CN112094195B - Separation method of volatile organic alkali - Google Patents
Separation method of volatile organic alkali Download PDFInfo
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- CN112094195B CN112094195B CN202010296721.7A CN202010296721A CN112094195B CN 112094195 B CN112094195 B CN 112094195B CN 202010296721 A CN202010296721 A CN 202010296721A CN 112094195 B CN112094195 B CN 112094195B
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Abstract
The invention provides a method for separating volatile organic alkali from materials containing volatile organic alkali and hydrogen chloride. The by-product of the method is chlorine-containing magnesium salt, and the chlorine-containing alkaline magnesium salt is obtained through thermal hydrolysis dechlorination and can be used as the alkaline magnesium salt to be applied to neutralization reaction, so that the recycling of the alkaline magnesium salt is realized, and other materials except water are not consumed. The method for recovering the volatile organic alkali realizes the separation of the volatile organic alkali and the hydrogen chloride, is a feasible method, and is easy to realize large-scale application.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a separation method of volatile organic alkali.
Background
In the organic chemical production activity, various organic bases are often needed, wherein the most representative variety is triethylamine, and other common varieties comprise diisopropylamine, diisopropylethylamine, pyridine, 2-methylpyridine and the like. According to historical statistical data, the yield of the triethylamine in 2013 years in China is 233 ten thousand tons, and the yield tends to rise year by year. Among the consumption structures of triethylamine, a large part is used as an acid-binding agent. When used as an acid scavenger, the vast majority of triethylamine ends up as a by-product as the hydrochloride salt or as an aqueous solution of the hydrochloride salt. Other common organic bases, such as diisopropylethylamine, pyridine, 2-methylpyridine, and the like, are also substantially similar. In the fine chemical industry, common organic bases have a common characteristic of moderate volatility. Compared with the organic base (such as trioctylamine) which is commonly used in the metallurgical industry and has high boiling point and difficult volatilization, the organic base which has moderate boiling point and certain volatility is more favored in the fine chemical industry. This tendency is caused by the fact that volatile organic bases are more easily recovered by distillation or rectification, which facilitates recycling. In practical terms, organic bases with boiling points not higher than 150 ℃ are more frequently selected by people and have higher yield and sales. Organic bases with too low boiling point and too high volatility are also widely used for industrial chain reasons or for reasons of atom economy. The volatile organic base refers to an organic base with a boiling point of not more than 150 ℃ under normal pressure.
From an economic point of view, it is necessary to recover the volatile organic bases which have become the hydrochloride or the aqueous hydrochloride solution, and there are many conventional separation methods.
One conventional separation method is to treat the hydrochloride of the volatile organic base (or a material containing the volatile organic base and hydrogen chloride) with sodium hydroxide as the base to release free volatile organic base, and then separate and recover the volatile organic base by extraction or distillation. The method is simple and effective, and not only has quick organic alkali release speed, but also is easy to completely release at one time. However, this process generates a large amount of secondary by-product sodium chloride. Due to the limited use of the sodium chloride, the market has larger and larger supply and demand as a whole, and the channel of comprehensive utilization is very limited. In severe cases, these by-products sodium chloride even need to be disposed of as hazardous waste, in which case the disposal of these by-products sodium chloride is quite costly. In the case of triethylamine, the theoretical amount of sodium chloride as a secondary by-product is 0.58 ton per 1 ton of triethylamine recovered, and the cost for treating only the sodium chloride as a by-product is considerable. More importantly, if all the recovered triethylamine hydrochloride is treated according to the method, a large amount of sodium chloride as a secondary byproduct is generated, and the proper treatment is a great problem.
Another conventional separation method is to treat the quicklime with water to obtain a slaked lime slurry, treat the hydrochloride of the volatile organic base (or the material containing the volatile organic base and hydrogen chloride) with the slaked lime as the base to release the free organic base, and then separate and recover the volatile organic base by distillation or extraction. The process releases the free organic base relatively slowly, but easily and completely. Volatile organic base is recovered according to the method, and secondary by-product is calcium chloride. In the consumer structure of calcium chloride, a large part is used as a road snow-melting agent. In recent years, with the development of the corrosive effect of chloride ions on the environment and reinforced concrete buildings, the application of chloride ions is greatly limited, the consumption is rapidly reduced, and the situation of production and marketing balance becomes more severe.
These conventional methods described above have been reasonable for some historical period, but have been difficult to adapt to the actual conditions of today due to the disposal of secondary by-products. Therefore, there is a need for a more desirable and sustainable method for recovering volatile organic bases throughout the industry.
To recover the volatile organic base, the problem of the method for liberating the volatile organic base, i.e., the problem of selecting a neutralizing agent, needs to be solved. Many people have made efforts in this regard.
Ren Fujian et al (recovery of triethylamine [ J ] by ammonia process pesticide 2006,45 (4).) propose the recovery of triethylamine by the "aqueous ammonia process" which uses a large excess of aqueous ammonia to liberate triethylamine. The process needs repeated washing with water, so that the secondary by-products are more, mainly the waste ammonia water containing hydrogen chloride. The method is complicated to operate, the water consumption is large, and secondary byproducts are difficult to find suitable downstream applications, so that the practical application is extremely limited.
Lei Lianglin (recovery of triethylamine in polycarbonate production [ J ]. Fine chemical intermediate 2012,42 (5).) proposes to treat triethylamine-containing wastewater by the "montmorillonite method", to desorb with alkali after enrichment, and to recover triethylamine by rectification. The method has complicated procedures, generates a large amount of secondary three wastes, has the recovery rate of only 70 percent, and has attraction only in special occasions.
Shen Jiangna (a bipolar membrane electrodialysis method for recovering triethylamine from triethylamine hydrochloride [ P ]. Chinese patent application 108409577,2018-08-17, zhejiang industrial university) discloses a method for recovering triethylamine using a "bipolar membrane process". The method adopts a bipolar membrane electrolysis scheme to dissociate triethylamine hydrochloride into hydrochloric acid and triethylamine. The method can realize the dissociation of triethylamine without consuming alkali theoretically. The method is used for releasing free triethylamine, and the ultimate goal of 'zero discharge of acid and alkali' can be expected to be realized. However, the reality is not ideal, and the scheme has various practical problems in application. The bipolar membrane method has complex equipment and processes, large early investment, unsatisfactory adaptability of the system to complex working conditions, delicate and tender bipolar membranes of key components, easy failure in practical application scenes and frequent replacement. Due to the high replacement cost of the bipolar membrane, the operation cost of the method is high and the investment risk is high. The practicability of the method also depends on the great improvement of the bipolar membrane technology.
Yang Xuefeng et al (regeneration of tertiary amine hydrochloride [ J ]. Proceedings of Chengdu scientific university, 1991 (5): 43-47.) report a method for regenerating free tertiary amines from tertiary amine hydrochloride by treating N235 hydrochloride with magnesium oxide under water-oil two-phase conditions, the free ratio can reach 99%. Owing to the three larger liposoluble organic groups (the total number of carbon atoms is generally about 24) connected to nitrogen atoms, N235 and its hydrochloride have better oil solubility and very poor water solubility, which means that the oil-water distribution coefficient is relatively large, and this characteristic makes the oil-water two-phase condition become a driving force, and under this condition, magnesium oxide is used to release N235, so that very high release ratio is easily obtained. However, this method is not suitable for the separation of volatile organic bases. This is because the organic groups on the nitrogen atoms of the volatile organic bases are not large enough (the total number of carbon atoms does not exceed 7), and their water solubility is better than that of N235, meaning that their oil-water partition coefficient is no longer as large as that of N235. The magnesium oxide is used for releasing volatile organic alkali under the oil-water two-phase condition, and the promotion effect under the oil-water two-phase condition is greatly reduced, so that the release ratio is not high. In actual attempts to release the volatile organic base in this way, it was found that the per-pass conversion was reduced to almost no longer practical. Further, since the separation of the solid and liquid in the system is difficult, the equipment is troublesome even if the extraction is modified to continuous extraction.
In summary, the prior art separation techniques are still not ideal for the separation of volatile organic bases and have various limitations.
As suggested by a method for the isolation of NH4Cl (Fuchsman C.H., a method for the recovery of ammonia from ammonium chloride: U.S. Pat. No. 2,981 [ P ]. 1958-2-18), we decided to attempt a similar method for the isolation of volatile organic bases and, as a result, demonstrated that this was in fact possible.
Disclosure of Invention
The invention discloses a method for separating volatile organic alkali from materials containing the volatile organic alkali and hydrogen chloride, which comprises the following steps: the material containing volatile organic alkali and hydrogen chloride is neutralized by alkaline magnesium salt in the presence of water, and free volatile organic alkali is separated by adopting a gasification process. Optionally, after the byproduct of the neutralization reaction, namely chlorine-containing magnesium salt, is subjected to thermal hydrolysis dechlorination, the byproduct can be used as alkaline magnesium salt for the neutralization reaction, so that the recycling of the alkaline magnesium salt is realized.
The volatile organic base refers to an organic base with a normal pressure boiling point of not more than 150 ℃, is not limited in the existence form and state in the material, and can exist in the form of a complex, a free base or both. The hydrogen chloride is a substance whose element composition is represented by HCl, and the form and state of the element composition in the material are not limited, and may be present in a salt-formed state or an unsalted state. The basic magnesium salt is a substance with the main component shown as general formula MgO. MH 2O. NMgCl2, wherein m and n are independent from each other and satisfy the following conditions: m is more than or equal to 0,0 and n is less than or equal to 1. The gasification process refers to a process for promoting the gasification of free volatile organic bases into a gas phase space.
The principle of the technical scheme of the invention is as follows: when the material containing the volatile organic alkali and the hydrogen chloride is contacted with the alkaline magnesium salt in the presence of water, part of the hydrogen chloride is neutralized by the alkaline magnesium salt, and the corresponding part of the volatile organic alkali is dissociated, so that a certain concentration of the dissociated volatile organic alkali is released in the system along with the reaction. Under gasification process conditions, the free volatile organic base enters the gas phase space and the hydrogen chloride is retained in the liquid phase reaction system by combination with the basic magnesium salt. As the gasification is carried out, the volatile organic alkali is continuously removed from the reaction system, and finally, the separation of most of the volatile organic alkali and hydrogen chloride is realized, and the hydrogen chloride is combined with the alkaline magnesium salt to form the byproduct chlorine-containing magnesium salt. It should be noted that, when the basic magnesium salt is used to release the volatile organic base instead of the conventional neutralizing agent, although the organic base in the system cannot be released quickly at one time, as the volatile organic base is continuously removed from the reaction system, the equilibrium of the system is pushed to the free side, and finally, a higher recovery rate can be achieved. Optionally, the technical scheme of the invention can also realize the recycling of the alkaline magnesium salt, and the technical principle is as follows: performing thermal hydrolysis dechlorination on The byproduct chlorine-containing magnesium salt (in The thermal hydrolysis dechlorination method, an method is a typical method, refer to Mark A.Shand, the Chemistry and Technology of Magnesia (Chapter 3.8-Aman Process) [ M ]. New York: wiley-Interscience, 2006.) to obtain The chlorine-containing alkaline magnesium salt with greatly reduced chlorine content, and mechanically applying The chlorine-containing alkaline magnesium salt to a neutralization reaction, thereby realizing recycling.
The volatile organic base can be organic amine or pyridine organic base. Experimental data show that the separation process of the present invention is still very effective when the atmospheric boiling point of the organic base is slightly below, but close to 150 ℃. When the atmospheric boiling point of the organic base is higher than 150 c, the overall separation effect may be deteriorated due to a decrease in efficiency of the gasification process. It should be clearly noted that the method of the present invention is not only applicable to organic bases commonly used as acid-binding agents, but also effective to organic bases with very low boiling points and extremely volatile at normal temperature, such as organic amines, e.g., dimethylamine, existing in a gaseous form at normal temperature and normal pressure.
Examples of common volatile organic bases to which the process of the invention is applicable are given in the following table. It is emphasized that the volatile organic bases listed in the following table are merely examples and should not be considered as limiting the scope of applicability of the process of the present invention.
The material containing the volatile organic base and the hydrogen chloride refers to a material containing both the volatile organic base and the hydrogen chloride, and can be a complex formed by the volatile organic base and the hydrogen chloride, such as hydrochloride of the organic base, or a solution containing both the volatile organic base and the hydrogen chloride. In the material of the volatile organic alkali and the hydrogen chloride, the volatile organic alkali and the hydrogen chloride can be equimolar, and one of the components can be excessive. When the organic base in the feed is excessive, part of the organic base may be present in a free state, and when the hydrogen chloride is excessive, part of the hydrogen chloride may be present in an unsalified state, which theoretically does not affect the performance of the process of the present invention.
The material of the volatile organic base and the hydrogen chloride can only contain one volatile organic base or can simultaneously contain two or more volatile organic bases, and theoretically, the implementation effect of the method of the invention is not influenced by the number of the types of the volatile organic bases contained in the material.
When the volatile organic alkali and hydrogen chloride material also contains one or more other inert components, the implementation effect of the invention is not obviously influenced. Common inert components are methanol, ethanol and the like, which do not have a significant effect on the performance of the process of the invention.
For the basic magnesium salt, when n =0, the basic magnesium salt is a chlorine-free basic magnesium salt. When m =0 and n =0, the basic magnesium salt is magnesium oxide. When m =1 and n =0, the basic magnesium salt is magnesium hydroxide. The main sources of these basic magnesium salts are various minerals, and the names of the commercial products are more, and the actual compositions of the basic magnesium salts vary according to the production area and the process. The essential difference between these basic magnesium salts, irrespective of impurities, can be seen as a difference in the degree of hydration. Since the process of the invention is carried out in the presence of water and the magnesium oxide is capable of hydrating to form magnesium hydroxide under the conditions of operation, the degree of hydration of the basic magnesium salt will, in theory, have no significant effect on the performance. In actual implementation, alkaline magnesium salts with different hydration degrees are used, and the implementation effect is not obviously influenced except that the metering of raw materials is influenced. The chlorine-free basic magnesium salt is mainly known as magnesium oxide, magnesium hydroxide, activated magnesium oxide, light burned magnesium oxide, or the like. It should be noted that these commercially available products may contain a small amount of chlorine depending on the actual production method. In addition, common commercial magnesium oxide products may actually be mixtures of magnesium oxide and magnesium hydroxide due to the difficulty in obtaining magnesium oxide free of magnesium hydroxide under typical manufacturing process conditions.
When n is greater than 0, the alkaline magnesium salt is a chlorine-containing alkaline magnesium salt. For chlorine-containing basic magnesium salt, the main quality index affecting the implementation effect is the molar ratio of magnesium element and chlorine element (hereinafter referred to as "magnesium-chlorine molar ratio", expressed by R, R =0.5+ 0.5/n). Theoretically, the larger the molar ratio R of magnesium to chlorine of the chlorine-containing basic magnesium salt used, the more moles of the organic base that can be released per mole of the basic magnesium salt (in terms of Mg, the same applies hereinafter), i.e., the higher the efficiency. Experiments prove that when the magnesium-chlorine molar ratio R of the chlorine-containing alkaline magnesium salt is sufficiently large, the effect of the chlorine-containing alkaline magnesium salt is close to that of magnesium oxide under the same molar amount. For example, when the molar ratio of magnesium to chlorine is R =90 (n = 0.0055), the effect is almost the same as that of magnesium oxide in the same molar amount (in terms of magnesium ions). When the magnesium chloride molar ratio R is reduced to near 1 (corresponding to n = 1), the chlorine-containing basic magnesium salt almost loses its ability to release free organic base. The experimental result shows that when the chlorine-containing alkaline magnesium salt with n <0.03 is used (the corresponding magnesium-chlorine molar ratio R is approximately equal to 17, and the corresponding chlorine content is 5.0 percent under the condition of low hydration degree), the application effect is acceptable. However, for chlorine-containing alkaline magnesium salts with n ≧ 0.03 and n ≦ 1.0, there is also a certain effect of releasing free volatile organic bases, and should still be considered as falling within the scope of the present invention. From the viewpoint of efficiency, it is preferable to use a chlorine-containing basic magnesium salt of R > 17.
As the amount of the basic magnesium salt to be used, it is suitably used in an amount of 0.5 to 2.0 times (in terms of a molar ratio of magnesium element to chlorine element in the final reaction system, the same shall apply hereinafter), preferably 1.0 to 2.0 times, more preferably 1.5 times.
The gasification process refers to a process for promoting the gasification of free volatile organic base into a gas phase space, and the specific method can be gas entrainment, distillation or the combination of the gas entrainment and the distillation. The gasification process can be operated under normal pressure or reduced pressure. For distillation, further improvement can be made to rectification. Since the free volatile organic base is more likely to leave the reaction system into the gas phase space upon heating to form water vapor entrainment and/or azeotropes, the separation is preferably carried out under conditions where the system boils, such conditions being readily understood and effected by those skilled in the art.
Optionally, the alkaline magnesium salt can also be obtained by thermal hydrolysis dechlorination of a byproduct of the neutralization reaction of the method, namely chlorine-containing magnesium salt, so that the recycling of the alkaline magnesium salt is realized. The by-product can be separated from the residue of the neutralization reaction by a filtration and leaching method, the filtrate and the leaching solution contain non-free volatile organic alkali and a very small amount of magnesium salt, and the material is economically treated by applying the material to the neutralization reaction of the next batch. The thermal hydrolysis dechlorination of magnesium chloride and magnesium chloride water solution is widely applied in the metallurgical industry, is a main production method of magnesium oxide, and belongs to the prior art. We have found that the chlorine-containing magnesium salt obtained by the neutralization reaction can be dechlorinated under the thermal hydrolysis condition, and the dechlorination degree can meet the requirement of recycling as the alkaline magnesium salt. When the thermal hydrolysis technology is used for dechlorinating the chlorine-containing magnesium salt, the key process parameter is the temperature, the higher the temperature is, the more complete the dechlorination is, but the energy consumption is relatively higher. It should be noted that high temperatures in excess of 1100 c may "burn" the magnesium salt, causing it to lose its partial neutralizing capacity. If the temperature is too low, the dechlorination is incomplete, and the application effect is affected. The preferred thermal hydrolysis temperature is 350-850 deg.C, more preferably 600-850 deg.C. The thermal hydrolysis can also be carried out under the condition of introducing steam, and the thermal hydrolysis is carried out in the steam atmosphere, so that the chlorine removal is more facilitated. It is noted that chlorine-containing alkaline magnesium salt obtained after thermal hydrolysis dechlorination can be further dechlorinated by washing with alkaline water, but the further dechlorination step is not necessary because the magnesium-chlorine molar ratio R value of the chlorine-containing alkaline magnesium salt is high enough (not less than 17) to meet the application requirement.
Compared with the prior art, the invention has the outstanding and beneficial technical effects that:
the initial byproduct of the method is chlorine-containing magnesium salt, and the byproduct can be thermally hydrolyzed and dechlorinated to obtain hydrogen chloride and chlorine-containing alkaline magnesium salt with relatively low chlorine content. The obtained hydrogen chloride is absorbed by water to obtain high-quality hydrochloric acid, and the comprehensive utilization value is better. The chlorine content of the obtained chlorine-containing alkaline magnesium salt can be conveniently controlled to be lower than 5.0 percent, the technology completely meets the requirement of recycling, and the chlorine-containing alkaline magnesium salt can be used as the alkaline magnesium salt to be recycled to the neutralization reaction, so that the recycling of the alkaline magnesium salt is realized.
Theoretically, the alkaline magnesium salt can be recycled for unlimited times, only mechanical loss needs to be supplemented, other materials except water are not consumed, and secondary byproducts are only hydrochloric acid with good comprehensive utilization value. The method for recovering the volatile organic alkali realizes the separation of the volatile organic alkali and the hydrogen chloride by using the traditional process conditions, is a feasible method, and is easy to realize large-scale application.
The following examples are typical applications of the process of the present invention and show how the process can be used to achieve some common separation of volatile organic bases and hydrogen chloride. It should be noted that these examples are not intended to limit the scope of the invention, which is defined by the claims, and that modifications and improvements can be readily made thereto by those skilled in the art after understanding the principles of the invention. It is intended that such modifications and improvements be considered as within the scope of the invention.
Detailed Description
Example 1
Monomethylamine hydrochloride 35.0g (0.52 mol), 400ml of water, and magnesium oxide 21.3g (light magnesium oxide, nominal content 98%,0.52mol, average particle diameter 50 μm, weight loss less than 1.0% by heating to 350 ℃) were mixed in a 500ml three-necked flask, heated and distilled in an oil bath at 130 ℃ (condenser tube circulating water temperature 0-5 ℃), and the distillate was absorbed with a small amount of water (receiver flask insulated at 0-10 ℃). When no obvious distillate is obtained by distillation, 300g of water is added, and the mixture is distilled again until no obvious liquid is obtained.
The distillate collected was significantly alkaline and analyzed by acid-base titration (indicator is methyl orange, blank subtracted) to show that it contained 0.40mol monomethylamine and a calculated recovery of 77% (based on monomethylamine hydrochloride).
Example 2
The procedure of example 1 was followed except that 30.5g of magnesium hydroxide (nominal content 99%,0.52mol, weight loss by heating to 350 ℃ C.) was used in place of magnesium oxide.
The final monomethylamine recovery was 77% (based on monomethylamine hydrochloride).
Examples 3 to 6
Examples 3-6 were conducted in the same manner as in example 1 except that only the amount of magnesium oxide was adjusted. The results of the experiments are shown in the following table.
| # | 98% of magnesium oxide | Recovery rate |
| Example 3 | 70.0g(1.70mol) | 88％ |
| Example 4 | 42.6g(1.04mol) | 83％ |
| Example 5 | 15.0g(0.36mol) | 56％ |
| Example 6 | 10.6g(0.26mol) | 40％ |
Example 7
Taking 210g (aqueous solution containing hydrogen chloride and ethylamine, which is determined to contain 7.9 percent of ethylamine, 0.37mol of ethylamine, 8.1 percent of hydrogen chloride, 0.47mol of ethylamine and hydrogen chloride, the molar ratio of the ethylamine to the hydrogen chloride is 1.26), 200ml of water and 31.4g (0.76 mol) of 98 percent magnesium oxide in a 500ml three-port reaction bottle, heating to 50 ℃ and stirring, simultaneously beginning to bubble with nitrogen, wherein the gas source is a 2L buffer gas bag, introducing the gas escaping from the bubbling into a 250ml receiving bottle, using 100ml of water to bubble at 0-10 ℃ to absorb the ethylamine, and introducing the gas escaping from the bubbling in the receiving bottle back to the 2L buffer gas bag to form gas circulating bubbling. The bubbling gas flow rate was maintained at about 1.5 liters/min, and after 16 hours a sample was taken from the receiver flask containing about 0.20mol of ethylamine with a recovery of 54% (based on ethylamine).
Stopping bubbling of nitrogen, placing a 500ml three-necked bottle in an oil bath at 130 ℃, heating and refluxing, distilling until no obvious distillate exists, supplementing 300g of water, and distilling again until no obvious liquid is distilled. The resulting distillate was analyzed to contain 0.09mol of ethylamine with a recovery of 24% (based on ethylamine).
The overall recovery of ethylamine was 78%.
Example 8
32.9g (0.30 mol) of n-butylamine hydrochloride, 400ml of water and 21.0g (0.51 mol) of 98% magnesium oxide were mixed in a 500ml three-necked flask, distilled in an oil bath at 130 ℃ and the evolved gases and distillates were absorbed in a small amount of water (25 ml of water were initially taken in the receiving flask and the flask was kept at 0-10 ℃). When no obvious distillate is obtained by distillation, 300g of water is added, and the mixture is distilled again until no obvious liquid is obtained.
The distillate was analyzed to contain 0.26mol of n-butylamine and a calculated recovery of 87% (based on n-butylamine hydrochloride).
Examples 9 to 16
The procedure of example 8 was followed, starting from other hydrochloride salts of primary, secondary and tertiary amines, instead of n-butylamine hydrochloride, while maintaining the same conditions and the experimental results are given in the following table:
| # | name of raw materials | Raw material dosage | The amount of magnesium oxide | Recovery rate | Remarks for note |
| Example 9 | N-propylamine hydrochloride | 28.7g,0.30mol | 14.8g,0.36mol | 80％ | |
| Example 10 | Isopropylamine hydrochloride | 28.7g,0.30mol | 14.8g,0.36mol | 81％ | |
| Example 11 | Isobutylamine hydrochloride | 32.9g,0.30mol | 14.8g,0.36mol | 80％ | |
| Example 12 | Sec-butylamine hydrochloride | 32.9g,0.30mol | 14.8g,0.36mol | 82％ | |
| Example 13 | Cyclopropylamine hydrochloride | 28.1g,0.30mol | 14.8g,0.36mol | 83％ | |
| Example 14 | Dimethylamine hydrochloride | 24.5g,0.30mol | 14.8g,0.36mol | 78％ | |
| Example 15 | Diethylamine hydrochloride | 32.9g,0.30mol | 14.8g,0.36mol | 79％ | |
| Example 16 | Diisopropylamine hydrochloride | 41.3g,0.30mol | 14.8g,0.36mol | 78％ | After methanol dilution to homogeneous phase titration |
Example 17
41.3g (0.30 mol) of diisopropylamine hydrochloride, 400ml of water and 21.0g (0.51 mol) of 98% magnesium oxide are mixed in a 500ml three-neck flask, the mixture is distilled under reduced pressure in an oil bath at 105 ℃ under vacuum of-0.075 MPa, and escaped gas and distillate are cooled by a condenser tube (the temperature of condensed water is 0-5 ℃) and absorbed by a small amount of water (25 ml of water is added in a receiving flask in advance and the temperature is kept at 0-10 ℃).
When no obvious distillate is obtained by distillation, 300g of water is added, and the mixture is distilled again until no obvious liquid is obtained.
The distillate was analyzed to contain 0.25mol of diisopropylamine and a calculated recovery of 83% (based on diisopropylamine hydrochloride).
Example 18
41.3g (0.30 mol) of diisopropylamine hydrochloride, 400ml of water and 14.8g (0.36 mol) of 98 percent magnesium oxide are mixed in a 500ml three-neck bottle, heated in an oil bath at 130 ℃, rectified under normal pressure by a 60cm glass spring packed column, taken out after the top temperature is stable, and the receiving bottle is insulated at 0-10 ℃. When no obvious distillate is obtained by distillation, 300g of water is added, and the mixture is distilled again until no obvious liquid is obtained.
The liquid in the receiver bottle was diluted to homogeneity with methanol and sampled for analysis, containing a total of 0.279mol of diisopropylamine, and the calculated recovery was 79% (based on diisopropylamine hydrochloride).
Example 19
Example 18 was followed by substituting triethylamine hydrochloride for diisopropylamine hydrochloride.
The distillate was diluted with methanol to a homogeneous phase and sampled for analysis, containing a total of 0.252mol triethylamine, with a calculated recovery of 84% (based on triethylamine hydrochloride).
Example 20
41.3g (0.30 mol) of triethylamine hydrochloride, 400ml of water and 14.8g (0.36 mol) of 98% magnesium oxide were mixed in a 500ml three-necked flask, distilled in an oil bath at 130 ℃ and the receiving flask was kept at 0 to 10 ℃.
When no obvious distillate is obtained by distillation, 300g of water is added, and the mixture is distilled again until no obvious liquid is obtained. This operation was repeated once.
The distillate was diluted with methanol to homogeneous phase, sampled and analyzed to contain triethylamine 0.246mol, and calculated to yield 82% (based on triethylamine hydrochloride).
200ml of water are added to the residue, the mixture is stirred uniformly and filtered, and the filter cake is rinsed with deionized water, dried at 105 ℃ and then crushed to obtain about 36.7g of solid powder.
The content of chloride ions in the solid powder (measured by a silver nitrate precipitation method after dissolving dilute sulfuric acid by heating) was measured, and the result was 24.5%.
Example 21
20.7g (0.15 mol) of triethylamine hydrochloride, 200ml of water, and 36.0g (0.36 mol in terms of magnesium element, chlorine content 24.9%, corresponding to m =3.46, n =0.54 in MgO. MH 2O. NMgCl 2) of the solid powder recovered in the same manner as in example 20 were mixed in a 500ml three-necked flask, distilled in an oil bath at 130 ℃ and the receiving flask was kept at 0-10 ℃.
When no obvious distillate is obtained by distillation, 200g of water is added, and the mixture is distilled again until no obvious liquid is obtained. This operation was repeated once.
The distillate was diluted with methanol to a homogeneous phase, which was sampled to analyze the presence of triethylamine at 0.023mol, and the calculated recovery was 15% (based on triethylamine hydrochloride).
Example 22
48.7g (content: 95%,0.40 mol) of pyridine hydrochloride and 24.7g (98% light magnesium oxide, reduced to 0.60 mol) of magnesium oxide were mixed in a 500ml three-necked flask, 350ml of water was added, and distillation was carried out under normal pressure with stirring until almost no liquid was distilled off, and further 300ml of water was added, and distillation was carried out again until no significant liquid was distilled off.
The distillate was taken for analysis of pyridine content and the recovery was calculated to be 56% (based on pyridine hydrochloride).
Example 23
53.4g (content: 97%,0.40 mol) of 2-methylpyridine hydrochloride and 24.7g (98% light magnesium oxide, reduced to 0.60 mol) of magnesium oxide were mixed in a 500ml three-necked flask, 350ml of water was added, and the mixture was subjected to atmospheric distillation through a 40cm glass-spring column with stirring until almost no liquid was distilled off.
The distillate was taken, diluted to a homogeneous phase with methanol, analyzed for 2-methylpyridine content and calculated for recovery, giving a 94% (based on 2-methylpyridine hydrochloride).
Examples 24 to 25
The same molar amounts of the hydrochloride salts of various other pyridine derivatives were used in place of 2-methylpyridine hydrochloride in the same manner as in example 22, and the following results were obtained:
| # | name of raw materials | Recovery rate | Remarks for note |
| Example 24 | 3-methylpyridine hydrochloride | 95％ | |
| Example 25 | 4-methylpyridine hydrochloride | 94％ |
Example 26
29.3g (content: 98%, equivalent to 0.20 mol) of 2,6-dimethylpyridine chloride, 200ml of water and 12.3g (98% light magnesium oxide, equivalent to 0.30 mol) of magnesium oxide were rectified under reduced pressure (vacuum-0.075 MPa) through a 40cm glass spring packed column until no significant liquid distilled off.
The distillate was diluted to a homogeneous phase with methanol and sampled for 2,6-lutidine content and the recovery calculated to be 96% (based on 2,6-lutidine hydrochloride).
Example 27
29.3g (98% content, reduced to 0.20 mol) of 2,6-lutidine hydrochloride, 200ml of water, 20.6g (98% light magnesium oxide, reduced to 0.50 mol) of magnesium oxide were rectified under reduced pressure (vacuum-0.075 MPa) through a 40cm glass spring packed column until no significant liquid distilled off.
The distillate was diluted to a homogeneous phase with methanol and sampled for 2,6-lutidine content and the recovery calculated to be 96% (based on 2,6-lutidine hydrochloride).
200ml of water is added into the residue, the mixture is stirred uniformly and then filtered, the obtained solid is washed by deionized water and dried at 105 ℃, and the solid powder is crushed to obtain 45.0g of solid powder.
The solid powder was analyzed for chloride ion content (dissolved by heating with dilute sulfuric acid and then measured by the silver nitrate precipitation method) and found to be 14.2%.
Example 28
27.5g (0.20 mol) of triethylamine hydrochloride, 300ml of water, and 13.0g of a basic magnesium salt containing chlorine (recovered from example 31, total amount of magnesium element was 0.30mol, chlorine was 4.5%, corresponding to the general formulae m =0.09 and n = 0.028) were mixed in a 500ml three-necked flask, distilled in an oil bath at 130 ℃ and the receiving flask was kept warm in an ice-water bath at 0-10 ℃.
When no obvious distillate is obtained by distillation, 200g of water is added, and the mixture is distilled again until no obvious liquid is obtained. This operation was repeated once.
The distillate was diluted with methanol to a homogeneous phase and sampled for analysis, and from the results a 83% recovery (based on triethylamine hydrochloride) was calculated.
Example 29
2,6-lutidine hydrochloride 29.3g (98% content, equivalent to 0.20 mol), 200ml water, and chlorine-containing basic magnesium salt 12.2g (recovered in example 32, 0.3% chlorine, 0.30mol of total magnesium element, equivalent to general formula m =0.015, n = 0.002) were charged into a 500ml three-necked flask and rectified under reduced pressure (vacuum-0.075 MPa) through a 40cm glass spring-packed column until no significant liquid distilled off.
The distillate was diluted to a homogeneous phase with methanol and sampled for 2,6-lutidine content and the recovery calculated to be 95% (based on 2,6-lutidine hydrochloride).
Example 30
270g (mass composition: 3.7% of monomethylamine, 6.7% of dimethylamine, 10.1% of hydrogen chloride, 4.1% of methanol, 0.32mol of monomethylamine, 0.40mol of dimethylamine and 0.75mol of hydrogen chloride) of a hydrochloride aqueous solution of a primary mixed amine was put into a 500ml three-necked flask, 150ml of water and 46.3g (1.126 mol) of 98% magnesium oxide were added thereto, and the mixture was stirred.
Heating in 130 deg.C oil bath, rectifying under normal pressure with 60cm glass spring packed column, and holding at 0-10 deg.C (adding 100ml ice water in advance). The distillation was stopped after distillation until no significant distillate was obtained.
The liquid in the receiving bottle is shaken up, sampled, titrated and analyzed, the total amount of the distilled organic amine is calculated, and the recovery rate is calculated, and the result is 80%.
Example 31 chlorine-containing magnesium salt recovery experiment
35.0g of the solid powder obtained in example 20 was weighed and calcined at 700-800 ℃ for 1.5 hours in a muffle furnace (HCl off-gas was absorbed in water through an induced draft hood). Taking out, cooling to normal temperature, and crushing to obtain 14.5g of chlorine-containing alkaline magnesium salt.
The chlorine content of the obtained solid powder was measured by a silver nitrate precipitation method, and found to be 4.5%.
Example 32 chlorine-containing magnesium salt recovery experiment
28.0g of the solid powder obtained in example 27 was weighed and calcined at 700-800 ℃ for 1.5 hours in a muffle furnace (HCl off-gas was absorbed into water through an induced draft hood). Taking out and cooling to normal temperature, then soaking with water, and placing in a muffle furnace again to bake for 1.5 hours at 700-800 ℃. After cooling to room temperature, the mixture was pulverized to obtain 12.9g of chlorine-containing basic magnesium salt, and the chlorine content was analyzed to be 1.7% (equivalent to R =35, n =0.014, regardless of the remaining trace amount of hydration).
Example 33
And (3) neutralization reaction:
41.3g (0.30 mol) of triethylamine hydrochloride, 300g of water, 14.8g (0.36 mol) of 98% magnesium oxide were mixed in a 500ml three-necked flask, distilled in an oil bath at 130 ℃ and the receiving flask was kept at 0 to 10 ℃. When no obvious distillate is obtained by distillation, 300g of water is added, and the mixture is distilled again until no obvious liquid is obtained. The distillate was diluted with methanol to a homogeneous phase, sampled and analyzed for a total of 0.246mol triethylamine, and calculated to yield 82% (based on triethylamine hydrochloride).
Treatment of the reaction residue:
200ml of water were added to the reaction residue, stirred well and filtered, rinsed with deionized water, and the filtrate and rinse were combined for priming of the next batch of reactions. The filter cake was dried at 105 ℃ and then pulverized to obtain about 36.7g of a solid powder. The obtained powder is roasted for 2.0 hours at 700-850 ℃ by a muffle furnace, a small amount of water vapor is introduced occasionally, and HCl tail gas is absorbed by water through an induced draft cover. The temperature was reduced to normal temperature, and the resulting mixture was pulverized to obtain 15.5g of a solid powder.
Experiment for applying alkaline magnesium salt:
the obtained solid powder was used in place of 14.8g of magnesium oxide, and the neutralization reaction was repeated while maintaining the other conditions, whereby the recovery rate of triethylamine was 80%.
Example 34
Thermal hydrolysis dechlorination was carried out according to the method of example 33, and then the temperature was reduced to normal temperature and powdering was carried out. 200ml of 5.0% aqueous sodium carbonate solution of the resulting powder was heated and slurried for further dechlorination, filtered and rinsed with water to a pH of about 8.
The cake was dried at 105 ℃ and then the chlorine content was measured to obtain 0.3% (R >200, n-woven fabrics 0.0025). The samples contained small amounts of carbonate (the amount was not accurately determined).
The neutralization reaction experiment of example 33 was repeated using the obtained filter cake instead of 14.8g of magnesium oxide, and the recovery rate of triethylamine was 81%.
Example 35
And (3) neutralization reaction:
the analytical data for the material to be treated are as follows: contains dimethylamine 12.1%, hydrogen chloride 10.3%, methanol 2.0% and water for the rest.
750g of the material (2.01 mol in terms of dimethylamine and 2.12mol in terms of hydrogen chloride) is taken and added into a 1000ml three-mouth reaction bottle, 128.1g (about 3.18 mol) of 98 percent magnesium oxide is added, stirring is started, the temperature is raised, and the escaped gas is absorbed by bubbling 500ml of water at 0-10 ℃ through a 1000ml receiving bottle. And after the internal temperature reaches 96 ℃, beginning to preserve heat, controlling the temperature within 96 +/-2 ℃, and continuously absorbing the escaped gas.
After 1 hour, bubbling with nitrogen gas in a reaction bottle by using a 2L buffer gas bag as a gas source, introducing gas escaping from the bubbling into a receiving bottle, absorbing dimethylamine in the receiving bottle by using a bubbling method, and introducing the gas escaping from the bubbling in the receiving bottle back to the 2L buffer gas bag to form gas flow circulation. The gas flow rate was maintained at 2.0 l/min and bubbling was continued for 7 hours.
Bubbling was stopped, a sample was taken for analysis, and the receiving bottle contained 1.51mol of dimethylamine, resulting in a recovery of 75%.
Treatment of the reaction residue:
and filtering the materials in the reaction bottle, and leaching a filter cake with deionized water to obtain a chlorine-containing magnesium salt wet product. The filtrate and the eluate were combined and distilled under normal pressure to about 650g to obtain a concentrated solution (containing about 0.50mol of dimethylamine and about 0.50mol of hydrogen chloride) for further use.
The wet product containing chlorine magnesium salt is dried at 105 ℃ and then crushed to obtain 210g of chlorine magnesium salt, and the chlorine magnesium salt is divided into 2 parts.
105g of the first chlorine-containing magnesium salt is placed in a muffle furnace to be roasted at 350-450 ℃, acid gas is absorbed by water through an induced draft hood, and the temperature is kept until no acid gas is generated. After cooling to normal temperature, the mixture was pulverized again to obtain 67.7g of chlorine-containing basic magnesium salt. A sample was taken to determine a chlorine content of 6.4% (irrespective of the residual traces of hydration, corresponding to R =13, n = 0.040)
And roasting the second part of chlorine-containing magnesium salt at 700-850 ℃ by using a muffle furnace, absorbing acid gas by using water through an induced draft cover, and keeping the temperature until no acid gas is generated. The temperature was reduced to normal temperature, and the mixture was pulverized again to obtain 66.8g of basic magnesium salt containing chlorine, and the chlorine content was measured to be 4.5% (not considering the remaining trace amount of hydration, which corresponds to R =19, n = 0.027).
The application experiment is as follows:
31.6g (equivalent to about 0.75 mol) of a chlorine-containing basic magnesium salt obtained by thermal hydrolysis and dechlorination of a second chlorine-containing magnesium salt was taken, and the obtained solution was charged into a 1000ml three-neck reaction flask together with the above concentrated solution, neutralized under the same process conditions, dimethylamine was separated by bubbling nitrogen gas, and bubbling was stopped after 7 hours. The absorption solution was analyzed, and 0.30mol of dimethylamine was recovered at a recovery rate of 15%.
The dimethylamine was obtained in 1.81mol by the total recovery of the two neutralizations, and the total recovery rate was 90%.
Example 36
And (3) neutralization reaction:
the content data of the materials to be treated (triethylamine and aqueous hydrogen chloride solution) are as follows: contains 16.1 percent of triethylamine and 7.5 percent of hydrogen chloride.
750g of the material (1.19 mol in terms of triethylamine and 1.54mol in terms of hydrogen chloride) is taken and added into a 1000ml three-mouth reaction bottle, 93.5g (about 2.32 mol) of 98 percent magnesium oxide is added, stirring is started, the temperature is raised by using a 130 ℃ oil bath, rectification is carried out through a glass spring packed column (random pile) with the height of 60cm, a receiving bottle is insulated by using ice bath at 0-5 ℃, the extraction is kept until the outlet temperature rises to be close to 100 ℃ and does not rise any more, and about 100ml of distillate is continuously extracted. Stopping rectification and cooling to room temperature.
After the distillate is diluted into a homogeneous phase by methanol, sampling analysis is carried out, the receiving bottle contains 0.99mol of triethylamine, and the recovery rate is 83 percent.
Treatment of the reaction residue:
and filtering the materials in the reaction bottle, and leaching a filter cake with deionized water to obtain a chlorine-containing magnesium salt wet product. The filtrate and the leacheate are combined and distilled to about 130g under normal pressure to obtain a concentrated solution (containing about 0.20mol of triethylamine and about 0.20mol of hydrogen chloride) for later use.
Drying wet products containing chlorine magnesium salt at 105 ℃, crushing to obtain 165g of chlorine magnesium salt, roasting the chlorine magnesium salt in a muffle furnace at 700-850 ℃, absorbing acid gas by water through an induced draft cover, and preserving heat and roasting until no acid gas is generated obviously. After cooling to room temperature, the mixture was pulverized again to obtain 96.7g of chlorine-containing basic magnesium salt, and the chlorine content was measured to be 4.6% (corresponding to R =18.3, n =0.028, regardless of the remaining trace amount of hydration).
The application experiment is as follows:
taking 94.0g (equivalent to about 2.25 mol) of chlorine-containing basic magnesium salt obtained by thermal hydrolysis dechlorination, adding the chlorine-containing basic magnesium salt into a 1000ml three-mouth reaction bottle, adding the concentrated solution, and finally adding 633g (equivalent to 1.01mol of triethylamine and 1.30mol of hydrogen chloride) of the material to be treated. According to the same process conditions of the neutralization reaction in the embodiment, 0.97mol of triethylamine is obtained by recovery, and the recovery rate is 80%.
Claims (6)
1. A process for separating a volatile organic base from a feed comprising the volatile organic base and hydrogen chloride, the process comprising: neutralizing a material containing volatile organic alkali and hydrogen chloride with alkaline magnesium salt in the presence of water, separating free volatile organic alkali by adopting a gasification process, wherein the volatile organic alkali is organic alkali with an atmospheric boiling point of not more than 150 ℃, is not limited in the presence of the material, can be in a complex form, can be in a free alkali form or both, and the hydrogen chloride is a substance with an element composition represented as HCl, and is not limited in the presence of the element composition represented as HClThe basic magnesium salt exists in the material in a salified state or an unsalified state, and the basic magnesium salt mainly comprises the general formula of MgO & mH 2 O·nMgCl 2 The substance shown in the formula, wherein m and n are independent of each other and satisfy the following conditions: m is not less than 0,0 and n is not less than 0.03, the gasification process is a process for promoting the gasification of free volatile organic alkali to enter a gas phase space, and the method further comprises the step of performing thermal hydrolysis and dechlorination on of a byproduct of the neutralization reaction, namely the chlorine-containing magnesium salt, to obtain the alkaline magnesium salt for recycling.
2. The method of claim 1, wherein: the volatile organic base is one of dimethylamine, triethylamine, diisopropylethylamine, pyridine, 2-methylpyridine, 4-methylpyridine or 2,6-dimethylpyridine or a mixture of the two, and is characterized in that: the main component of the basic magnesium salt is one of magnesium oxide (namely m =0, n =0 in the general formula), magnesium hydroxide (namely m =1, n =0 in the general formula) or a mixture of the magnesium oxide and the magnesium hydroxide.
3. The method of claim 1, wherein: the volatile organic base is one or a mixture of dimethylamine, triethylamine and diisopropylethylamine, and is characterized in that: the main component of the basic magnesium salt is one of magnesium oxide (namely m =0, n =0 in the general formula), magnesium hydroxide (namely m =1, n =0 in the general formula) or a mixture of the magnesium oxide and the magnesium hydroxide.
4. The method of claim 1, wherein: the gasification process is distillation.
5. The method of claim 1, wherein: the volatile organic base is one of dimethylamine, triethylamine, diisopropylethylamine, pyridine, 2-methylpyridine, 4-methylpyridine or 2,6-dimethylpyridine or a mixture of the dimethylamine, the triethylamine, the diisopropylethylamine and the pyridine.
6. The method of claim 1, wherein: the volatile organic base is one of dimethylamine, triethylamine and diisopropylethylamine or a mixture of dimethylamine, triethylamine and diisopropylethylamine, and the gasification process is distillation.
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