CN103483376B - Tobacco waste extracts the extraction process of inositol hexaphosphate calcium magnesium coproduction nicotine - Google Patents

Abstract

The invention discloses an extraction method for co-producing nicotine by extracting inositol hexaphosphate calcium magnesium from tobacco waste. The method takes tobacco roots, leaves, stalks or fireworks, pulverizes them, and extracts nicotine first under slightly acidic conditions. , and under this condition, phytic acid cannot be freed. Continue to adjust the pH to 2.0-3.0 to extract phytic acid and further generate inositol calcium magnesium hexaphosphate. The biggest advantage of this process is that it can be produced simultaneously by continuously adjusting the pH value. Inositol calcium magnesium hexaphosphate and nicotine reduce production costs; this process has high extraction efficiency, can simultaneously obtain phytin and nicotine, greatly reduces sewage discharge, reduces production costs, and is more practical for making full use of tobacco waste resources meaning.

Description

Extraction Technology of Inositol Hexaphosphate Calcium Magnesium and Co-production of Nicotine from Tobacco Waste

technical field

The invention relates to an extraction process for extracting inositol hexaphosphate calcium magnesium and co-producing nicotine from tobacco waste.

Background technique

my country has a large tobacco planting area, and a certain amount of tobacco leaves cannot be used for cigarette production during the harvesting process. At the same time, a lot of waste such as stalks, roots and fireworks are left behind. It is a pity to discard them if they cannot be used. Tobacco waste contains a variety of chemical components, mainly including alkaloids, proteins, amino acids, glycosides, sugars, organic acids and other substances. Among them, nicotine, solanesol, organic acid, tobacco protein, etc. all have high utilization value. The comprehensive utilization of waste tobacco leaves has always been valued by researchers at home and abroad, and many relatively mature extraction processes and methods have been produced. There are mainly the following three types: ① extraction of nicotine; ② extraction of solanesol; ③ extraction of tobacco protein. In 2010, Li Jun and others mentioned in the article "Research on the Utilization of Tobacco Wastes" that tobacco wastes contain phytin (calcium magnesium hexaphosphate) substances, which are harmful to the tobacco planted in Dayingjie Town, Yuxi City, Yunnan Province. The content of phytin in roots, stems, leaves, and flowers was determined, and it was found that its content was 1.0% to 5.0%. Phytin is widely used in pharmaceutical, chemical, food, daily chemical and other industries. In recent years, the demand for phytin in the pharmaceutical industry has increased rapidly, and the international market is relatively active. However, there are few reports on the extraction process of phytin from tobacco waste. Therefore, it is of practical significance to optimize the extraction process of phytin and improve the utilization rate of tobacco waste.

The extraction process of phytin in corn steep liquor, peanut shell, bran, distiller's grains and rice bran has been reported at home and abroad. The corresponding extraction methods include acid extraction, alkali neutralization, ion exchange, macroporous resin elution, microwave-assisted and ultrasonic acid leaching extraction etc.; the above method has certain applicability, but there are also many problems, which limit the extraction and utilization of phytin. It is simple and easy to operate, but it needs to discharge 6-7 tons of sewage for processing 1 ton of raw materials, and the amount of wastewater discharged per ton of Phytin produced is as high as 60-70 tons, and the environmental pollution is relatively serious; ② The ion exchange method (CN 102702250 A) is adopted Phytic acid in corn steep liquor is adsorbed by an ion exchange column, then eluted with acid, neutralized with lime water to pH 4.0-6.0, precipitated, dried, and crushed to obtain phytin. This method is simple to operate, but the output is low, and the acid elution has great damage to the ion exchange material, and the resin material needs to be replaced at any time, which increases the production cost. ②Microwave extraction (CN200710170689.2) can shorten production time, reduce energy and solvent consumption, but microwave extraction requires high technological conditions, the extraction process is cumbersome, and cannot be scaled up for pilot testing; ③Ultrasonic extraction can increase the leaching rate, It saves energy and avoids the influence of high temperature on the extracted components, but the ultrasonic generator has high manufacturing cost and is easily damaged, so it is not suitable for large-scale industrial production. In view of the above problems, based on the extraction method of acid extraction and alkali neutralization, the extraction process of nicotine and phytin in the tobacco waste of Yuxi cigarette factory in Yunnan was studied for the first time, and the acid leaching solution was recycled to ensure that the extraction rate did not decrease. Under the prerequisite conditions, the sewage discharge is greatly reduced and the environmental pollution is reduced.

Contents of the invention

The object of the present invention is to provide an extraction process for extracting inositol hexaphosphate calcium magnesium and co-producing nicotine from tobacco waste. The method has low production cost, low pollution and high utilization rate of tobacco waste.

The concrete operating steps of the inventive method are as follows:

1. Nicotine extraction

(1) Collect the tobacco roots, residual tobacco leaves, tobacco stalks or fireworks after the tobacco farmers harvest the tobacco leaves, and crush them into tobacco fragments with a length of less than 3 mm for later use;

(2) Take 100-200kg of tobacco shreds, put them in a soaking tank, add 300-600kg of hot water at 60-70°C, mix well, and adjust the pH of the mixture to 5.0-6.0 with industrial sulfuric acid with a concentration of 90% by mass , soaked for 3-4 hours, during which the soaking temperature was kept at 60-70°C, acid was added to keep the soaking pH at 5.0-6.0, and stirred every 10-15 minutes; then steam was introduced to raise the soaking temperature to 85-90°C and kept constant Change, keep the pH 5.0~6.0 unchanged, extract for 1~1.5h, filter, the filtrate is set aside, repeat the above operation steps with the filter residue as the raw material, carry out the second extraction, combine the two extraction filtrates, and use the filter residue for standby; fully stir the filtrate, adjust pH is 6.0～7.0, cooling;

(3) Add chloroform to the filtrate in step (2) for extraction, the addition amount is 100-150 kg, take the extract phase and recover the chloroform to obtain nicotine sulfate, and use the raffinate phase for later use;

2. Extraction of phytin (calcium magnesium hexaphosphate)

(1) Primary immersion: the raffinate obtained after extracting nicotine is combined with the filter residue, and water is added or the third immersion solution in the subsequent process is added. The mass ratio of solid to liquid is 1:3-1:5, fully stirred, and adjusted by adding acid The pH of the mixture is 2.0-3.0 and remains unchanged, maintain the extraction temperature at 25-30°C, extract for 2-3 hours, and stir once every 10-15 minutes;

(2) Second immersion: Step (1) the mixture is filtered, the filtrate is the first immersion solution for use, the filter residue is mixed with water or the third immersion solution, the process conditions of step (1) are repeated, the second leaching is performed, and the second immersion solution is obtained by filtration;

(3) Production of inositol calcium magnesium hexaphosphate (phytin): combine the first soaking liquid and the second soaking liquid, adjust the pH to 4.0 to 4.5 with calcium hydroxide with a mass percentage concentration of 10% to 15%, and stir for 10 to 15 min, use sodium hydroxide with a mass percentage concentration of 10% to 15% to neutralize the pH value of 6.5 to 7.0, stir fully, let it stand, take the precipitate and dry it to obtain calcium magnesium hexaphosphate, and the supernatant is used for production of calcium sulfate;

(4) Three leaching: the filter residue obtained from the second leaching is placed in the leaching tank, soaked in clean water, the solid-liquid mass ratio is 1:2-1:3, leaching for 12-15 hours, stirring once every 30-60 minutes, and filtering. The third soaking solution and the third soaking residue are obtained, the third soaking solution is used for later use, mainly used to supplement the extraction water for the first soaking and the second soaking, and the third soaking residue is used for feed or extraction of solanesol.

Advantage of the present invention and technical effect are as follows:

1. The method of the present invention can extract nicotine first under slightly acidic conditions (pH5.0-6.0), but phytic acid cannot be freed under this condition, and the phytic acid can be extracted by continuing to adjust the pH to 2.0-3.0 , and further generate inositol calcium magnesium hexaphosphate. The biggest advantage of this process is that through continuous adjustment of the pH value, simultaneous production of inositol calcium magnesium hexaphosphate and nicotine reduces production costs. In addition, the protein content in tobacco waste is relatively high (greater than 10%), and the protein may be leached from it during the extraction process of nicotine and phytic acid. It is neutral, and sodium sulfate is generated during this process, which can passivate the protein, avoid co-precipitation of protein, and improve product quality; after extracting nicotine and phytin, the feed produced by the filter residue has higher acidity and palatability than ordinary feed. Strong, can increase the activity of pepsin, delay the residence time of protein in the stomach, and facilitate the absorption of protein, thereby improving the utilization rate of tobacco waste;

2. For the first time, the extraction process of phytin from tobacco waste was reported; after the extraction of nicotine was adjusted to pH 2.0-3.0 with sulfuric acid, the extraction of phytin was continued, and the production cost was greatly reduced; part of the extract was recycled to reduce environmental pollution. pollute;

3. This process has high extraction efficiency, can simultaneously obtain phytin and nicotine, greatly reduces sewage discharge, reduces production costs, and has practical significance for making full use of tobacco waste resources.

Detailed ways

The present invention will be described in further detail below through the examples, but the protection scope of the present invention is not limited to the content.

Embodiment 1: The extraction method of extracting inositol hexaphosphate calcium magnesium hexaphosphate and co-producing nicotine from tobacco waste, the specific operation is as follows:

(1) Collect the tobacco roots after the tobacco farmers harvest the tobacco leaves and crush them to the tobacco root fragments with a length of less than 3 mm and a diameter of less than 1 mm;

(2) Take 100kg of tobacco root fragments, put them in the soaking tank, add 300kg of hot water at 65°C, adjust the pH to 5.0 with industrial sulfuric acid with a concentration of 90% by mass, keep the soaking temperature at 65°C, and add acid to maintain The soaking pH is 5.0, stir once every 10 minutes, soak for 3 hours, then pass in water vapor, raise the soaking temperature to 85°C and keep it constant, keep the pH 5.0, extract for 1 hour, filter, and the filtrate is used as raw material; the filter residue is used as raw material Repeat the above operation steps, carry out the second extraction, combine the two extraction filtrates, and filter the residue for later use; fully stir the filtrate, adjust the pH to 7.0, and cool;

(3) Add chloroform to the neutralized filtrate for extraction, the addition amount is 100 kg, take the extract phase and recover chloroform to obtain nicotine sulfate, and use the raffinate phase for later use;

(4) The raffinate obtained after extracting nicotine is combined with the filter residue, water is added to keep the solid-to-liquid mass ratio at 1:3, fully stirred, and the pH is adjusted to 2.0 with industrial sulfuric acid with a mass percentage concentration of 90% and remains unchanged. The leaching temperature is 25°C, leaching for 3 hours, stirring once every 15 minutes;

(5) Filtration, the filtrate is the first immersion solution for later use, the filter residue is mixed with water, and the process conditions of step (4) are repeated, the second leaching is performed, and the second immersion solution is obtained by filtration;

(6) Combine the first soaking solution and the second soaking solution, adjust the pH to 4.0 with calcium hydroxide with a concentration of 10% by mass, stir for 10 min, and neutralize to 7.0 with sodium hydroxide with a concentration of 10% by mass, fully Stir, stand still, take the precipitate and dry to obtain calcium magnesium hexaphosphate, and the supernatant is used to produce calcium sulfate;

(7) The filter residue obtained from the second leaching is placed in the extraction tank, soaked in clean water, and the solid-to-liquid mass ratio is kept at 1:2, stirred every 30 minutes, leached for 12 hours, and filtered to obtain the third immersion liquid and the third leaching residue. The soaking liquid is reserved, mainly used as supplementary water for the first and second soaking in the next extraction, and the residue of the third soaking is used for feed or extraction of solanesol.

The purity of the nicotine obtained in this example is 65%, and the purity reaches 98% through further refining, and the extraction rate of nicotine is 79%; the purity of the obtained inositol calcium magnesium hexaphosphate is 80%, and the extraction rate is 4%.

Embodiment 2: The extraction method of extracting inositol calcium magnesium hexaphosphate and co-producing nicotine from tobacco waste, the specific operation is as follows:

(1) Collect the tobacco stalks after harvesting tobacco leaves by tobacco farmers and crush them into tobacco stalk fragments with a length of less than 3 mm and a diameter of less than 1 mm;

(2) Take 100kg of tobacco stalk scraps, put them in the soaking tank, add 350kg of hot water at 70°C, adjust the pH to 5.2 with 90% industrial sulfuric acid, keep the soaking temperature at 70°C, and add acid to keep the soaking pH at 5.2 , stirred once every 10 minutes, soaked for 3 hours, then introduced water vapor, raised the soaking temperature to 85°C and kept it constant, kept the pH 5.2, extracted for 1 hour, filtered, and the filtrate was used for later use; repeat the above steps with the filter residue as raw material , carry out secondary extraction, merge twice to extract filtrate, and filter residue is standby; Fully stir filtrate, adjust pH to be 7.0, cool down;

(3) Add chloroform to the neutralized filtrate for extraction, the addition amount is 120 kg, take the extract phase and recover chloroform to obtain nicotine sulfate, and use the raffinate phase for later use;

(4) The raffinate obtained after extracting nicotine is combined with the filter residue, and the three immersion liquid produced in Example 1 is added to keep the solid-liquid mass ratio at 1:3, fully stirred, and adjusted with industrial sulfuric acid with a mass percentage concentration of 90%. The pH is 2.5 and remains unchanged, the leaching temperature is 25°C, leaching for 3 hours, stirring once every 15 minutes;

(5) Filtration, the filtrate is the first immersion solution for later use, the filter residue is mixed with the third immersion solution produced in Example 1, the process conditions of step (4) are repeated, the second leaching is performed, and the second immersion solution is obtained by filtration;

(6) Combine the first soaking solution and the second soaking solution, adjust the pH to 4.0 with calcium hydroxide with a concentration of 10% by mass, stir for 10 min, and neutralize to 7.0 with sodium hydroxide with a concentration of 10% by mass, fully Stir, stand still, take the precipitate and dry to obtain calcium magnesium hexaphosphate, and the supernatant is used to produce calcium sulfate;

(7) The filter residue obtained from the second leaching is placed in the extraction tank, soaked in clean water, and the solid-to-liquid mass ratio is kept at 1:2, stirred every 30 minutes, leached for 12 hours, and filtered to obtain the third immersion liquid and the third leaching residue. The soaking liquid is reserved, mainly used as supplementary water for the first and second soaking in the next extraction, and the residue of the third soaking is used for feed or extraction of solanesol.

The purity of the nicotine obtained in this example is 60%, and the purity reaches 96% through further refining, and the nicotine extraction rate is 75%; the obtained inositol calcium magnesium hexaphosphate has a purity of 77%, and the extraction rate is 2%.

Embodiment 3: The extraction method of extracting inositol hexaphosphate calcium magnesium hexaphosphate and co-producing nicotine from tobacco waste, the specific operation is as follows:

(1) Collect the remaining tobacco leaves after the tobacco farmers harvest the tobacco leaves and crush them into pieces of tobacco leaves less than 3 mm in length;

(2) Take 150kg of tobacco leaf fragments, put them in the soaking tank, add 500kg of hot water at 65°C, adjust the pH to 6.0 with 90% industrial sulfuric acid, keep the soaking temperature at 65°C, add acid to keep the soaking pH at 6.0, Stir once every 15 minutes, soak for 3.5 hours, then pass in steam, raise the soaking temperature to 90°C and keep it constant, keep the pH at 6.0, extract for 1.5 hours, filter, and use the filtrate for later use; repeat the above steps with the filter residue as raw material , carry out secondary extraction, merge two times to extract filtrate, and filter residue is standby; Fully stir filtrate, adjust pH to be 6.0, cool down;

(3) Add chloroform to the neutralized filtrate for extraction, the addition amount is 120kg, take the extract phase and recover chloroform to obtain nicotine sulfate, and use the raffinate phase for later use;

(4) Combine the raffinate and filter residue obtained after extracting nicotine, add water or three immersion liquids, keep the solid-liquid mass ratio at 1:4, stir well, adjust the pH to 2.0 with industrial sulfuric acid with a mass percentage concentration of 90% and Keep it unchanged, the extraction temperature is 25°C, extract for 2 hours, and stir once every 12 minutes;

(5) Filtration, the filtrate is the first immersion solution for later use, the filter residue is mixed with the third immersion solution produced in Example 2, the process conditions of step (4) are repeated, the secondary leaching is performed, and the second immersion solution is obtained by filtration;

(6) Combine the primary immersion liquid and the secondary immersion liquid, adjust the pH to 4.5 with calcium hydroxide with a concentration of 15% by mass, stir for 15 min, and neutralize with sodium hydroxide with a concentration of 15% by mass until the pH is 6.5 , fully stirred, allowed to stand, and the precipitate was dried to obtain inositol calcium magnesium hexaphosphate, and the supernatant was used to produce calcium sulfate;

(7) Put the filter residue obtained from the second leaching into the leaching tank, add clear water to soak, keep the solid-liquid mass ratio at 1:3, stir once every 40 minutes, leaching for 13 hours, and filter to obtain the third immersion liquid and the third leaching residue. The soaking liquid is reserved, mainly used as supplementary water for the first and second soaking in the next extraction, and the residue of the third soaking is used for feed or extraction of solanesol.

The purity of the nicotine obtained in this example was 58%, and the purity reached 97% through further refining, and the extraction rate of nicotine was 78%; the purity of the obtained inositol calcium magnesium hexaphosphate was 79%, and the extraction rate was 3%.

Embodiment 4: The extraction method of extracting inositol calcium magnesium hexaphosphate and co-producing nicotine from tobacco waste, the specific operation is as follows:

(1) Collect the fireworks after the tobacco farmers harvest the tobacco leaves and crush them to the fireworks fragments with a length of less than 3 mm;

(2) Take 200kg of fireworks scraps, put them in the soaking tank, add 600kg of hot water at 60°C, adjust the pH to 5.5 with industrial sulfuric acid with a concentration of 90% by mass, keep the soaking temperature at 60°C, add acid to keep soaking The pH is 5.5, stir once every 12 minutes, soak for 4 hours, then pass in water vapor, raise the soaking temperature to 88°C and keep it constant, keep the pH 5.5 unchanged, extract for 1.4 hours, filter, and the filtrate is used for later use; the filter residue is used as raw material Repeat the above operation steps, carry out the second extraction, combine the two extraction filtrates, and filter the residue for later use; fully stir the filtrate, adjust the pH to 6.5, and cool;

(3) Add chloroform to the neutralized filtrate for extraction, the addition amount is 150 kg, take the extract phase and recover chloroform to obtain nicotine sulfate, and use the raffinate phase for later use;

(4) Combine the raffinate phase obtained after extracting nicotine with the filter residue, add water, keep the solid-to-liquid mass ratio at 1:5, stir well, adjust the pH to 3.0 with industrial sulfuric acid with a mass percentage concentration of 90% and keep it unchanged, The extraction temperature is 30°C, the extraction time is 2.5 hours, and stirring is performed every 10 minutes;

(5) Filtration, the filtrate is the first immersion solution for later use, the filter residue is mixed with water, and the process conditions of step (4) are repeated, the second leaching is performed, and the second immersion solution is obtained by filtration;

(6) Combine the first soaking solution and the second soaking solution, adjust the pH to 4.0 with calcium hydroxide with a concentration of 12% by mass, stir for 12 minutes, and neutralize it to 7.0 with sodium hydroxide with a concentration of 10% by mass, fully Stir, stand still, take the precipitate and dry to obtain calcium magnesium hexaphosphate, and the supernatant is used to produce calcium sulfate;

(7) Put the filter residue obtained from the second leaching into the leaching tank, soak it in clean water, keep the solid-liquid mass ratio at 1:2.5, stir once every 60 minutes, leaching for 15 hours, and filter to obtain the third immersion liquid and the third leaching residue. The soaking liquid is reserved, mainly used as supplementary water for the first and second soaking in the next extraction, and the residue of the third soaking is used for feed or extraction of solanesol.

The purity of the nicotine obtained in this example is 50%, and the purity reaches 98% through further refining, and the extraction rate of nicotine is 48%; the purity of the obtained inositol calcium magnesium hexaphosphate is 65%, and the extraction rate is 1.8%.

Claims (1)

1. an extracting method that extracts inositol hexaphosphate calcium magnesium co-production nicotine from tobacco waste, is characterized in that carrying out as follows: A. Extract nicotine (1) Collect tobacco roots, residual tobacco leaves, tobacco stalks or fireworks after harvesting tobacco leaves, and crush them into tobacco scraps with a length of less than 3 mm, and set them aside; (2) Take 100-200 kg of tobacco scraps and add them to 300-600 kg of hot water at 60-70°C and mix them evenly, adjust the pH of the mixture to 5.0-6.0, soak for 3-4 hours, keep the soaking temperature at 60-70°C, add acid Keep the soaking pH at 5.0-6.0, stir once every 10-15 minutes; add water vapor, raise the soaking temperature to 85-90°C and keep it unchanged, keep the pH 5.0-6.0 unchanged, extract for 1-1.5 hours, filter , the filtrate is standby; take the filter residue as the raw material and repeat the above operation steps, carry out secondary extraction, combine the filtrate extracted twice, and the filter residue is standby; fully stir the filtrate, adjust the pH to 6.0-7.0, and cool; (3) Add chloroform to the filtrate in step (2) for extraction, the addition amount is 100-150 kg, take the extract phase and recover the chloroform to obtain nicotine sulfate, and use the raffinate phase for later use; B. Inositol Hexaphosphate Calcium Magnesium Extraction (1) Primary immersion: the raffinate phase obtained after extracting nicotine is combined with the filter residue, and water or the third immersion solution in the subsequent process is added. The mass ratio of solid to liquid is 1:3~1:5, and the mixture is fully stirred to adjust the pH of the mixture. 2.0-3.0 and keep it unchanged, maintain the extraction temperature at 25-30°C, extract for 2-3 hours, and stir once every 10-15 minutes; (2) Second immersion: the mixture is filtered, the filtrate is the first immersion solution for later use, the filter residue is mixed with water or the third immersion solution, the process conditions of step (1) are repeated, the second leaching is performed, and the second immersion solution is obtained by filtration; (3) Production of inositol calcium magnesium hexaphosphate: Combine the first soaking solution and the second soaking solution, adjust the pH to 4.0-4.5 with calcium hydroxide with a concentration of 10%-15% by mass, stir for 10-15 minutes, and use Sodium hydroxide with a mass percentage concentration of 10% to 15% neutralizes the pH value of 6.5 to 7.0, fully stirs, stands still, takes the precipitate and dries to obtain inositol calcium magnesium hexaphosphate, and the supernatant is used to produce calcium sulfate ; (4) Three leaching: the filter residue obtained from the second leaching is placed in the leaching tank, soaked in clean water, the solid-liquid mass ratio is 1:2-1:3, leaching for 12-15 hours, stirring once every 30-60 minutes, and filtering. Obtain the third immersion liquid and the third leaching residue, the third immersion liquid is for use, mainly used to supplement the extraction water for the first immersion and the second immersion, and the third immersion residue is used as feed or extraction of solanesol; Wherein the pH value of the mixture is adjusted with the industrial sulfuric acid with a mass percent concentration of 90%.