusaku crude product 150Kg, content is 72%.
Result shows, in the production technique of comparative example 1 Nafusaku, 30% the concentrated hydrochloric acid of producing the Nafusaku consumption of 150Kg is 125Kg, and 46% sodium hydroxide 150Kg can produce the acid waste water that a large amount of pH values is 2 simultaneously.And in the production technique of embodiment 1 Nafusaku, produce 150Kg Nafusaku and just consume 30% concentrated hydrochloric acid 20Kg, 46% sodium hydroxide 85Kg, the solution of separating out Nafusaku can add and steam the use of naphthalene step cycle, the discharge of no acidic waste water through the centrifugal filtrate obtaining.Visible, production technique provided by the invention can reduce the consumption of raw material hydrochloric acid and sodium hydroxide, in the production of this technique, directly separates out Nafusaku with salting-out process, has solved reusing of former technique soda acid, has reduced the production cost of Nafusaku; Production technique provided by the invention can reduce industrial acid waste water discharge, in this technique, the solution of separating out Nafusaku can add and steam the use of naphthalene step cycle through the centrifugal filtrate obtaining, and substantially can reach zero discharge of industrial waste water, solve the pressure of environmental protection, reached the requirement of cleaner production.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a production technique for Nafusaku, is characterized in that, comprises the steps:
Under the condition existing at catalyzer, naphthalene and chloroacetate reaction, obtain the synthetic liquid of naphthylacetic acid;
Get the synthetic liquid of described naphthylacetic acid and sodium hydroxide reaction, obtain Nafusaku water liquid;
Get described Nafusaku water liquid acidifying removal of impurities, obtain filtrate, in described filtrate, add sodium-chlor, through saltouing, centrifugal, obtain Nafusaku.
2. production technique according to claim 1, is characterized in that, the mass ratio of described sodium-chlor and described filtrate is (18～25): (75～82).
3. production technique according to claim 1, is characterized in that, described in saltout and be specially: be naturally down to 15 DEG C～30 DEG C, stir.
4. production technique according to claim 1, is characterized in that, described in time of saltouing be 8～10h.
5. production technique according to claim 3, is characterized in that, the time of described stirring is 2～4h.
6. production technique according to claim 1, is characterized in that, also comprises step dry, that pulverize between described centrifugal and described acquisition Nafusaku.
7. production technique according to claim 1, is characterized in that, described catalyzer is a kind of in iron powder or Potassium Bromide or both mixtures.
8. production technique according to claim 1, is characterized in that, described acidifying removal of impurities is specially: regulate pH value to 5～6, filter.
9. production technique according to claim 1, is characterized in that, the reagent that described adjusting pH value adopts is hydrochloric acid.
10. production technique according to claim 1, is characterized in that, the temperature of described acidifying removal of impurities is 35 DEG C～45 DEG C.
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| CN201410336395.2A CN104086400A (en) | 2014-07-15 | 2014-07-15 | Production process of sodium naphthalene acetate |
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| CN201410336395.2A CN104086400A (en) | 2014-07-15 | 2014-07-15 | Production process of sodium naphthalene acetate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796324A (en) * | 2019-02-16 | 2019-05-24 | 河南大学 | Methyl α-naphthyl acetate preparation method |
| CN111153787A (en) * | 2020-01-19 | 2020-05-15 | 浙江大鹏药业股份有限公司 | Preparation method of 1-naphthylacetic acid |
| CN111499504A (en) * | 2019-12-24 | 2020-08-07 | 浙江理工大学 | Preparation method of α -naphthylacetic acid |
| CN115735921A (en) * | 2022-12-21 | 2023-03-07 | 郑州农达生化制品有限公司 | Preparation method of high-content naphthylacetic acid soluble powder |
-
2014
- 2014-07-15 CN CN201410336395.2A patent/CN104086400A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 张袖丽等: "用萘和氯乙酸合成萘乙酸的研究", 《安徽农业大学学报》 * |
| 王选良: "谷氨酸单钠盐的提纯分离方法", 《发酵科技通讯》 * |
| 马冰洁等: "α-萘乙酸合成工艺研究", 《农药》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796324A (en) * | 2019-02-16 | 2019-05-24 | 河南大学 | Methyl α-naphthyl acetate preparation method |
| CN111499504A (en) * | 2019-12-24 | 2020-08-07 | 浙江理工大学 | Preparation method of α -naphthylacetic acid |
| CN111153787A (en) * | 2020-01-19 | 2020-05-15 | 浙江大鹏药业股份有限公司 | Preparation method of 1-naphthylacetic acid |
| CN111153787B (en) * | 2020-01-19 | 2022-06-24 | 浙江大鹏药业股份有限公司 | Preparation method of 1-naphthylacetic acid |
| CN115735921A (en) * | 2022-12-21 | 2023-03-07 | 郑州农达生化制品有限公司 | Preparation method of high-content naphthylacetic acid soluble powder |
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Application publication date: 20141008 |