A method for purifying cashmerone raw material indan

Abstract

The present invention belongs to organic chemical industry, and specifically relates to a method for purifying indane, a raw material of cashmerone. 1. A method for purifying indane, a raw material of cashmerone, comprises the following steps: S1, alkali washing and water washing of galaxol indane to obtain crude cashmerone indane; S2, adding aluminum-magnesium modified hydroxymethyl cellulose coagulant to the crude cashmerone indane obtained in S1, stirring it fully, standing it, and obtaining a supernatant after enhanced coagulation treatment; S3, adding redox-treated graphene powder to the supernatant obtained in S2, stirring it fully, standing it, and obtaining a supernatant after adsorption treatment; S4, injecting the supernatant after adsorption treatment obtained in S3 into an indane distillation tower, and obtaining fine indane for making cashmerone by distillation. The beneficial effect of the present invention is: the pentamethyl indane in the basic essence galaxol is purified to synthesize the advanced essence cashmerone, thereby increasing the economic benefits of the enterprise.

Description

Technical Field

[0001] The invention belongs to organic chemical industry, and specifically relates to a method for purifying indan, a raw material of cashmeranone. Background Art

[0002] Cashmeranone is a musk fragrance compound first successfully developed by the International Flavor & Fragrance Company (IFF) in the 1970s. It has a strong musk, floral and ambergris scent and is a raw material for preparing high-end perfumes and cosmetics, and is particularly favored by perfumers.

[0003] In the industrial production of cashmeridian, pentamethylindane is used as the raw material and Raney nickel is used as the catalyst. Tetrahydropentamethylindane is first prepared by selective hydrogenation, and then a mixture of sodium dichromate and glacial acetic acid is used as the oxidant for oxidation to obtain cashmeridian. The reaction mechanism is as follows:

[0004]

[0005] The synthesis process of galaxolide is as follows: first, methyl styrene and isopentene undergo Friedel-Crafts alkylation ring-closing reaction under the catalysis of phosphorus pentoxide to generate pentamethyl indane, then the pentamethyl indane undergoes hydroxyalkylation reaction with propylene oxide under the conditions of chlorobenzene solvent and aluminum chloride catalyst to generate pentamethyl indanol, and finally undergoes cyclization reaction with methylal to generate galaxolide; in the preparation process of galaxolide, the requirements for pentamethyl indane as a raw material are relatively low, and it can be used directly after the Friedel-Crafts alkylation ring-closing reaction, but when it is used as a raw material for the synthesis of cashmerone, since the pentamethyl indane contains phosphorus ions, it will cause corrosion when participating in the high-pressure hydrogenation reaction, and at the same time, the expensive cashmerone catalyst Raney nickel will be deactivated, and it cannot be repeatedly used, resulting in excessively high production costs, so it is necessary to perform secondary treatment on the galaxolide indane (including pentamethyl indane and phosphorus ions) to obtain qualified cashmerone indane (including pentamethyl indane and not containing phosphorus ions) for the synthesis of cashmerone. Summary of the invention

[0006] In order to solve the above problems, the present invention provides a method for purifying indane, a raw material of cashmerone, which removes phosphorus ions, suspended matter and other organic matter in indane through alkali washing and water washing, aluminum-magnesium modified hydroxymethyl cellulose coagulant, redox treated graphene powder and distillation, thereby increasing the content of pentamethylindane and obtaining qualified high-quality pentamethylindane to synthesize cashmerone.

[0007] The present invention provides the following technical solutions:

[0008] A method for purifying indan, a raw material of cashmeranone, comprises the following steps:

[0009] S1, adding lye to the galaxol indane, heating and stirring to wash, standing and stratifying to separate the lower alkali water, adding pure water, stirring and washing, standing and stratifying to separate the lower water phase, to obtain the crude cashmeran ketone indane;

[0010] S2, adding aluminum-magnesium-modified hydroxymethyl cellulose coagulant to the crude cashmerone indane obtained in S1, stirring thoroughly, and standing to obtain a supernatant after enhanced coagulation treatment;

[0011] S3, adding the redox-treated graphene powder to the supernatant obtained in S2, stirring thoroughly, and standing to obtain a supernatant after adsorption treatment;

[0012] S4, injecting the supernatant obtained after the adsorption treatment in S3 into an indane distillation tower, and obtaining fine indane for making cashmeranone through distillation.

[0013] Preferably, the aluminum-magnesium modified hydroxymethyl cellulose coagulant in S2 is composed of aluminum sulfate, magnesium sulfate and hydroxymethyl cellulose in a mass ratio of (8-10):(1-3):1.

[0014] Preferably, the preparation method of the redox treated graphene powder is as follows: sulfuric acid and nitric acid are stirred in an ice bath, then graphite powder is added to the mixed acid, stirring continuously, potassium persulfate is slowly added to the mixed solution in batches, the ice bath temperature is controlled to be lower than 10°C, then the temperature is raised to 60-70°C, stirring continuously for 10-20h, cooling to no higher than 30°C, diluting with deionized water, adding 30% hydrogen peroxide and stirring, the solution color changes to bright yellow, filtering, washing the filter cake with 10% dilute hydrochloric acid in turn, washing with deionized water until neutral, and drying to obtain graphene oxide;

[0015] Graphene oxide is dissolved in deionized water, ultrasonically formed into a suspension, the pH is adjusted to alkaline with ammonia water, sodium thiosulfate is added and heated to react, and after the reaction is completed, deionized water is washed to neutrality and dried to obtain redox-treated graphene powder.

[0016] Preferably, the galaxol indane comprises more than 80% of pentamethyl indane, 0.5%-2% of phosphorus-containing substances, 1%-3% of other organic substances, and less than 1% of suspended solids.

[0017] Preferably, in S1, the mass ratio of galaxol indane to alkali solution is 1:(5-10), and the alkali solution is a sodium hydroxide aqueous solution with a mass fraction of 10%;

[0018] The mass ratio of the galaxol indane to deionized water is 1:(5-10).

[0019] Preferably, the mass ratio of the sulfuric acid, nitric acid, graphite powder and potassium persulfate is 10:1:(0.5-1):2.

[0020] Preferably, the added mass of the 30% hydrogen peroxide is 3-5 times the mass of the graphite powder.

[0021] Preferably, the mass ratio of graphene oxide to sodium thiosulfate is 1:(5-10).

[0022] Preferably, the pH is adjusted to 10-11 with aqueous ammonia.

[0023] Preferably, the heating reaction condition is 60-80° C. and stirring for 1-3 h.

[0024] The beneficial effects of the present invention are:

[0025] 1. Purify the pentamethylindane in the basic flavor galaxolone to synthesize the advanced flavor cashmerone to increase the economic benefits of the enterprise. The purified pentamethylindane does not contain phosphorus ions, which will not cause the deactivation of the catalyst Raney nickel of cashmerone. The catalyst can be used repeatedly to reduce production costs.

[0026] 2. The present invention uses aluminum-magnesium modified hydroxymethyl cellulose coagulant to remove suspended solids of galaxol indane by utilizing its powerful coagulation effect. The formed flocs are dense in shape and low in water content, making it easy to achieve solid-liquid separation, thereby removing most of the suspended solids.

[0027] 3. The graphite powder of the present invention is oxidized by mixed treatment of mixed acid, persulfate and hydrogen peroxide, and the OO bond in the persulfate is broken and activated to SO4 with a higher redox potential and a longer half-life. 2- At the same time, the graphene surface points quickly reach high temperatures, thereby forming active centers and generating vacancies on the graphene surface to adsorb phosphorus-containing substances and other organic matter. DETAILED DESCRIPTION

[0028] The present invention is described in detail below with reference to specific embodiments.

[0029] Example 1

[0030] A method for purifying indan, a raw material of cashmeranone, comprises the following steps:

[0031] S1. Add 300 kg of galaxol indane, including more than 80% of pentamethyl indane, 0.5%-2% of phosphorus-containing substances, 1%-3% of other organic substances, and less than 1% of suspended solids, to a 500L synthesis kettle, turn on the heating, raise the temperature in the kettle to 40°C, add 30 kg of 10% sodium hydroxide solution to the synthesis kettle, stir for 2 hours, stop heating and let stand for 1 hour to separate the lower alkaline water phase, add 30 kg of pure water to the synthesis kettle, stir for 2 hours, let stand for 1 hour to separate the lower water phase, and obtain crude cashmeran ketone indane;

[0032] S2, adding 3 kg of aluminum-magnesium-modified hydroxymethyl cellulose coagulant to the crude cashmerone indane obtained in S1, stirring thoroughly for 2 h, and standing for 1 h to obtain a supernatant after enhanced coagulation treatment;

[0033] The aluminum-magnesium modified hydroxymethyl cellulose coagulant is composed of aluminum sulfate, magnesium sulfate, and hydroxymethyl cellulose in a mass ratio of 10:1:1;

[0034] S3, adding 3k redox-treated graphene powder to the supernatant obtained in S2, stirring thoroughly for 2 hours, and standing for 1 hour to obtain a supernatant after adsorption treatment;

[0035] The preparation method of the redox treated graphene powder is as follows: 50 kg of sulfuric acid and 5 kg of nitric acid are stirred in an ice bath for 30 minutes, then 5 kg of graphite powder is added to the mixed acid, and the stirring is continued for 1 hour, 10 kg of potassium persulfate is slowly added to the mixed solution in batches, the ice bath temperature is controlled to be lower than 10° C., and then the temperature is raised to 60° C., and the stirring reaction is continued for 10 hours. After cooling to no higher than 30° C., it is diluted with deionized water, 25 kg of 30% hydrogen peroxide is added and stirred, and the color of the solution changes to bright yellow, and the filter cake is washed with 10% dilute hydrochloric acid in turn, washed with deionized water until neutral, and dried to obtain graphene oxide;

[0036] 5 kg of graphene oxide was dissolved in 500 kg of deionized water, and a suspension was formed by ultrasonic treatment. The pH value was adjusted to 10 with aqueous ammonia, and 25 kg of sodium thiosulfate was added. The mixture was reacted at 60° C. for 2 h. After the reaction was completed, the mixture was washed with deionized water until neutral, and dried to obtain redox-treated graphene powder.

[0037] S4, injecting the supernatant obtained after the adsorption treatment in S3 into an indane distillation tower, and obtaining fine indane for making cashmeranone through distillation.

[0038] After testing, the pentamethylindane content was 90%, and no phosphorus-containing substances, other organic matter and suspended matter were detected.

[0039] Example 2

[0040] A method for purifying indan, a raw material of cashmeranone, comprises the following steps:

[0041] S1. Add 300 kg of galaxol indane, including more than 80% of pentamethyl indane, 0.5%-2% of phosphorus-containing substances, 1%-3% of other organic substances, and less than 1% of suspended solids, to a 500L synthesis kettle, turn on the heating, raise the temperature in the kettle to 40°C, add 30 kg of 10% sodium hydroxide solution to the synthesis kettle, stir for 2 hours, stop heating and let stand for 1 hour to separate the lower alkaline water phase, add 30 kg of pure water to the synthesis kettle, stir for 2 hours, let stand for 1 hour to separate the lower water phase, and obtain crude cashmeran ketone indane;

[0042] S2, adding 3 kg of aluminum-magnesium-modified hydroxymethyl cellulose coagulant to the crude cashmerone indane obtained in S1, stirring thoroughly for 2 h, and standing for 1 h to obtain a supernatant after enhanced coagulation treatment;

[0043] The aluminum-magnesium modified hydroxymethyl cellulose coagulant is composed of aluminum sulfate, magnesium sulfate, and hydroxymethyl cellulose in a mass ratio of 8:3:1;

[0044] S3, adding 3k redox-treated graphene powder to the supernatant obtained in S2, stirring thoroughly for 2 hours, and standing for 1 hour to obtain a supernatant after adsorption treatment;

[0045] The preparation method of the redox treated graphene powder is as follows: 100 kg of sulfuric acid and 10 kg of nitric acid are stirred in an ice bath for 30 minutes, then 5 kg of graphite powder is added to the mixed acid, and the stirring is continued for 1 hour, 20 kg of potassium persulfate is slowly added to the mixed solution in batches, the ice bath temperature is controlled to be lower than 10° C., and then the temperature is raised to 60° C., and the stirring reaction is continued for 10 hours. After cooling to no higher than 30° C., it is diluted with deionized water, and 25 kg of 30% hydrogen peroxide is added and stirred until the color of the solution changes to bright yellow, and the filter cake is washed with 10% dilute hydrochloric acid in turn, washed with deionized water until neutral, and dried to obtain graphene oxide;

[0046] 5 kg of graphene oxide was dissolved in 500 kg of deionized water, and a suspension was formed by ultrasonic treatment. The pH value was adjusted to 10 with aqueous ammonia, and 50 kg of sodium thiosulfate was added. The mixture was reacted at 60° C. for 2 h. After the reaction was completed, the mixture was washed with deionized water until neutral, and dried to obtain redox-treated graphene powder.

[0047] S4, injecting the supernatant obtained after the adsorption treatment in S3 into an indane distillation tower, and obtaining fine indane for making cashmeranone through distillation.

[0048] After testing, the pentamethylindane content was 92%, and no phosphorus-containing substances, other organic matter and suspended matter were detected.

[0049] Example 3

[0050] A method for purifying indan, a raw material of cashmeranone, comprises the following steps:

[0051] S1. Add 300 kg of galaxol indane, including more than 80% of pentamethyl indane, 0.5%-2% of phosphorus-containing substances, 1%-3% of other organic substances, and less than 1% of suspended solids, to a 500L synthesis kettle, turn on the heating, raise the temperature in the kettle to 40°C, add 30 kg of 10% sodium hydroxide solution to the synthesis kettle, stir for 2 hours, stop heating and let stand for 1 hour to separate the lower alkaline water phase, add 30 kg of pure water to the synthesis kettle, stir for 2 hours, let stand for 1 hour to separate the lower water phase, and obtain crude cashmeran ketone indane;

[0052] S2, adding 3 kg of aluminum-magnesium-modified hydroxymethyl cellulose coagulant to the crude cashmerone indane obtained in S1, stirring thoroughly for 2 h, and standing for 1 h to obtain a supernatant after enhanced coagulation treatment;

[0053] The aluminum-magnesium modified hydroxymethyl cellulose coagulant is composed of aluminum sulfate, magnesium sulfate, and hydroxymethyl cellulose in a mass ratio of 10:2:1;

[0054] S3, adding 3k redox-treated graphene powder to the supernatant obtained in S2, stirring thoroughly for 2 hours, and standing for 1 hour to obtain a supernatant after adsorption treatment;

[0055] The preparation method of the redox treated graphene powder is as follows: 100 kg of sulfuric acid and 10 kg of nitric acid are stirred in an ice bath for 30 minutes, then 5 kg of graphite powder is added to the mixed acid, and the stirring is continued for 1 hour, 20 kg of potassium persulfate is slowly added to the mixed solution in batches, the ice bath temperature is controlled to be lower than 10° C., and then the temperature is raised to 60° C., and the stirring reaction is continued for 10 hours. After cooling to no higher than 30° C., it is diluted with deionized water, and 15 kg of 30% hydrogen peroxide is added and stirred until the color of the solution changes to bright yellow, and the filter cake is washed with 10% dilute hydrochloric acid in turn, washed with deionized water until neutral, and dried to obtain graphene oxide;

[0056] 5 kg of graphene oxide was dissolved in 500 kg of deionized water, and a suspension was formed by ultrasonic treatment. The pH value was adjusted to 10 with aqueous ammonia, and 30 kg of sodium thiosulfate was added. The mixture was reacted at 60° C. for 2 h. After the reaction was completed, the mixture was washed with deionized water until neutral, and dried to obtain redox-treated graphene powder.

[0057] S4, injecting the supernatant obtained after the adsorption treatment in S3 into an indane distillation tower, and obtaining fine indane for making cashmeranone through distillation.

[0058] After testing, the pentamethylindane content was 95%, and no phosphorus-containing substances, other organic matter and suspended matter were detected.

[0059] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention is described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for purifying pentamethylindan, a raw material of cashmeranone, characterized in that: The steps include: S1, adding galaxol pentamethyl indane to an alkali solution, heating and stirring to wash, standing and stratifying to separate the lower alkali water phase, adding pure water to stir and wash, standing and stratifying to separate the lower water phase, and obtaining a crude product of cashmeran ketone pentamethyl indane; S2, adding aluminum-magnesium-modified hydroxymethyl cellulose coagulant to the crude pentamethyl indane of cashmerone obtained in S1, stirring thoroughly, and standing to obtain a supernatant after enhanced coagulation treatment; S3, adding the redox-treated graphene powder to the supernatant obtained in S2, stirring thoroughly, and standing to obtain a supernatant after adsorption treatment; S4, injecting the supernatant obtained in S3 after the adsorption treatment into a pentamethylindane distillation tower, and obtaining the fine pentamethylindane for making cashmeranone by distillation; The galaxol pentamethylindane comprises more than 80% pentamethylindane, 0.5%-2% phosphorus-containing substances, 1%-3% other organic substances, and less than 1% suspended solids; The aluminum-magnesium modified hydroxymethyl cellulose coagulant in S2 is composed of aluminum sulfate, magnesium sulfate, and hydroxymethyl cellulose in a mass ratio of (8-10): (1-3): 1; The preparation method of the redox treated graphene powder is as follows: sulfuric acid and nitric acid are stirred in an ice bath, then graphite powder is added to the mixed acid, and the stirring is continued, potassium persulfate is slowly added to the mixed solution in batches, the ice bath temperature is controlled to be lower than 10° C., and then the temperature is raised to 60-70° C., and the stirring is continued for 10-20 hours. After cooling to no higher than 30° C., it is diluted with deionized water, 30% hydrogen peroxide is added and stirred, and the color of the solution changes to bright yellow, and the filter cake is washed with 10% dilute hydrochloric acid, washed with deionized water until neutral, and dried to obtain graphene oxide; Graphene oxide is dissolved in deionized water, ultrasonically formed into a suspension, the pH is adjusted to alkaline with ammonia water, sodium thiosulfate is added and heated to react, and after the reaction is completed, deionized water is washed to neutrality and dried to obtain redox-treated graphene powder.

2. The method for purifying pentamethylindan, a raw material of cashmerone, according to claim 1, characterized in that: The mass ratio of the sulfuric acid, nitric acid, graphite powder and potassium persulfate is 10:1:(0.5-1):

2.

3. The method for purifying pentamethylindan, a raw material of cashmerone according to claim 1, characterized in that: The added mass of the 30% hydrogen peroxide is 3-5 times the mass of the graphite powder.

4. The method for purifying pentamethylindan, a raw material of cashmerone, according to claim 1, characterized in that: The mass ratio of the graphene oxide to sodium thiosulfate is 1:(5-10).

5. The method for purifying pentamethylindan, a raw material of cashmerone, according to claim 1, characterized in that: Adjust the pH to 10-11 with aqueous ammonia.

6. The method for purifying pentamethylindan, a raw material of cashmerone according to claim 1, characterized in that: The heating reaction conditions are 60-80°C and stirring for 1-3h.

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