CN113277949B - Method for processing, producing or refining aliphatic hydrocarbon amines or derivatives thereof - Google Patents
Method for processing, producing or refining aliphatic hydrocarbon amines or derivatives thereof Download PDFInfo
- Publication number
- CN113277949B CN113277949B CN202010100917.4A CN202010100917A CN113277949B CN 113277949 B CN113277949 B CN 113277949B CN 202010100917 A CN202010100917 A CN 202010100917A CN 113277949 B CN113277949 B CN 113277949B
- Authority
- CN
- China
- Prior art keywords
- alkyl
- amine
- aliphatic hydrocarbon
- derivative
- alkyl group
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for processing an aliphatic hydrocarbon amine or a derivative thereof, which comprises: treating the aliphatic hydrocarbon amine or derivative thereof with a hydroxycarboxylic acid. Also relates to a process for producing or refining an aliphatic hydrocarbon amine or a derivative thereof and to a novel use of a hydroxycarboxylic acid, in particular its use for treating an aliphatic hydrocarbon amine or a derivative thereof to prevent or eliminate the pink color of said amine or derivative thereof or to prevent or eliminate the pink color of said amine or derivative thereof when derivatized.
Description
Technical Field
The present invention relates to a process for processing an aliphatic hydrocarbon amine or a derivative thereof, to a process for producing or refining an aliphatic hydrocarbon amine or a derivative thereof and to a novel use of a hydroxycarboxylic acid, in particular its use for treating an aliphatic hydrocarbon amine or a derivative thereof to prevent or eliminate the pink color of said amine or derivative thereof or to prevent or eliminate the pink color of said amine or derivative thereof when derivatized.
Background
Aliphatic hydrocarbon amines (e.g. with carbon chain lengths C) 8 -C 22 Fatty tertiary amine) and derivatives thereof are important organic chemical products and intermediates, and are widely applied to petrochemical industry, medicine, agricultural chemicals, surfactant manufacturing and other industries. In the production process of fatty hydrocarbon amine derivative products (such as amine hydrochloride, quaternary ammonium salt and betaine), pink products are easy to appear. The pink color of the product results in a reduction in product quality, thereby affecting downstream product applications.
Patent US4347381 describes that the pink color problem of the product can be effectively eliminated by adding small or even trace amount of bleaching agent (such as sodium sulfite, sodium bisulfite, sodium thiosulfate, hydrogen peroxide, etc.), wherein the most preferable condition is to add small amount of hydrogen peroxide and stir at 30-60 ℃ for 5-30 minutes. However, hydrogen peroxide is a strong oxidizing agent and is easy to generate amine oxide with tertiary amine, so that the yield of the product is reduced, the quality of the product is also reduced, and the product is even rectified again to obtain a qualified product when necessary.
Patent US3922306 describes another method for effectively eliminating the colour of tertiary amines or their derivatives under acidic conditions by adding small amounts of alkali metal borohydrides. However, this method actually uses an aqueous solution of an alkali metal borohydride to treat the tertiary amine by extraction. Not only is the operation difficult, and the production equipment is difficult to match, and the waste water discharge is big, and alkali metal borohydride is dangerous chemical moreover, and the fire hazard easily takes place for improper operation or storage, and the cost is higher.
Patent US5359139 shows that tertiary amines containing acid activated color change precursors can be prevented from turning pink under acidic conditions by contact with ascorbic acid or its derivatives. It has been found that ascorbic acid prevents the tertiary amines or derivatives thereof containing acid activated color-changing potential from turning pink under acidic conditions. However, ascorbic acid is susceptible to oxidative discoloration during distillation resulting in discoloration of the tertiary amine product.
Disclosure of Invention
In a first aspect, the present application provides a method of processing an aliphatic hydrocarbon amine or derivative thereof, comprising:
treating the aliphatic hydrocarbon amine or derivative thereof with a hydroxycarboxylic acid.
In a second aspect, the present application provides a method for producing or refining an aliphatic hydrocarbon amine or a derivative thereof, comprising:
treating the crude aliphatic hydrocarbon amine or its derivative with hydroxy carboxylic acid.
In some embodiments of any of the above aspects, the method further comprises:
distilling the aliphatic hydrocarbon amine or the derivative thereof after the hydroxycarboxylic acid treatment.
In some embodiments of any of the aspects above, wherein the distilling is performed at a temperature of 50 ℃ to 250 ℃ or 120 ℃ to 230 ℃.
In some embodiments, the distillation is vacuum distillation or rectification.
In some embodiments, the pressure of the reduced pressure distillation is from 0.1mbar to 10mbar.
In some embodiments, the rectifying comprises feeding the aliphatic hydrocarbon amine or derivative thereof and the hydroxycarboxylic acid to a rectification column for rectification.
In some embodiments, the adding is adding the aliphatic hydrocarbon amine or derivative thereof and the hydroxycarboxylic acid to the rectification column simultaneously or sequentially.
In some embodiments, the addition is the simultaneous pumping of the aliphatic hydrocarbon amine or derivative thereof and the hydroxycarboxylic acid into a rectification column.
In a third aspect, the present application provides the use of a hydroxycarboxylic acid for the treatment of an aliphatic hydrocarbon amine or derivative thereof.
In some embodiments of any of the foregoing aspects, the aliphatic hydrocarbon amine contains at least one C attached to the amino nitrogen 8 -C 22 An alkyl group.
In some embodiments of any of the above aspects, the hydroxycarboxylic acid is selected from a monohydroxymonocarboxylic acid, a monohydroxypolycarboxylic acid, a polyhydroxymonocarboxylic acid, a polyhydroxypolycarboxylic acid, or a combination thereof.
In some embodiments of any of the above aspects, the hydroxycarboxylic acid is selected from citric acid, tartaric acid, malic acid, salicylic acid, gallic acid, lactic acid, or a combination thereof.
In some embodiments of any of the above aspects, the hydroxycarboxylic acid is selected from citric acid, tartaric acid, or a combination thereof.
In some embodiments of any of the foregoing aspects, the aliphatic hydrocarbon amine is a compound of the formula RR' R "N, wherein:
r, R 'and R' are each independently selected from H, C optionally substituted with hydroxy 1 -C 22 Alkyl and C 8 -C 22 An alkyl group; and
wherein at least one of R, R 'and R' is C 8 -C 22 An alkyl group.
In some embodiments, the C optionally substituted with hydroxy 1 -C 22 Alkyl is C optionally substituted by hydroxy 8 -C 22 Alkyl, C optionally substituted by hydroxy 1 -C 6 Alkyl, C optionally substituted by hydroxy 1 -C 4 Alkyl or C optionally substituted by hydroxy 1 -C 2 An alkyl group.
In some embodiments, the C optionally substituted with hydroxy 1 -C 22 The alkyl group is selected from methyl, ethyl, hydroxyethyl or C 8 -C 22 An alkyl group.
In some embodiments, the aliphatic hydrocarbon amine is an aliphatic tertiary amine.
In some embodiments, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are each independently C optionally substituted by hydroxy 1 -C 22 Alkyl, C optionally substituted by hydroxy 8 -C 22 Alkyl, C optionally substituted by hydroxy 1 -C 6 Alkyl, C optionally substituted by hydroxy 1 -C 4 Alkyl or C optionally substituted by hydroxy 1 -C 2 An alkyl group.
In some embodiments, wherein one of R, R 'and R' is C 8 -C 22 Alkyl and the other two are each independently C optionally substituted by hydroxy 1 -C 6 Alkyl, C optionally substituted by hydroxy 1 -C 4 Alkyl or C optionally substituted by hydroxy 1 -C 2 An alkyl group.
In some embodiments, wherein one of R, R 'and R' is C optionally substituted with hydroxy 1 -C 6 Alkyl, C optionally substituted by hydroxy 1 -C 4 Alkyl or C optionally substituted by hydroxy 1 -C 2 Alkyl and the other two are C 8 -C 22 An alkyl group.
In some embodiments, wherein R, R' and R "One of them is C 8 -C 22 Alkyl and the other two are each independently selected from methyl, ethyl and hydroxyethyl.
In some embodiments, wherein one of R, R 'and R' is C 8 -C 22 Alkyl and the other two are methyl.
In some embodiments, wherein one of R, R' and R "is methyl, ethyl or hydroxyethyl and the other two are C 8 -C 22 An alkyl group.
In some embodiments of any of the above aspects, wherein the derivative thereof is selected from a salt thereof, an amine oxide, a betaine, a quaternary ammonium compound, or other compound derived from the aliphatic hydrocarbon amine; in some embodiments, the salt is a hydrochloride salt.
In some embodiments of any of the aspects above, wherein: the amount of the hydroxycarboxylic acid is 0.01% to 0.5% or 0.01% to 0.05% by weight of the aliphatic hydrocarbon amine or derivative thereof.
In some embodiments of any of the above aspects, the hydroxycarboxylic acid is used to treat the aliphatic hydrocarbon amine or derivative thereof to prevent or eliminate the pink color of the amine or derivative thereof or to prevent or eliminate the pink color of the amine or derivative thereof when derivatized.
In some embodiments, the derivatizing is converting the amine or derivative thereof to an amine salt or exposing to acidic conditions.
Drawings
Fig. 1 is a process flow diagram of an exemplary method of producing an aliphatic hydrocarbon amine derivative according to the present invention.
Fig. 2a and 2b show photographs of the effect of a tertiary amine-derived product without a hydroxycarboxylic acid treatment and a tertiary amine-derived product after a hydroxycarboxylic acid treatment, respectively, in which fig. 2a shows that the tertiary amine-derived product without a hydroxycarboxylic acid treatment is pink in color under acidic conditions, and fig. 2b shows that the tertiary amine-derived product after a hydroxycarboxylic acid treatment is colorless.
Detailed Description
Definition of
The following definitions and methods are provided to better define the present application and to guide those of ordinary skill in the art in the practice of the present application. Unless otherwise indicated, terms are to be understood in accordance with their ordinary usage by those of ordinary skill in the relevant art.
As used herein, the terms "comprises" and "comprising" are to be interpreted as inclusive and open-ended, rather than exclusive. In particular, the terms "comprises" and "comprising," and variations thereof, as used in the specification and claims, are intended to cover the inclusion of the stated features, steps or components. These terms are not to be interpreted to exclude the presence of other features, steps or components.
The term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
The term "aliphatic hydrocarbon amine" refers to an organic derivative of ammonia, which is an organic amine compound and can be classified into primary, secondary and tertiary amines, polyamines, and the like. The term "derivatives thereof" includes, but is not limited to, salts thereof, amine oxides, betaines, quaternaries or other compounds derived from aliphatic hydrocarbon amines, and the like.
The term "hydroxycarboxylic acid" refers to an organic acid that contains both hydroxyl and carboxyl groups. The hydroxycarboxylic acid may have one or more than one hydroxyl group and may have one or more than one carboxyl group in its molecule, that is, it may be a monohydroxymonocarboxylic acid, a monohydroxypolycarboxylic acid, a polyhydroxymonocarboxylic acid, or a polyhydroxypolycarboxylic acid. Examples of hydroxycarboxylic acids include, but are not limited to, tartaric acid, malic acid, salicylic acid, gallic acid, lactic acid, and the like. In some embodiments, the hydroxycarboxylic acid contains or does not contain an aromatic group. In some embodiments, the hydroxycarboxylic acid is a monohydroxypolycarboxylic acid or a polyhydroxy polycarboxylic acid.
The term "C 1 -C 22 Alkyl "refers to a saturated straight or branched chain hydrocarbon group having 1 to 22 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22) carbon atoms and linked through any one carbon atom, e.g., methyl, ethyl, propyl, isopropylA group such as a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, a n-heptadecyl group, a n-octadecyl group, a n-nonadecyl group, and a n-eicosyl group.
The term "C optionally substituted by hydroxy 1 -C 22 Alkyl "means unsubstituted or substituted by hydroxy as defined above C 1 -C 22 An alkyl group.
The term "C 8 -C 22 Alkyl "refers to a saturated straight or branched chain hydrocarbon group having from 8 to 22 (e.g., 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22) carbon atoms and connected by any one carbon atom.
Where a range of numerical values is recited herein, the range includes the endpoints thereof, and all the individual integers and fractions within the range, and also includes each of the narrower ranges therein formed by all the various possible combinations of those endpoints and internal integers and fractions to form subgroups of the larger group of values within the stated range to the same extent as if each of those narrower ranges were explicitly recited. For example, distillation at a temperature of 50 ℃ to 250 ℃ means that the temperature can be, for example, 50 ℃,60 ℃,70 ℃,80 ℃,90 ℃,100 ℃,110 ℃,120 ℃,124 ℃,126 ℃,127 ℃,129 ℃,130 ℃,132 ℃,135 ℃,138 ℃,140 ℃,143 ℃,145 ℃,148 ℃,150 ℃,152 ℃,154 ℃,157 ℃,160 ℃,162 ℃,165 ℃,168 ℃,170 ℃,173 ℃,175 ℃,177 ℃,180 ℃,182 ℃,184 ℃,187 ℃,189 ℃,190 ℃,193 ℃,198 ℃,200 ℃,204 ℃,206 ℃,208 ℃,210 ℃,213 ℃,215 ℃,218 ℃,220 ℃,222 ℃,224 ℃,227 ℃, 230 ℃, 235 ℃, 238 ℃, 240 ℃, 243 ℃, 247 ℃, or 250 ℃ and the like, and ranges formed therefrom, and the like.
Detailed Description
In a first aspect, the present application provides a method of processing an aliphatic hydrocarbon amine or a derivative thereof, comprising:
treating the aliphatic hydrocarbon amine or derivative thereof with a hydroxycarboxylic acid.
In a second aspect, the present application provides a method for producing or refining an aliphatic hydrocarbon amine or a derivative thereof, comprising:
treating the crude aliphatic hydrocarbon amine or its derivative with hydroxy carboxylic acid.
In some embodiments of any of the above aspects, the method further comprises:
distilling the aliphatic hydrocarbon amine or the derivative thereof treated with the hydroxycarboxylic acid.
In some embodiments of any of the above aspects, wherein the distillation is performed at a temperature of 50 ℃ to 250 ℃ (e.g., 50 ℃,60 ℃,70 ℃,80 ℃,90 ℃,100 ℃,110 ℃,120 ℃,124 ℃,126 ℃,127 ℃,129 ℃,130 ℃,132 ℃,135 ℃,138 ℃,140 ℃,143 ℃,145 ℃,148 ℃,150 ℃,152 ℃,154 ℃,157 ℃,160 ℃,162 ℃,165 ℃,168 ℃,170 ℃,173 ℃,175 ℃,177 ℃,180 ℃,182 ℃,184 ℃,187 ℃,189 ℃,190 ℃,193 ℃,195 ℃,198 ℃,200 ℃,204 ℃,206 ℃,208 ℃,210 ℃,213 ℃,215 ℃,218 ℃,220 ℃,222 ℃,224 ℃,227 ℃, 230 ℃, 235 ℃, 238 ℃, 240 ℃, 243 ℃, 247 ℃, or 250 ℃, etc.), or 120 ℃ to 230 ℃.
In some embodiments, the distillation is vacuum distillation or rectification.
In some embodiments, the reduced pressure distillation is at a pressure of 0.1mbar to 10mbar (e.g., 0.1mbar, 0.2mbar, 0.3mbar, 0.4mbar, 0.5mbar, 0.6mbar, 0.7mbar, 0.8mbar, 0.9mbar, 1mbar, 2mbar, 3mbar, 4mbar, 5mbar, 6mbar, 7mbar, 8mbar, 9mbar, or 10mbar, etc.).
In some embodiments of any of the above aspects, the crude product has a purity of less than 99%, or less than 95%, or 70% to 95%, or 80% to 95%, or 90% to 95%, or 93% to 95%.
In some embodiments, the rectifying comprises feeding the aliphatic hydrocarbon amine or derivative thereof and the hydroxycarboxylic acid to a rectification column for rectification.
In some embodiments, the adding is adding the aliphatic hydrocarbon amine or derivative thereof and the hydroxycarboxylic acid to the rectification column simultaneously or sequentially.
In some embodiments, the addition is the simultaneous pumping of the aliphatic hydrocarbon amine or derivative thereof and the hydroxycarboxylic acid into a rectification column.
In a third aspect, the present application provides the use of a hydroxycarboxylic acid for the treatment of an aliphatic hydrocarbon amine or derivative thereof.
In some embodiments of any of the foregoing aspects, the aliphatic hydrocarbon amine contains at least one C attached to the amino nitrogen 8 -C 22 An alkyl group.
In some embodiments of any of the above aspects, the hydroxycarboxylic acid is selected from a monohydroxy monocarboxylic acid, a monohydroxy polycarboxylic acid, a polyhydroxy monocarboxylic acid, a polyhydroxy polycarboxylic acid, or a combination thereof.
In some embodiments of any of the above aspects, the hydroxycarboxylic acid is selected from citric acid, tartaric acid, malic acid, salicylic acid, gallic acid, lactic acid, or a combination thereof.
In some embodiments of any of the above aspects, the hydroxycarboxylic acid is selected from citric acid, tartaric acid, or a combination thereof.
In some embodiments of any of the foregoing aspects, the aliphatic hydrocarbon amine is a compound of the formula RR' R "N, wherein:
r, R 'and R' are each independently selected from H, C optionally substituted with hydroxy 1 -C 22 Alkyl and C 8 -C 22 An alkyl group; and
wherein at least one of R, R 'and R' is C 8 -C 22 An alkyl group.
In some embodiments, the C optionally substituted with hydroxy 1 -C 22 Alkyl is C optionally substituted by hydroxy 8 -C 22 Alkyl, C optionally substituted by hydroxy 1 -C 6 Alkyl, C optionally substituted by hydroxy 1 -C 4 Alkyl or C optionally substituted by hydroxy 1 -C 2 An alkyl group.
In some casesIn embodiments, the C optionally substituted with hydroxy 1 -C 22 The alkyl group is selected from methyl, ethyl, hydroxyethyl or C 8 -C 22 An alkyl group.
In some embodiments, the aliphatic hydrocarbon amine is an aliphatic tertiary amine.
In some embodiments, wherein one of R, R 'and R' is C 8 -C 22 Alkyl and the other two are each independently C optionally substituted by hydroxy 1 -C 22 Alkyl, C optionally substituted by hydroxy 8 -C 22 Alkyl, C optionally substituted by hydroxy 1 -C 6 Alkyl, C optionally substituted by hydroxy 1 -C 4 Alkyl or C optionally substituted by hydroxy 1 -C 2 An alkyl group.
In some embodiments, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are each independently C optionally substituted by hydroxy 1 -C 6 Alkyl, C optionally substituted by hydroxy 1 -C 4 Alkyl or C optionally substituted by hydroxy 1 -C 2 An alkyl group.
In some embodiments, wherein one of R, R' and R "is C optionally substituted with hydroxy 1 -C 6 Alkyl, C optionally substituted by hydroxy 1 -C 4 Alkyl or C optionally substituted by hydroxy 1 -C 2 Alkyl and the other two are C 8 -C 22 An alkyl group.
In some embodiments, wherein one of R, R 'and R' is C 8 -C 22 Alkyl and the other two are each independently selected from methyl, ethyl and hydroxyethyl.
In some embodiments, wherein one of R, R 'and R' is C 8 -C 22 Alkyl and the other two are methyl.
In some embodiments, wherein one of R, R' and R "is methyl, ethyl or hydroxyethyl and the other two are C 8 -C 22 An alkyl group.
In some embodiments of any of the above aspects, wherein the derivative thereof is selected from a salt thereof, an amine oxide, a betaine, a quaternary ammonium compound, or other compound derived from the aliphatic hydrocarbon amine; in some embodiments, the salt is a hydrochloride salt.
In some embodiments of any of the aspects above, wherein: the amount of the hydroxycarboxylic acid is 0.01% to 0.5% (e.g., 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.12%, 0.15%, 0.18%, 0.2%, 0.23%, 0.25%, 0.27%, 0.30%, 0.34%, 0.38%, 0.40%, 0.42%, 0.45%, 0.48%, or 0.50%, etc.) or 0.01% to 0.05% by weight of the aliphatic hydrocarbon amine or derivative thereof.
In some embodiments of any of the above aspects, the hydroxycarboxylic acid is used to treat the aliphatic hydrocarbon amine or derivative thereof to prevent or eliminate the pink color of the amine or derivative thereof, or to prevent or eliminate the pink color of the amine or derivative thereof when derivatized.
In some embodiments, the derivatization is conversion of the amine or derivative thereof to an amine salt or exposure to acidic conditions.
In some embodiments, one to five ten-thousandths of hydroxycarboxylic acid can be added into the crude fatty hydrocarbon amine (such as monoalkyl dimethyl tertiary amine) produced, the temperature is raised to 120-230 ℃, and the reduced pressure distillation is carried out, so as to obtain the fatty tertiary amine meeting the requirements.
The treated tertiary amine was subjected to derivatization test under acidic condition as shown in FIG. 1, and the test phenomenon was observed. A blank control may be performed for comparison purposes.
The method of the invention can be used in industrial production: the aliphatic hydrocarbon amine (such as monoalkyl dimethyl tertiary amine) obtained by the preparation is produced, and after the catalyst is removed by filtration, crude aliphatic hydrocarbon amine is obtained and pumped into a rectifying tower through a pipeline. The hydroxycarboxylic acid to be added can be uniformly diluted by using a proper amount of deionized water or tertiary amine product, and is synchronously pumped into a rectifying tower through a metering pump, and the full effect is achieved in a rectifying section, so that the aliphatic hydrocarbon amine meeting the requirements is obtained.
The inventions of the present application provide one or more of the following advantages:
1. the problem that the pink phenomenon occurs in the aliphatic hydrocarbon amine and the derivative products thereof can be effectively solved;
2. the hydroxycarboxylic acid is stable in chemical property and does not increase color;
3. the hydroxycarboxylic acid is not a dangerous chemical, is simple and convenient to operate, can be used in a small amount, and does not generate extra waste;
4. the industrial production is easy to realize, and the hydroxycarboxylic acid can be directly and synchronously treated in a distillation section without additionally increasing the step of the section, and can be synchronously operated in a tertiary amine rectifying tower;
5. the product yield and the product quality are not influenced at all.
Examples
The following examples are for the purpose of illustration only and are not intended to limit the scope of the present application.
Example 1 (blank control)
200g of crude hexadecyl/octadecyl dimethyl tertiary amine (noted as TA-1816, wherein the purity is 93% by weight for hexadecyl dimethyl tertiary amine about 20% to 30% by weight and for octadecyl dimethyl tertiary amine about 70% to 80% by weight) are weighed and heated to 220 ℃ for distillation under reduced pressure (pressure 3 mbar). After completion of the distillation operation, 196.9g of a distilled product of TA-1816 tertiary amine was obtained in a yield of 98.45%. The hydrochloride derivative of the tertiary amine distillate untreated with hydroxycarboxylic acid is pink in color under acidic conditions.
Example 2
200g of crude TA-1816 tertiary amine are weighed, 0.02g of citric acid (ten thousandth) are added, the temperature is raised to 220 ℃ and distillation is carried out under reduced pressure (pressure 3 mbar). After completion of the distillation operation, 196.6g of a distilled tertiary amine product was obtained in a yield of 98.3%. The hydrochloride derivative was colorless under acidic conditions in the tertiary amine distillate treated with one in ten thousand citric acid.
Example 3
200g of the crude TA-1816 tertiary amine was weighed, 0.20g of aqueous citric acid (50% by mass in five parts per million) was added, and the mixture was heated to 220 ℃ and distilled under reduced pressure (pressure 3 mbar). After completion of the distillation operation, 196.5g of a distilled tertiary amine was obtained in a yield of 98.25%. The hydrochloride derivative was colorless under acidic conditions in the tertiary amine distillate treated with five parts per million citric acid.
Example 4
200g of crude TA-1816 tertiary amine was weighed, 0.40g of aqueous citric acid solution (50% by mass in one thousandth) was added, and the mixture was heated to 220 ℃ and distilled under reduced pressure (pressure 3 mbar). After completion of the distillation operation, 196.0g of a distilled tertiary amine product was obtained in a yield of 98.0%. The hydrochloride derivative was colorless under acidic conditions in the tertiary amine distillate treated with one-thousandth of citric acid.
Example 5
200g of crude TA-1816 amine are weighed, 0.1g of tartaric acid are added, the temperature is raised to 220 ℃ and distillation is carried out under reduced pressure (pressure 3 mbar). After completion of the distillation operation, 196.0g of a distilled tertiary amine product was obtained in a yield of 98%. The hydrochloride derivative of the tertiary amine distillate treated with penta-mellitic acid was colorless under acidic conditions.
Example 6
200g of crude TA-1816 are weighed, 0.06g of tartaric acid are added, the temperature is raised to 220 ℃ and distillation is carried out under reduced pressure (pressure 3 mbar). After completion of the distillation operation, 196.3g of a distilled tertiary amine product was obtained in a yield of 98.2%. The hydrochloride derivative was colorless under acidic conditions in the tertiary amine distillate treated with three parts per million tartaric acid.
Comparative example 1
200g of crude TA-1816 tertiary amine are weighed, 0.2g of sodium hypophosphite (a strong reducing agent) are added, the temperature is raised to 220 ℃ and the distillation is carried out under reduced pressure (pressure 3 mbar). 195.8g of tertiary amine distillate was obtained with a yield of 98.0% by completion of the distillation operation. The hydrochloride derivative was pink in color under acidic conditions in the tertiary amine distillate treated with one thousandth of sodium hypophosphite.
Comparative example 2
200g of crude TA-1816 tertiary amine are weighed, 0.2g of ascorbic acid are added, the temperature is raised to 220 ℃ and distillation is carried out under reduced pressure (pressure 3 mbar). After completion of the distillation operation, 196.8g of a distilled tertiary amine product was obtained in a yield of 98.4%. The hydrochloride derivative of the tertiary amine distillate treated with one-thousandth ascorbic acid was not pink-red under acidic conditions. ( Note: the tertiary amine distillate treated with ascorbic acid has light yellow color, and the product quality is reduced )
Comparative example 3
200g of crude TA-1816 tertiary amine was weighed, 0.2g of BHT (2, 6-di-tert-butyl-p-cresol, a fat-soluble antioxidant) was added, the temperature was raised to 220 ℃ and distillation was carried out under reduced pressure (pressure 3 mbar). After completion of the distillation operation, 196.8g of a distilled tertiary amine product was obtained in a yield of 98.4%. The hydrochloride salt derivative was pink in color under acidic conditions in the tertiary amine distillate treated with one thousandth of BHT.
The derivatization experiments referred to in the examples are as follows:
a solvent (e.g., ethanol and water) is added to the tertiary amine sample to produce a tertiary amine solution, and then an excess of hydrochloric acid is added to form the tertiary amine hydrochloride salt in an acidic system.
The derivatization experiment was specifically performed as follows:
1. weighing 10.0g of TA-1816 tertiary amine sample in a 100ml beaker;
2. sequentially adding 10ml of ethanol, 5ml of water and 10ml of hydrochloric acid (36%);
3. stirring uniformly, placing in a water bath at 50-60 ℃ and keeping the temperature for 20min;
4. visually, the solution color was observed and recorded.
While the invention has been described in detail by way of the general description and the specific embodiments, it will be apparent to those skilled in the art that certain modifications or improvements may be made in the invention and any combination may be made as required. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (39)
1. A method of processing an aliphatic hydrocarbon amine or derivative thereof comprising:
treating the aliphatic hydrocarbon amine or derivative thereof with a hydroxycarboxylic acid;
wherein the hydroxycarboxylic acid is selected from citric acid, tartaric acid, or combinations thereof;
the aliphatic hydrocarbon amine contains at least one C attached to an amino nitrogen 8 -C 22 An alkyl group;
the aliphatic hydrocarbon amine is aliphatic tertiary amine; and
the derivatives thereof are selected from salts, amine oxides, betaines, and quaternaries thereof.
2. A method for producing or refining an aliphatic hydrocarbon amine or a derivative thereof, comprising:
treating the crude aliphatic hydrocarbon amine or its derivative with hydroxycarboxylic acid;
wherein the hydroxycarboxylic acid is selected from citric acid, tartaric acid, or combinations thereof;
the aliphatic hydrocarbon amine contains at least one C attached to an amino nitrogen 8 -C 22 An alkyl group;
the aliphatic hydrocarbon amine is aliphatic tertiary amine; and
the derivatives are selected from salts, amine oxides, betaines and quaternaries thereof.
3. The method of claim 1 or 2, further comprising:
distilling the aliphatic hydrocarbon amine or the derivative thereof treated with the hydroxycarboxylic acid.
4. The process of claim 3, wherein the distillation is carried out at a temperature of 50 ℃ to 250 ℃.
5. The process of claim 3, wherein the distillation is carried out at a temperature of 120 ℃ to 230 ℃.
6. The process of claim 3, wherein the distillation is vacuum distillation or rectification.
7. The process of claim 6, wherein the reduced pressure distillation is at a pressure of from 0.1mbar to 10mbar.
8. The method of claim 6, wherein the rectifying comprises adding the aliphatic hydrocarbon amine or derivative thereof and the hydroxycarboxylic acid to a rectification column for rectification.
9. The method of claim 8, wherein the adding is adding the aliphatic hydrocarbon amine or derivative thereof and the hydroxycarboxylic acid to the rectification column simultaneously or sequentially.
10. The method of claim 8, wherein the adding is pumping the aliphatic hydrocarbon amine or derivative thereof and the hydroxycarboxylic acid simultaneously into a rectification column.
11. The method of claim 1 or 2, wherein the aliphatic hydrocarbon amine is a compound of formula RR' R "N, wherein:
r, R 'and R' are each independently selected from C 1 -C 22 Alkyl and C 8 -C 22 An alkyl group; and
wherein at least one of R, R 'and R' is C 8 -C 22 An alkyl group.
12. The method of claim 11, wherein:
said C is 1 -C 22 Alkyl is C 8 -C 22 Alkyl radical, C 1 -C 6 Alkyl radical, C 1 -C 4 Alkyl or C 1 -C 2 An alkyl group.
13. The method of claim 11, wherein:
said C is 1 -C 22 The alkyl group is selected from methyl, ethyl, or C 8 -C 22 An alkyl group.
14. The method of claim 11, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are each independently C 1 -C 22 Alkyl radical, C 8 -C 22 Alkyl radical, C 1 -C 6 Alkyl radical, C 1 -C 4 Alkyl or C 1 -C 2 An alkyl group.
15. The method of claim 11, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are each independently C 1 -C 6 Alkyl radical, C 1 -C 4 Alkyl or C 1 -C 2 An alkyl group.
16. The method of claim 11, wherein one of R, R' and R "is C 1 -C 6 Alkyl radical, C 1 -C 4 Alkyl or C 1 -C 2 Alkyl and the other two are C 8 -C 22 An alkyl group.
17. The method of claim 11, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are each independently selected from methyl and ethyl.
18. The method of claim 11, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are methyl.
19. The method of claim 11, wherein one of R, R' and R "is methyl or ethyl and the other two are C 8 -C 22 An alkyl group.
20. The method of claim 1 or 2, wherein the salt is a hydrochloride salt.
21. The method of claim 1 or 2, wherein: the amount of the hydroxycarboxylic acid is 0.01 to 0.5% by weight of the aliphatic hydrocarbon amine or derivative thereof.
22. The method of claim 1 or 2, wherein: the amount of the hydroxycarboxylic acid is 0.01 to 0.05% by weight of the aliphatic hydrocarbon amine or derivative thereof.
23. A process according to claim 1 or 2, wherein the hydroxy carboxylic acid is used to treat the aliphatic hydrocarbon amine or derivative thereof to prevent or eliminate the pink colour of the amine or derivative thereof or when derivatised.
24. The method of claim 23, the derivatizing is to convert the amine or derivative thereof to an amine salt or to exposure to acidic conditions.
25. Use of a hydroxycarboxylic acid for treating an aliphatic hydrocarbon amine or derivative thereof;
wherein the hydroxycarboxylic acid is selected from citric acid, tartaric acid, or combinations thereof;
the aliphatic hydrocarbon amine contains at least one C attached to an amino nitrogen 8 -C 22 An alkyl group;
the aliphatic hydrocarbon amine is aliphatic tertiary amine; and
the derivatives thereof are selected from salts, amine oxides, betaines, and quaternaries thereof.
26. The use of claim 25, wherein the aliphatic hydrocarbon amine is a compound of formula RR' R "N, wherein:
r, R 'and R' are each independently selected from C 1 -C 22 Alkyl and C 8 -C 22 An alkyl group; and
wherein at least one of R, R 'and R' is C 8 -C 22 An alkyl group.
27. The use of claim 26, wherein:
said C is 1 -C 22 Alkyl is C 8 -C 22 Alkyl radical, C 1 -C 6 Alkyl radical, C 1 -C 4 Alkyl or C 1 -C 2 An alkyl group.
28. The use of claim 26, wherein:
said C is 1 -C 22 The alkyl group is selected from methyl, ethyl, or C 8 -C 22 An alkyl group.
29. The use of claim 26, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are each independently C 1 -C 22 Alkyl radical, C 8 -C 22 Alkyl radical, C 1 -C 6 Alkyl radical, C 1 -C 4 Alkyl or C 1 -C 2 An alkyl group.
30. The use of claim 26, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are each independently C 1 -C 6 Alkyl radical, C 1 -C 4 Alkyl or C 1 -C 2 An alkyl group.
31. The use of claim 26, wherein one of R, R' and R "is C 1 -C 6 Alkyl radical, C 1 -C 4 Alkyl or C 1 -C 2 Alkyl and the other two are C 8 -C 22 An alkyl group.
32. The use of claim 26, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are each independently selected from methyl and ethyl.
33. The use of claim 26, wherein one of R, R' and R "is C 8 -C 22 Alkyl and the other two are methyl.
34. The use of claim 26, wherein one of R, R' and R "is methyl or ethyl and the other two are C 8 -C 22 An alkyl group.
35. The use of claim 25, wherein the salt is the hydrochloride salt.
36. The use of claim 25, wherein: the amount of the hydroxycarboxylic acid is 0.01 to 0.5% by weight of the aliphatic hydrocarbon amine or derivative thereof.
37. The use of claim 25, wherein: the amount of the hydroxycarboxylic acid is 0.01 to 0.05% by weight of the aliphatic hydrocarbon amine or derivative thereof.
38. Use according to claim 25, wherein the hydroxycarboxylic acid is used to treat the aliphatic hydrocarbon amine or derivative thereof to prevent or eliminate the pink colour of the amine or derivative thereof or to prevent or eliminate the pink colour of the amine or derivative thereof when derivatised.
39. The use of claim 38, said derivatizing being converting said amine or derivative thereof to an amine salt or exposing to acidic conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010100917.4A CN113277949B (en) | 2020-02-19 | 2020-02-19 | Method for processing, producing or refining aliphatic hydrocarbon amines or derivatives thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010100917.4A CN113277949B (en) | 2020-02-19 | 2020-02-19 | Method for processing, producing or refining aliphatic hydrocarbon amines or derivatives thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113277949A CN113277949A (en) | 2021-08-20 |
| CN113277949B true CN113277949B (en) | 2023-03-14 |
Family
ID=77274839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010100917.4A Active CN113277949B (en) | 2020-02-19 | 2020-02-19 | Method for processing, producing or refining aliphatic hydrocarbon amines or derivatives thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113277949B (en) |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1125621A (en) * | 1965-01-08 | 1968-08-28 | Ici Ltd | Stabilisation of amines |
| US3922306A (en) * | 1973-01-24 | 1975-11-25 | Kao Corp | Process for refining amines |
| EP0007983A1 (en) * | 1978-08-04 | 1980-02-20 | Chemische Werke Hüls Ag | Process for the purification of tertiary amines |
| US4347381A (en) * | 1978-01-24 | 1982-08-31 | Ethyl Corporation | Method of treating long chain alkyl amines or products derived therefrom |
| US5103053A (en) * | 1991-03-18 | 1992-04-07 | Ethyl Corporation | Process for treating tert-amines |
| US5103052A (en) * | 1991-03-18 | 1992-04-07 | Ethyl Corporation | Tertiary amine treatment |
| US5107028A (en) * | 1991-03-18 | 1992-04-21 | Ethyl Corporation | Process for treating tert-amines |
| US5113017A (en) * | 1991-03-18 | 1992-05-12 | Ethyl Corporation | Process for treating tertiary amines |
| US5118852A (en) * | 1991-03-18 | 1992-06-02 | Ethyl Corporation | Tert-amine treatment |
| US5136092A (en) * | 1991-03-18 | 1992-08-04 | Ethyl Corporation | Process for treating tertiary amines |
| EP0500038A2 (en) * | 1991-02-22 | 1992-08-26 | Kao Corporation | Process for producing aliphatic amines |
| EP0504628A2 (en) * | 1991-03-18 | 1992-09-23 | Ethyl Corporation | Process for treating tertiary amines |
| US5324857A (en) * | 1992-04-28 | 1994-06-28 | Solvay Interox | Inhibition of the formation of nitrosamines |
| US5359139A (en) * | 1991-03-18 | 1994-10-25 | Albemarle Corporation | Tertiary amine treatment |
| US5543515A (en) * | 1991-12-06 | 1996-08-06 | Basf Aktiengesellschaft | Preparation of tertiary amine oxides |
| US5866718A (en) * | 1997-03-20 | 1999-02-02 | General Electric Company | Synthesis of tertiary amine oxides |
| JPH11116539A (en) * | 1997-10-07 | 1999-04-27 | Kao Corp | Production of high-quality tertiary amine |
| JP2002060374A (en) * | 2000-08-18 | 2002-02-26 | New Japan Chem Co Ltd | Method for purifying aliphatic tertiary amine |
| WO2005107423A2 (en) * | 2004-05-06 | 2005-11-17 | The Procter & Gamble Company | Process and method for treating alkylamines |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006055283A1 (en) * | 2004-11-15 | 2006-05-26 | The Procter & Gamble Company | Process for making long chain internal fatty tertiary amines |
-
2020
- 2020-02-19 CN CN202010100917.4A patent/CN113277949B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1125621A (en) * | 1965-01-08 | 1968-08-28 | Ici Ltd | Stabilisation of amines |
| US3922306A (en) * | 1973-01-24 | 1975-11-25 | Kao Corp | Process for refining amines |
| US4347381A (en) * | 1978-01-24 | 1982-08-31 | Ethyl Corporation | Method of treating long chain alkyl amines or products derived therefrom |
| EP0007983A1 (en) * | 1978-08-04 | 1980-02-20 | Chemische Werke Hüls Ag | Process for the purification of tertiary amines |
| EP0500038A2 (en) * | 1991-02-22 | 1992-08-26 | Kao Corporation | Process for producing aliphatic amines |
| US5118852A (en) * | 1991-03-18 | 1992-06-02 | Ethyl Corporation | Tert-amine treatment |
| US5113017A (en) * | 1991-03-18 | 1992-05-12 | Ethyl Corporation | Process for treating tertiary amines |
| US5103052A (en) * | 1991-03-18 | 1992-04-07 | Ethyl Corporation | Tertiary amine treatment |
| US5136092A (en) * | 1991-03-18 | 1992-08-04 | Ethyl Corporation | Process for treating tertiary amines |
| US5103053A (en) * | 1991-03-18 | 1992-04-07 | Ethyl Corporation | Process for treating tert-amines |
| EP0504628A2 (en) * | 1991-03-18 | 1992-09-23 | Ethyl Corporation | Process for treating tertiary amines |
| US5107028A (en) * | 1991-03-18 | 1992-04-21 | Ethyl Corporation | Process for treating tert-amines |
| US5359139A (en) * | 1991-03-18 | 1994-10-25 | Albemarle Corporation | Tertiary amine treatment |
| US5543515A (en) * | 1991-12-06 | 1996-08-06 | Basf Aktiengesellschaft | Preparation of tertiary amine oxides |
| US5324857A (en) * | 1992-04-28 | 1994-06-28 | Solvay Interox | Inhibition of the formation of nitrosamines |
| US5866718A (en) * | 1997-03-20 | 1999-02-02 | General Electric Company | Synthesis of tertiary amine oxides |
| JPH11116539A (en) * | 1997-10-07 | 1999-04-27 | Kao Corp | Production of high-quality tertiary amine |
| JP2002060374A (en) * | 2000-08-18 | 2002-02-26 | New Japan Chem Co Ltd | Method for purifying aliphatic tertiary amine |
| WO2005107423A2 (en) * | 2004-05-06 | 2005-11-17 | The Procter & Gamble Company | Process and method for treating alkylamines |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113277949A (en) | 2021-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2379488A1 (en) | Method for producing pure triethanolamine (teoa) | |
| Pagano et al. | Peroxymonosulfate–Co (II) oxidation system for the removal of the non-ionic surfactant Brij 35 from aqueous solution | |
| EP1132371B2 (en) | Process for the preparation of triethanolamine or N-(2-aminoethyl)-ethanolamine with improved colour quality | |
| EP3992186B1 (en) | Safe, environmentally friendly and controllable process for synthesizing diepoxide | |
| EP0009080B1 (en) | Corrosion inhibitors; compositions for protecting ferrous metals and the protected metals | |
| DE4319297A1 (en) | Acid anhydride esters as oilfield corrosion inhibitors | |
| CN113277949B (en) | Method for processing, producing or refining aliphatic hydrocarbon amines or derivatives thereof | |
| RU2385315C2 (en) | Method of producing triethanolamine | |
| MX2014006098A (en) | Stabilized choline solutions and methods for preparing the same. | |
| EP0098802A2 (en) | Process for the preparation of quaternary ammonium salts | |
| US4347381A (en) | Method of treating long chain alkyl amines or products derived therefrom | |
| KR20180059472A (en) | High purity carboxylic acid esters and methods for their preparation | |
| EP1354905B1 (en) | Use of ether-carboxylic acids having low pour point | |
| US20080163793A1 (en) | Method of inhibiting nitrosamine formation in waterborne coating | |
| EP0001620B1 (en) | Quaternary amine-amide condensation products and their application in oily compositions used for the treatment of fibres | |
| RU2500835C1 (en) | Inhibitor of carbon-dioxide corrosion for aminat sc-3 steam-condensate plants | |
| WO1996022964A1 (en) | Use of tri-acids based on alkoxylated tertiary amines as complex formers | |
| AU2004265601B2 (en) | Inhibition of corrosion in fluid systems | |
| EP1572624B1 (en) | Method for producing light coloured polyalkylene glycol diethyl ether of fatty acid alcanolamine | |
| DE102011111757A1 (en) | Sealant and its use and sealed metallic substrate | |
| CA1333804C (en) | Method of preparing low color fatty amides | |
| CN108290825B (en) | Method for reducing color in alkanolamine compositions and compositions produced thereby | |
| US282488A (en) | Alexander bohbinger | |
| RU2811415C1 (en) | Mixture containing hydroxy analogue of methionine and its oligomer, and method of its preparation | |
| KR101905257B1 (en) | Method for storage of triethanolamine for preventing discoloring |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |