CN107335401B - Method for removing pesticide residues in traditional Chinese medicine ointment formula by using inorganic adsorbent - Google Patents
Method for removing pesticide residues in traditional Chinese medicine ointment formula by using inorganic adsorbent Download PDFInfo
- Publication number
- CN107335401B CN107335401B CN201611088410.1A CN201611088410A CN107335401B CN 107335401 B CN107335401 B CN 107335401B CN 201611088410 A CN201611088410 A CN 201611088410A CN 107335401 B CN107335401 B CN 107335401B
- Authority
- CN
- China
- Prior art keywords
- medicinal materials
- inorganic adsorbent
- paste
- time
- pesticide residues
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The invention relates to a method for removing pesticide residues in a traditional Chinese medicine ointment formula by using an inorganic adsorbent, which comprises the following steps: (1) preparing inorganic materials such as ZSM-5 molecular sieve, magnesium aluminum hydrotalcite and the like to obtain an inorganic adsorbent; (2) extracting rare medicinal materials and common medicinal materials in the paste formula separately, crushing respectively, adding water, adding inorganic adsorbent, heating, stirring for extraction, filtering to obtain extractive solution, and extracting the residue again; (3) mixing the extractive solutions of rare and common medicinal materials, placing in a low-pressure concentrating device, heating, concentrating, adding into paste, and making into ointment. The method is simple and convenient, and is more suitable for the production process of the paste of one person and one party; the inorganic adsorbent used in the invention is safe to use, can selectively remove pesticide residues in the paste formula extracting solution, and does not adsorb active ingredients of the paste formula; compared with the traditional paste preparation method, the extraction time is shortened, the concentration temperature is reduced, and the heat-sensitive active ingredients are better reserved.
Description
Technical Field
The invention belongs to the field of removing exogenous harmful substances in traditional Chinese medicines and Chinese patent medicines, and particularly relates to a method for removing pesticide residues in a traditional Chinese medicine ointment formula by using an inorganic adsorbent.
Background
The traditional Chinese medicine ointment formula, also called ointment and soft extract, is a traditional Chinese medicine dosage form which is popular in ancient China and is eaten in an oral taking mode. The traditional Chinese medicine ointment formula can not only nourish physique, but also is an effective means for treating chronic diseases. With the rapid development of economy in China, urban sub-health people are increasing day by day, the population aging is more serious, chronic patients in China are increasing continuously, more than 3 hundred million of currently diagnosed chronic patients are diagnosed, and the trend of the patients to be younger is presented. Therefore, the ointment formula is more and more favored by people, and the number of people who take the ointment formula for nourishing in winter is increased year by year. The traditional Chinese medicine ointment formula is very common in Jiang, Zhe and Shanghai in China and gradually develops to other areas in China. In addition, the ointment formula is more vigorous and lively in harbor, Australia, Taiwan and southeast Asia in China.
However, some common herbs in the ointment formula are mostly planted artificially, such as ginseng, astragalus, medlar, liquorice and the like, and often contain various pesticide residues. (Kanghei et al, discussion of pesticide residue research status of Chinese medicinal materials [ J ]. Chinese medicine J2016, 41(02): 155-159). During the preparation process of the ointment formula, pesticide residues contained in the medicinal materials can enter the ointment formula, so that the ointment formula is polluted. On the other hand, the ointment needs to be taken for a long time (generally 2-3 months); if the ointment formulation polluted by pesticide residues is taken for a long time, immeasurable potential harm exists on the body of a user.
At present, no literature report and relevant patent publications for removing pesticide residues in the traditional Chinese medicine ointment formula exist in China. Only a few patents relate to the removal of pesticide residues from a single traditional Chinese medicine or traditional Chinese medicine extract, and can be classified into the following four categories according to the removal principle: (1) supercritical CO2An extraction method comprises the following steps: chinese patents CN1319545C and CN103305343B utilize supercritical CO2Organic chlorine pesticide and organic phosphorus pesticide in the ginseng and citrus essential oil are respectively removed by extraction. (2) Subcritical fluid extraction method: chinese patent CN103549236A uses dry cleaning solvent propane to remove pesticide residue attached on plant surface. (3) Macroporous resin adsorption method: chinese patents CN103739731A and CN104490966A respectively use macroporous resin adsorption columns to remove pesticide residues in lentinan extracts and ginseng stem leaf extracts. (4) Activated carbon adsorption method: chinese patents CN101731493A and CN101711777B reduce pesticide residue in folium Ginkgo extract and Ganoderma extract by activated carbon adsorption.
The traditional Chinese medicine ointment formula is different according to the constitution of patientsThe medicine is changed to be customized by a hospital pharmacy, and the amount of each batch of medicine is not more than 5 kg. Supercritical CO2The extraction method and the subcritical fluid extraction method need high-pressure equipment, and are not convenient to popularize and use. The paste formula is decocted by water, macroporous resin, active carbon and the like are nonpolar, and if the macroporous resin, the active carbon and the like are directly used for adsorbing and removing pesticide residues in the paste formula extracting solution, the loss of active ingredients can be caused. Therefore, the selective adsorbent capable of effectively removing pesticide residues in the paste during the decoction process of the paste is urgently needed to be developed, and the pesticide residues are removed while the effective components in the paste are not adsorbed, so that the pesticide residues in the paste are reduced to be within the safety limit value.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for removing pesticide residues in a traditional Chinese medicine ointment formula by using an inorganic adsorbent.
The purpose of the invention can be realized by the following technical scheme:
a method for removing pesticide residues in a traditional Chinese medicine ointment formula by using an inorganic adsorbent comprises the following steps:
(1) preparing an inorganic adsorbent;
(2) separately extracting rare medicinal materials and common medicinal materials in the paste formula, crushing by using a crusher respectively, adding water, adding the inorganic adsorbent in the step (1), placing on a water bath heating device, heating, stirring for extraction, filtering to obtain an extracting solution, and extracting the dregs of a decoction again;
(3) mixing the rare medicinal material extract and the common medicinal material extract in the step (2), placing in a low-pressure concentration device, heating, concentrating, adding into paste, and making into paste.
The preparation of the inorganic adsorbent in the step (1) specifically comprises the following steps:
(1-1) activating ZSM-5 molecular sieve raw powder, and cooling to obtain ZSM-5 molecular sieve activated powder;
(1-2) activating the raw powder of the magnesium-aluminum hydrotalcite, and cooling to obtain activated powder of the magnesium-aluminum hydrotalcite;
(1-3) mixing ZSM-5 molecular sieve activated powder and magnesium aluminum hydrotalcite activated powder, adding a small amount of water and activated alumina as a binder, fully mixing, extruding into strips by using an extruder, activating, and storing in a dry environment for later use.
The silicon-aluminum ratio of the ZSM-5 molecular sieve in the step (1-1) is 5-50, and preferably 10-25.
In the step (1-3), the mass ratio of the ZSM-5 molecular sieve activated powder to the magnesium-aluminum hydrotalcite activated powder is (0.1-1) to (0.1-1), and the mass of the activated alumina is 1/5 of the sum of the mass of the ZSM-5 molecular sieve activated powder and the mass of the magnesium-aluminum hydrotalcite activated powder.
In the step (1-1), the ZSM-5 molecular sieve raw powder is activated for more than 1 hour under the condition of 250-450 ℃, and the preferred activation condition is as follows: activating for 2-4 hours at the temperature of 350-400 ℃;
in the step (1-2), the activation condition of the magnesium aluminum hydrotalcite raw powder is 250-400 ℃, the activation time is more than 1 hour, and the preferable activation condition is as follows: activating for 2-4 hours at the temperature of 350-400 ℃;
activating for more than 1 hour at 250-400 ℃ after the extrusion molding in the step (1-3), preferably: activating for 2-4 hours at the temperature of 350-400 ℃.
The rare medicinal materials comprise one or more of ginseng, red ginseng, pseudo-ginseng and lucid ganoderma; crushing the rare medicinal materials until the rare medicinal materials pass through a standard sieve mesh of 10 meshes; when the rare medicinal materials are extracted, the water amount is 15 liters/kg of the medicinal materials for the first time, the water amount is 14 liters/kg of the medicinal materials for the second time, 1/100-1/50 of the inorganic adsorbent in mass of the rare medicinal materials is added, the water bath heating temperature is 60-90 ℃, the optimal temperature is 70 ℃, and the water bath heating time is more than 1 hour, and the optimal time is 2-3 hours each time.
The common medicinal materials are medicinal materials except for rare medicinal materials, and are crushed to pass through a standard sieve mesh of 10 meshes; when the common medicinal materials are extracted, 10 liters of water per kilogram of the medicinal materials are added for the first time, 9 liters of water per kilogram of the medicinal materials are added for the second time, 1/50-1/20 of inorganic adsorbent in mass of the common medicinal materials are added, the water bath heating temperature is 60-100 ℃, the preferred temperature is 80 ℃, and the water bath heating time is more than 0.5 hour each time, and the preferred time is 1-2 hours.
The pesticide residue in the medicinal material extracting solution can be adsorbed and removed by the inorganic adsorbent, wherein the types and concentration ranges of the pesticide residue capable of being adsorbed and removed by the inorganic adsorbent comprise one or more of 0.005-1.0 mg/L of quintozene, 0.001-0.5 mg/L of total hexalium, 0.001-0.5 mg/L of total dichloro-diphenyl-trichloroethane, 0.005-1.0 mg/L of omethoate, 0.005-1.0 mg/L of methyl parathion, 0.005-1.0 mg/L of cypermethrin, 0.005-1.0 mg/L of fenvalerate and 0.005-1.0 mg/L of cyfluthrin.
The low-pressure concentration device is a rotary evaporator with a heating part and a vacuum pump part, the heating temperature is 40-80 ℃, and the vacuum degree of the rotary evaporator is 60-95 kPa; the volume of the concentrated solution is 1/10-1/5 of the volume of the extracting solution.
The paste is one or more of white sugar, xylitol, rock sugar and honey, and the dosage of the paste is 0.1-0.3 kg of the paste added in each liter of concentrated solution.
Compared with the prior technology for removing pesticide residues in single traditional Chinese medicinal materials or traditional Chinese medicinal extract and the traditional paste formula preparation process, the invention has the following advantages:
(1) the method is simple and convenient, and is more suitable for the production process of the paste formula of one person and one party. The formula of the traditional Chinese medicine ointment formula changes due to different constitutions of patients, and each batch of the traditional Chinese medicine ointment formula has a small quantity of medicinal materials and a large number of processing batches. Supercritical CO2The extraction method and the subcritical fluid extraction method need high-pressure equipment, and are not convenient to popularize. The method of the invention only needs to add the inorganic adsorbent along with the medicinal materials in the process of decocting the ointment formula, can achieve the effect of adsorbing and removing pesticide residues, and does not need to add any additional equipment.
(2) The main component of the adsorbent is an artificially synthesized inorganic porous material, the adsorbent is safe to use, can selectively remove pesticide residues in the paste extract, and basically does not adsorb active ingredients of the paste. The macroporous resin is a high molecular polymer and can be generally used only in an environment of lower than 40 ℃. When the use temperature is higher than 70 ℃, the macroporous resin can be degraded and release toxic substances. In addition, the macroporous resin and the activated carbon have macroporous structures>50nm) and is non-polar, so that the active ingredients in the plaster are easily adsorbed, and the curative effect of the plaster is influenced. The main components of the inorganic adsorbent are ZSM-5 molecular sieve and magnesium-aluminum water-soluble polymerAnd (4) stone. ZSM-5 molecular sieve is aluminosilicate component with molecular formula of Nan(H2O)16[AlnSi96-nO192](wherein n is<27). The Mg-Al hydrotalcite is layered bimetal oxide with molecular formula of Mg6Al2(OH)16CO3·4H2And O. The two materials can be safely used in the environment of room temperature to 100 ℃ without releasing toxic substances. In addition, the polarity of the ZSM-5 molecular sieve can be adjusted through the silica-alumina ratio, and when the silica-alumina ratio is 10-25, the polarity of the ZSM-5 molecular sieve is similar to that of pesticide molecules, so that the pesticide molecules in the paste formula extracting solution can be selectively adsorbed. The interlayer spacing of the magnesium-aluminum hydrotalcite is 0.4-0.8 nm, the size of the magnesium-aluminum hydrotalcite is similar to that of pesticide molecules, and the effective components in the paste formula are generally larger in molecular size (>2 nm). Therefore, the magnalium hydrotalcite can adsorb and remove pesticide molecules in the paste formula through size sieving.
(3) Compared with the traditional paste preparation method, the preparation method of the paste formula shortens the extraction time, reduces the concentration temperature and better retains the heat-sensitive active ingredients. In the preparation process of the traditional ointment formula, the medicinal materials are usually soaked for more than 8 hours and then decocted. According to the invention, the medicinal materials are directly decocted after being crushed, so that the soaking time is saved, and the powdered medicinal materials only need to be decocted for a short time. According to the invention, a low-pressure concentration technology is utilized, the heating temperature is lower by 40-80 ℃, the heat-sensitive active ingredients are favorably kept, and the time required by the concentration process is further shortened.
Detailed Description
The method for removing pesticide residue in the traditional Chinese medicine ointment formula by using the inorganic adsorbent comprises the following steps:
(1) preparing an inorganic adsorbent;
(2) separately extracting rare medicinal materials and common medicinal materials in the paste formula, crushing by using a crusher respectively, adding water, adding the inorganic adsorbent in the step (1), placing on a water bath heating device, heating, stirring for extraction, filtering to obtain an extracting solution, and extracting the dregs of a decoction again;
(3) mixing the rare medicinal material extract and the common medicinal material extract in the step (2), placing in a low-pressure concentration device, heating, concentrating, adding into paste, and making into paste.
The preparation of the inorganic adsorbent in the step (1) specifically comprises the following steps:
(1-1) activating ZSM-5 molecular sieve raw powder for more than 1 hour at 250-450 ℃, and cooling to obtain ZSM-5 molecular sieve activated powder; the preferable temperature is 350-400 ℃, the preferable time is 2-4 hours, wherein the silicon-aluminum ratio of the ZSM-5 molecular sieve is 5-50, and the preferable silicon-aluminum ratio is 10-25;
(1-2) activating the raw powder of the magnesium-aluminum hydrotalcite at 250-400 ℃ for more than 1 hour, and cooling to obtain activated powder of the magnesium-aluminum hydrotalcite; the preferred temperature is 350-400 ℃, and the preferred time is 2-4 hours;
(1-3) mixing ZSM-5 molecular sieve activated powder and magnesium-aluminum hydrotalcite activated powder, adding a small amount of water and activated alumina as a binder, wherein the mass ratio of the ZSM-5 molecular sieve activated powder to the magnesium-aluminum hydrotalcite activated powder is (0.1-1): 0.1-1), the mass of the activated alumina is 1/5 of the sum of the ZSM-5 molecular sieve activated powder and the magnesium-aluminum hydrotalcite activated powder, fully mixing, extruding and molding by using an extruder, activating at 250-400 ℃ for more than 1 hour, and storing in a dry environment for later use; the activation temperature is preferably 350-400 ℃, and the activation time is preferably 2-4 hours.
Wherein the rare medicinal materials comprise one or more of Ginseng radix, Ginseng radix Rubri, Notoginseng radix, and Ganoderma; crushing the rare medicinal materials until the rare medicinal materials pass through a standard sieve mesh of 10 meshes; when the rare medicinal materials are extracted, the water amount is 15 liters/kg of the medicinal materials for the first time, the water amount is 14 liters/kg of the medicinal materials for the second time, 1/100-1/50 of the inorganic adsorbent in mass of the rare medicinal materials is added, the water bath heating temperature is 60-90 ℃, the optimal temperature is 70 ℃, and the water bath heating time is more than 1 hour, and the optimal time is 2-3 hours each time.
The common medicinal materials are medicinal materials except for rare medicinal materials, and are crushed to pass through a standard sieve mesh of 10 meshes; when the common medicinal materials are extracted, 10 liters of water per kilogram of the medicinal materials are added for the first time, 9 liters of water per kilogram of the medicinal materials are added for the second time, 1/50-1/20 of inorganic adsorbent in mass of the common medicinal materials are added, the water bath heating temperature is 60-100 ℃, the preferred temperature is 80 ℃, and the water bath heating time is more than 0.5 hour each time, and the preferred time is 1-2 hours.
The low-pressure concentration device is a rotary evaporator with a heating part and a vacuum pump part, the heating temperature is 40-80 ℃, and the vacuum degree of the rotary evaporator is 60-95 kPa; the volume of the concentrated solution is 1/10-1/5 of the volume of the extracting solution.
The paste is one or more of white sugar, xylitol, rock sugar and honey, and the dosage of the paste is 0.1-0.3 kg of paste added per liter of concentrated solution.
The types and concentration ranges of the pesticide residues which can be adsorbed and removed by the inorganic adsorbent comprise one or more of quintozene (0.005-1.0 mg/L), total hexalium (0.001-0.5 mg/L), total dichlorodiphenyl trichloroethane (0.001-0.5 mg/L), omethoate (0.005-1.0 mg/L), methyl parathion (0.005-1.0 mg/L), cypermethrin (0.005-1.0 mg/L), fenvalerate (0.005-1.0 mg/L) and cyfluthrin (0.005-1.0 mg/L).
The present invention will be described in detail with reference to specific examples.
Example 1 preparation of paste of Ginseng and Atractylodis rhizoma
Preparation of inorganic adsorbent: 0.1 kg of ZSM-5 molecular sieve raw powder (the ratio of ZSM-5 to silica to alumina is 10.3) is put into a muffle furnace at 250 ℃ to be activated for 4 hours, and then the raw powder is taken out and put into a dryer to be cooled; 1 kg of magnesium-aluminum hydrotalcite raw powder is put in a muffle furnace at 400 ℃ for activation for 2 hours, taken out and put in a dryer for cooling; adding 0.22 kg of activated alumina into the two materials, uniformly stirring, adding a small amount of water to enable the surface of the powder to have a moist feeling, extruding the mixture into a strip shape with the thickness of 1.8 mm by using an extruder, activating the strip shape in a muffle furnace at the temperature of 250 ℃ for 4 hours, taking out the strip shape, and placing the strip shape in a dryer for cooling for later use.
Extracting ginseng and atractylodes paste: the prescription of the Shenshu ointment is 120 g of ginseng (without reed), 240 g of largehead atractylodes rhizome (fried with soil), 120 g of fried coix seed, 90 g of lotus seed (peeled and without core), 90 g of astragalus (fried with honey), 60 g of white poria (peeled), 60 g of medicated leaven (fried), 9 g of rhizoma alismatis and 9 g of honey-fried licorice root. Wherein Ginseng radix is a rare medicinal material, and needs to be extracted separately, and the other medicinal materials are common medicinal materials, and can be extracted together. Crushing 120 g of ginseng by using a food crusher until the ginseng passes through a standard sieve of 10 meshes, adding 1.8 liters of water, adding 1.2 g of inorganic adsorbent, heating in a water bath at 60 ℃, and stirring and extracting for 3 hours; filtering to obtain about 1.6L filtrate; adding 1.68L water into the filter residue, extracting again, heating to 60 deg.C in water bath, stirring and extracting for 3 hr, and filtering to obtain about 1.5L filtrate; the 3.1 liters of extract were obtained by mixing. 678 g of the other eight common medicinal materials are respectively crushed and sieved by a 10-mesh sieve, and then the mixture is mixed, 6.8 liters of water is added, 13.6 grams of inorganic adsorbent is added, the mixture is heated in a water bath at 60 ℃, and the mixture is stirred and extracted for 2 hours; filtering to obtain 5.3L filtrate; adding 6.1L water into the filter residue for extraction again, heating the filter residue to 60 ℃ in a water bath, stirring and extracting for 2 hours, and filtering to obtain about 5.1L filtrate; the extracts were combined to give 10.4 liters. Mixing the Ginseng radix extractive solution with other medicinal materials extractive solution to obtain 13.5L extractive solution.
Concentrating and forming ginseng and atractylodes paste: adding 13.5 liters of extract into a rotary evaporator in batches, heating the extract at the temperature of 40 ℃ and keeping the vacuum degree at 95 kPa; concentrating to 1.35L, adding 0.135 kg white sugar while hot, stirring thoroughly to dissolve, and forming into viscous paste.
According to 2341, pesticide residue determination method in the fourth volume of the pharmacopoeia 2015 edition, 8 pesticide residues such as quintozene, total hexalium, total dichlorodiphenyl trichloroethane, omethoate, methyl parathion, cypermethrin, fenvalerate, cyfluthrin and the like in the Shenshu ointment are determined by gas chromatography-tandem mass spectrometry and are not detected, and the determination results are shown in table 1. Compared with comparative example 1, the inorganic adsorbent used is shown to have a better removal effect on the 8 pesticide residues. Compared with comparative example 2, the inorganic adsorbent used is shown to have better effect on removing pesticide residues than activated carbon.
According to the ginseng in the first volume of the Chinese pharmacopoeia 2015 edition, the content of the total ginsenoside in the ginseng-atractylodes paste is 521 mg/L measured by using a high performance liquid chromatography, compared with the comparative example 1, the loss of the total ginsenoside caused by the used inorganic adsorbent is not shown, compared with the comparative example 2, the loss of the effective components of the medicine caused by the used inorganic adsorbent is shown, and the loss of the effective components of the medicine caused by the active carbon is shown.
Comparative example 1 preparation of paste of ginseng and atractylodes rhizome by conventional method
Extracting ginseng and atractylodes paste: the prescription of the Shenshu ointment is the same as that in example 1. Wherein Ginseng radix is extracted separately, and the other materials are combined and extracted together. Slicing 120 g of ginseng, adding 5 liters of water, soaking for 8 hours, boiling with big fire, and decocting with slow fire for 4 hours; about 3 liters of extract was obtained by filtration. 678 g of the other eight medicinal materials are cut or cut, mixed, added with 15 liters of water, soaked for 8 hours, boiled by big fire and decocted by slow fire for 4 hours; the filtrate was filtered to obtain about 10 liters of extract. Mixing the Ginseng radix extractive solution with other medicinal materials extractive solution to obtain 13L extractive solution.
Concentrating and forming ginseng and atractylodes paste: concentrating 13L of the extractive solution with slow fire to 1.35L, adding 0.135 kg of white sugar while hot, stirring thoroughly to dissolve, and making into viscous paste.
According to 2341, pesticide residue determination method, of China pharmacopoeia 2015 edition, in the fourth volume, 8 pesticide residues such as quintozene, total hexalium, total dichlorodiphenyl trichloroethane, omethoate, methyl parathion, cypermethrin, fenvalerate, cyfluthrin and the like in Shenshu ointment are determined by gas chromatography-tandem mass spectrometry. Compared with example 1, 8 pesticide residues in the cream formula are detected, and specific data are shown in table 1.
The content of total ginsenoside in the ginseng extract is 440 mg/L measured by high performance liquid chromatography according to ginseng in the first volume of the Chinese pharmacopoeia 2015 edition compared with the example 1, the content of total ginsenoside is reduced, probably caused by incomplete extraction of ginsenoside in the flaky ginseng and longer heating time.
Comparative example 2 preparation of ginseng extract using activated carbon as adsorbent
The extraction, concentration and ointment formation process of the ginseng and atractylodes paste are the same as the example 1. Only the inorganic adsorbent is changed into medical powdered activated carbon with equal mass.
According to 2341, pesticide residue determination method, of China pharmacopoeia 2015 edition, in the fourth volume, 8 pesticide residues such as quintozene, total hexalium, total dichlorodiphenyl trichloroethane, omethoate, methyl parathion, cypermethrin, fenvalerate, cyfluthrin and the like in Shenshu ointment are determined by gas chromatography-tandem mass spectrometry. The results show that the activated carbon has a certain adsorption-removal effect on 8 kinds of pesticide residues, but the adsorption-removal effect is inferior to that of the inorganic adsorbent used in example 1, as compared with example 1 and comparative example 1, and the specific data are shown in table 1.
According to ginseng in the first volume of the 'Chinese pharmacopoeia 2015 edition', the content of total ginsenoside in the ginseng-atractylodes paste is measured to be 461 mg/L by using high performance liquid chromatography, compared with the example 1, the content of total ginsenoside is reduced, which shows that active carbon can cause the loss of effective ingredients of traditional Chinese medicines.
TABLE 1 test results
EXAMPLE 2 preparation of paste containing Ginseng, Poria and Atractylodis rhizoma
Preparation of inorganic adsorbent: 1 kg of ZSM-5 molecular sieve raw powder (the ratio of ZSM-5 to silica to alumina is 24.6) is put in a muffle furnace at 450 ℃ to be activated for 2 hours, and then the raw powder is taken out and put in a dryer to be cooled; putting 0.1 kg of magnesium-aluminum hydrotalcite raw powder into a muffle furnace at 250 ℃ for activation for 4 hours, taking out and putting into a dryer for cooling; adding 0.22 kg of activated alumina into the two materials, uniformly stirring, adding a small amount of water to enable the surface of the powder to have a moist feeling, extruding the mixture into a strip shape with the thickness of 1.8 mm by using an extruder, activating the strip shape in a muffle furnace at the temperature of 400 ℃ for 2 hours, taking out the strip shape, and placing the strip shape in a dryer for cooling for later use.
Extracting ginseng, poria cocos and bighead atractylodes rhizome paste: the plaster formula of the ginseng, poria cocos and white atractylodes rhizome comprises 200 g of ginseng, 200 g of white poria cocos, 200 g of liquorice, 200 g of white atractylodes rhizome, 200 g of Chinese yam, 150 g of white hyacinth bean (soaked in ginger juice and slightly fried), 100 g of lotus seed meat, 100 g of coix seed, 100 g of fructus amomi and 100 g of platycodon grandiflorum. Pulverizing 200 g of ginseng to pass through a 10-mesh sieve, adding 3 liters of water, adding 4 g of inorganic adsorbent, heating in a water bath at 90 ℃, and stirring and extracting for 2 hours; filtering to obtain 2.6 liters of filtrate; adding 2.8L water into the filter residue for extraction again, heating the filter residue to 90 ℃ in a water bath, stirring and extracting for 2 hours, and filtering to obtain about 2.5L filtrate; the 5.1 liters of extract were obtained by mixing. Pulverizing 1350 g of the rest nine medicinal materials, sieving with a 10-mesh sieve, adding 13.5L of water, adding 67.5 g of inorganic adsorbent, heating in water bath at 100 deg.C, stirring, and extracting for 1 hr; filtering to obtain 10.5L filtrate; adding 12.2L water into the filter residue, extracting again, heating in water bath at 100 deg.C, stirring and extracting for 1 hr, and filtering to obtain 10L filtrate; mixing to obtain 20.5L extractive solution. The two extracts were mixed to obtain 25.6 liters of extract.
Concentrating and forming ginseng, poria cocos and bighead atractylodes rhizome paste: adding 25.6 liters of extract into a rotary evaporator in batches, heating to 80 ℃, and keeping the vacuum degree at 60 kPa; concentrating to 5.1L, adding 1.53 kg of crystal sugar while the mixture is hot, and fully stirring and dissolving to form thick ginseng, poria cocos and bighead atractylodes rhizome paste.
According to 2341, pesticide residue determination method in the fourth volume of the book of Chinese pharmacopoeia 2015 edition, 8 pesticide residues such as quintozene, total hexalium, total dichlorodiphenyl trichloroethane, omethoate, methyl parathion, cypermethrin, fenvalerate, cyfluthrin and the like in the Shenling Baizhu ointment are determined by gas chromatography-tandem mass spectrometry, and are not detected, and the results are shown in table 2.
According to the ginseng in the first volume of the Chinese pharmacopoeia 2015 edition, the content of total ginsenoside in the Shenling Baizhu paste is 268 mg/L by utilizing high performance liquid chromatography, compared with the comparative example 3, the inorganic adsorbent is proved not to adsorb the effective ingredients of the medicine, and the D101 macroporous resin can cause the loss of the effective ingredients of the medicine.
Comparative example 3 preparation of Ginseng, poria and Atractylodis rhizoma paste with D101 macroporous resin as adsorbent
The extraction, concentration and formation process of the Shenling Baizhu plaster are the same as the example 2. Only the inorganic adsorbent used was changed to D101 macroporous resin of equal mass (based on the dry weight of the macroporous resin).
According to 2341, pesticide residue determination method in the fourth volume of China pharmacopoeia 2015 edition, 8 pesticide residues such as quintozene, total hexalium, total dichloro-diphenyl-trichloroethane, omethoate, methyl parathion, cypermethrin, fenvalerate, cyfluthrin and the like in the Shenling Baizhu ointment are determined by gas chromatography-tandem mass spectrometry, and three pesticide residues are detected. Compared with example 2, the D101 macroporous resin is proved to have inferior effect on removing pesticide residue to the inorganic adsorbent, and specific data are shown in Table 2.
According to the ginseng in the first volume of the Chinese pharmacopoeia 2015 edition, the content of the total ginsenoside in the Shenling Baizhu paste is measured to be 212 mg/L by utilizing high performance liquid chromatography, compared with the example 2, the D101 macroporous resin can cause the loss of the effective ingredients of the medicine.
TABLE 2 test results
EXAMPLE 3 preparation of Atractylodis rhizoma ointment
Preparation of inorganic adsorbent: 0.5 kg of ZSM-5 molecular sieve raw powder (the ratio of silicon to aluminum is 19.6) is put into a muffle furnace at 350 ℃ for activation for 1 hour, taken out and put into a dryer for cooling; putting 0.5 kg of magnesium-aluminum hydrotalcite raw powder into a muffle furnace at 350 ℃ for activation for 1 hour, taking out and putting into a dryer for cooling; adding 0.2 kg of activated alumina into the two materials, uniformly stirring, adding a small amount of water to enable the surface of the powder to have a moist feeling, extruding the mixture into a thin strip shape with the thickness of 1.8 mm by using an extruder, activating the thin strip shape in a muffle furnace at the temperature of 350 ℃ for 1 hour, taking out the thin strip shape, and placing the thin strip shape in a dryer for cooling for later use.
Extracting the bighead atractylodes rhizome paste: the prescription of the white atractylodes rhizome paste is 500 g of white atractylodes rhizome and 120 g of dried orange peel. Both of them are common medicinal materials. Pulverizing Atractylodis rhizoma and pericarpium Citri Tangerinae respectively, and sieving with 10 mesh sieve. Mixing the two medicinal granules, adding 6.2L of water, adding 25 g of inorganic adsorbent, heating in water bath at 80 deg.C, stirring and extracting for 0.5 hr; filtering to obtain 5 liters of filtrate; adding 5.6L water into the filter residue, extracting again, heating to 80 deg.C in water bath, stirring and extracting for 0.5 hr, and filtering to obtain about 4.8L filtrate; the 9.8 liters of extract were obtained by mixing.
Concentrating and forming the white atractylodes rhizome paste: adding 9.8L of the extract into a rotary evaporator in batches, heating to 60 ℃ and keeping the vacuum degree at 80 kPa; concentrating to 1.9L, adding 0.57 kg xylitol while the solution is hot, and fully stirring and dissolving to form viscous rhizoma Atractylodis Macrocephalae paste.
According to 2341, pesticide residue determination method in the fourth volume of the pharmacopoeia 2015 edition, 8 pesticide residues such as quintozene, total hexachlorobenzene, total dichlorodiphenyl trichloroethane, omethoate, methyl parathion, cypermethrin, fenvalerate, cyfluthrin and the like are determined by gas chromatography-tandem mass spectrometry and are not detected.
EXAMPLE 4 preparation of wolfberry paste
Preparation of inorganic adsorbent: 0.5 kg of ZSM-5 molecular sieve raw powder (the silica-alumina ratio is 15.2) is put into a 400 ℃ muffle furnace to be activated for 1 hour, taken out and put into a dryer to be cooled; putting 0.5 kg of magnesium-aluminum hydrotalcite raw powder into a muffle furnace at 400 ℃ for activation for 1 hour, taking out and putting into a dryer for cooling; adding 0.2 kg of activated alumina into the two materials, uniformly stirring, adding a small amount of water to enable the surface of the powder to have a moist feeling, extruding the mixture into a strip shape with the thickness of 1.8 mm by using an extruder, activating the strip shape in a muffle furnace at the temperature of 400 ℃ for 1 hour, taking out the strip shape, and placing the strip shape in a dryer for cooling for later use.
And (3) extraction of the Chinese wolfberry fruit paste: the prescription of the medlar ointment is 1000 g of medlar and 60 g of schisandra chinensis. The medlar and the schisandra are common medicinal materials. Pulverizing fructus Lycii and fructus Schisandrae chinensis respectively, and sieving with 10 mesh sieve. Mixing the two, adding 10.6L of water, adding 30 g of inorganic adsorbent, heating in water bath at 80 ℃, and stirring and extracting for 1.5 hours; filtering to obtain 8.5L filtrate; adding 9.5L water into the filter residue for extraction again, heating to 80 deg.C in water bath, stirring for extraction for 1.5 hr, and filtering to obtain about 8.5L filtrate; 17 liters of extract are obtained after combination.
Concentrating and forming the medlar paste: adding 17 liters of extract into a rotary evaporator in batches, heating to 60 ℃, and keeping the vacuum degree at 80 kPa; concentrating to 2L, adding 0.4 kg of crystal sugar while the mixture is hot, and fully stirring and dissolving to form viscous wolfberry fruit paste.
According to 2341, pesticide residue determination method in the fourth volume of the pharmacopoeia 2015 edition, 8 pesticide residues such as quintozene, total hexachlorobenzene, total dichlorodiphenyl trichloroethane, omethoate, methyl parathion, cypermethrin, fenvalerate, cyfluthrin and the like are determined by gas chromatography-tandem mass spectrometry and are not detected.
EXAMPLE 5 preparation of two pastes
Preparation of inorganic adsorbent: 0.5 kg of ZSM-5 molecular sieve raw powder is put into a muffle furnace at 400 ℃ to be activated for 1 hour, taken out and put into a dryer to be cooled; putting 0.5 kg of magnesium-aluminum hydrotalcite raw powder into a muffle furnace at 400 ℃ for activation for 1 hour, taking out and putting into a dryer for cooling; adding 0.2 kg of activated alumina into the two materials, uniformly stirring, adding a small amount of water to enable the surface of the powder to have a moist feeling, extruding the mixture into a strip shape with the thickness of 1.8 mm by using an extruder, activating the strip shape in a muffle furnace at the temperature of 400 ℃ for 1 hour, taking out the strip shape, and placing the strip shape in a dryer for cooling for later use.
Extracting two kinds of ointment: the prescription of the two kinds of ointment is 250 g of ginseng and 250 g of prepared rhizome of rehmannia. Pulverizing 250 g of ginseng, sieving with a 10-mesh sieve, adding 3.75 l of water, adding 5 g of inorganic adsorbent, heating in a water bath at 70 ℃, and extracting for 1 hour; filtering to obtain 3.1L filtrate; adding 3.5L water into the filter residue for extraction again, heating to 70 ℃ in a water bath, stirring and extracting for 1 hour, and filtering to obtain about 3.1L filtrate; the 6.2 l of extract was obtained by mixing. 250 g of rehmannia glutinosa is crushed and sieved by a sieve of 10 meshes, 2.5 liters of water is added, 5 g of inorganic adsorbent is added, the mixture is heated in water bath at 80 ℃, and stirred and extracted for 1 hour; filtering to obtain 2 liters of filtrate; adding 2.25L water into the filter residue, extracting again, heating in water bath to 80 deg.C, stirring and extracting for 1 hr, and filtering to obtain 1.9L filtrate; the 3.9 liters of extract were obtained by mixing. The two extracts were mixed to obtain 10.1 liters of extract.
Concentrating and forming the two kinds of ointment: adding 10.1L of the extract into a rotary evaporator in batches, heating to 60 deg.C and vacuum degree of 80 kPa; concentrating to 2L, adding 0.2 kg of honey while the mixture is hot, and fully stirring and dissolving to form a sticky two-instrument paste.
According to 2341, pesticide residue determination method in the fourth volume of the pharmacopoeia 2015 edition, 8 pesticide residues such as quintozene, total hexachlorobenzene, total dichlorodiphenyl trichloroethane, omethoate, methyl parathion, cypermethrin, fenvalerate, cyfluthrin and the like are determined by gas chromatography-tandem mass spectrometry and are not detected.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for removing pesticide residues in a traditional Chinese medicine ointment formula by using an inorganic adsorbent is characterized by comprising the following steps:
(1) preparing an inorganic adsorbent;
(2) separately extracting rare medicinal materials and common medicinal materials in the paste formula, respectively crushing, adding water, adding the inorganic adsorbent in the step (1), heating the rare medicinal materials at 60-90 ℃ and the common medicinal materials at 60-100 ℃, stirring and extracting, filtering to obtain an extracting solution, and extracting the dregs of a decoction again;
(3) mixing the rare medicinal material extract and the common medicinal material extract in the step (2), placing in a low-pressure concentration device, heating, concentrating, adding into paste to obtain paste;
the preparation of the inorganic adsorbent in the step (1) specifically comprises the following steps:
(1-1) activating ZSM-5 molecular sieve raw powder, and cooling to obtain ZSM-5 molecular sieve activated powder;
(1-2) activating the raw powder of the magnesium-aluminum hydrotalcite, and cooling to obtain activated powder of the magnesium-aluminum hydrotalcite;
(1-3) mixing ZSM-5 molecular sieve activated powder and magnesium aluminum hydrotalcite activated powder, adding water and activated alumina as a binder, fully mixing, extruding into strips, activating, and storing in a dry environment for later use;
the silica-alumina ratio of the ZSM-5 molecular sieve in the step (1-1) is 10-25;
the ZSM-5 molecular sieve raw powder activation condition in the step (1-1) is 250-450 ℃, and the activation time is more than 1 hour;
in the step (1-2), the activation condition of the magnesium aluminum hydrotalcite raw powder is 250-400 ℃, and the activation lasts for more than 1 hour;
and (3) after the extrusion molding, activating for more than 1 hour at the temperature of 250-400 ℃.
2. The method for removing pesticide residues in the traditional Chinese medicine ointment formula by using the inorganic adsorbent according to claim 1, wherein the mass ratio of the ZSM-5 molecular sieve activated powder to the magnesium aluminum hydrotalcite activated powder in the step (1-3) is (0.1-1): 0.1-1, and the mass of the activated alumina is 1/5 of the sum of the mass of the ZSM-5 molecular sieve activated powder and the mass of the magnesium aluminum hydrotalcite activated powder.
3. The method for removing pesticide residues in the traditional Chinese medicine ointment formula by using the inorganic adsorbent according to claim 1, wherein the activation conditions of the raw powder of the ZSM-5 molecular sieve in the step (1-1) are as follows: activating for 2-4 hours at the temperature of 350-400 ℃;
the activation conditions of the magnesium-aluminum hydrotalcite raw powder in the step (1-2) are as follows: activating for 2-4 hours at the temperature of 350-400 ℃;
the activation conditions after the extrusion molding in the step (1-3) are as follows: activating for 2-4 hours at the temperature of 350-400 ℃.
4. The method for removing pesticide residues in the traditional Chinese medicine ointment formula by using the inorganic adsorbent according to claim 1, wherein the famous and precious medicinal materials comprise one or more of ginseng, red ginseng, pseudo-ginseng and ganoderma lucidum; crushing the rare medicinal materials until the rare medicinal materials pass through a standard sieve mesh of 10 meshes; when the rare medicinal materials are extracted, the water amount is 15 liters/kg of the medicinal materials for the first time, the water amount is 14 liters/kg of the medicinal materials for the second time, 1/100-1/50 of the inorganic adsorbent in the mass of the rare medicinal materials is added, and the water bath heating time is more than 1 hour each time.
5. The method for removing pesticide residues in the traditional Chinese medicine ointment formula by using the inorganic adsorbent according to claim 4, wherein the famous and precious medicinal materials comprise one or more of ginseng, red ginseng, pseudo-ginseng and ganoderma lucidum; crushing the rare medicinal materials until the rare medicinal materials pass through a standard sieve mesh of 10 meshes; when the rare medicinal materials are extracted, the water amount is 15 liters/kg of the medicinal materials for the first time, the water amount is 14 liters/kg of the medicinal materials for the second time, 1/100-1/50 of the inorganic adsorbent in mass of the rare medicinal materials is added, the water bath heating is 70 ℃, and the water bath heating time is 2-3 hours each time.
6. The method of claim 1, wherein the common herbs are herbs except famous and precious herbs, and the common herbs are crushed to pass through a 10-mesh standard sieve; when the common medicinal materials are extracted, the water amount is 10 liters/kg of the medicinal materials for the first time, the water amount is 9 liters/kg of the medicinal materials for the second time, 1/50-1/20 of the inorganic adsorbent in the mass of the common medicinal materials is added, and the water bath heating time is more than 0.5 hour each time.
7. The method of claim 6, wherein the common herbs are herbs except famous and precious herbs, and the common herbs are crushed to pass through a 10-mesh standard sieve; when the common medicinal materials are extracted, the water amount is 10 liters/kg of the medicinal materials for the first time, the water amount is 9 liters/kg of the medicinal materials for the second time, 1/50-1/20 of the inorganic adsorbent in mass of the common medicinal materials is added, the water bath heating temperature is 80 ℃, and the water bath heating time is 1-2 hours each time.
8. The method for removing pesticide residues in the traditional Chinese medicine ointment formula by using the inorganic adsorbent according to claim 1, wherein the types and concentration ranges of the pesticide residues which can be adsorbed and removed by the inorganic adsorbent comprise one or more of 0.005-1.0 mg/L of quintozene, 0.001-0.5 mg/L of total hexachlorobenzene, 0.001-0.5 mg/L of total dichlorodiphenyl trichloroethane, 0.005-1.0 mg/L of omethoate, 0.005-1.0 mg/L of methyl parathion, 0.005-1.0 mg/L of cypermethrin, 0.005-1.0 mg/L of fenvalerate and 0.005-1.0 mg/L of cyfluthrin.
9. The method for removing pesticide residues in the traditional Chinese medicine ointment formula by using the inorganic adsorbent according to claim 1, wherein the low-pressure concentration device is a rotary evaporator with a heating part and a vacuum pump part, the heating temperature is 40-80 ℃, and the vacuum degree of the rotary evaporator is 60-95 kPa; the volume of the concentrated solution is 1/10-1/5 of the volume of the extracting solution.
10. The method for removing pesticide residues in the traditional Chinese medicine ointment formula by using the inorganic adsorbent according to claim 1, wherein the paste forming agent is one or more of white sugar, xylitol, rock candy and honey, and the dosage of the paste forming agent is 0.1-0.3 kg of paste forming agent added per liter of concentrated solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611088410.1A CN107335401B (en) | 2016-12-01 | 2016-12-01 | Method for removing pesticide residues in traditional Chinese medicine ointment formula by using inorganic adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611088410.1A CN107335401B (en) | 2016-12-01 | 2016-12-01 | Method for removing pesticide residues in traditional Chinese medicine ointment formula by using inorganic adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107335401A CN107335401A (en) | 2017-11-10 |
| CN107335401B true CN107335401B (en) | 2020-07-14 |
Family
ID=60222455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611088410.1A Active CN107335401B (en) | 2016-12-01 | 2016-12-01 | Method for removing pesticide residues in traditional Chinese medicine ointment formula by using inorganic adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107335401B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108925929A (en) * | 2018-06-15 | 2018-12-04 | 黄钱英 | The minimizing technology of remains of pesticide parathion-methyl in a kind of honey |
| CN109809548B (en) * | 2019-04-03 | 2022-02-15 | 长垣县农林畜牧局 | Organic nitrogen pesticide wastewater remover and preparation method thereof |
| CN111965291B (en) * | 2020-05-12 | 2022-06-07 | 长治市农产品质量安全检验监测中心 | Pesticide residue sample treatment method |
| CN112108116B (en) * | 2020-09-21 | 2023-03-28 | 中国科学院新疆理化技术研究所 | Preparation method and testing device of formed carbon composite material capable of removing various pesticide residues and antibiotics simultaneously |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1833748A (en) * | 2006-02-28 | 2006-09-20 | 南开大学 | Method of removing pesticide residual in natural extracts by adsorbing resin process |
| CN101711777A (en) * | 2009-12-14 | 2010-05-26 | 湖南省中药提取工程研究中心有限公司 | Method for removing pesticide residue in production process of lucid ganoderma extract |
| CN103529148A (en) * | 2013-10-21 | 2014-01-22 | 福建出入境检验检疫局检验检疫技术中心 | Method for detecting residual quantity of glyphosate and aminomethyl phosphonic acid metabolite of glyphosate in food |
| CN103156897B (en) * | 2013-03-28 | 2015-05-27 | 宁波立华植物提取技术有限公司 | Method for removing pesticide residue dichloro-diphenyl trichloroethane (DDT) and benzene hexachloride from American ginseng extract |
| CN104758323A (en) * | 2015-04-14 | 2015-07-08 | 江苏贝斯康药业有限公司 | Method for removing residual pesticide in ginkgol biloba extract |
| CN104474739B (en) * | 2014-12-04 | 2016-08-31 | 上海绿强新材料有限公司 | The application in removing traditional Chinese medicine heavy metal of a kind of molecular sieve adsorption material |
-
2016
- 2016-12-01 CN CN201611088410.1A patent/CN107335401B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1833748A (en) * | 2006-02-28 | 2006-09-20 | 南开大学 | Method of removing pesticide residual in natural extracts by adsorbing resin process |
| CN101711777A (en) * | 2009-12-14 | 2010-05-26 | 湖南省中药提取工程研究中心有限公司 | Method for removing pesticide residue in production process of lucid ganoderma extract |
| CN103156897B (en) * | 2013-03-28 | 2015-05-27 | 宁波立华植物提取技术有限公司 | Method for removing pesticide residue dichloro-diphenyl trichloroethane (DDT) and benzene hexachloride from American ginseng extract |
| CN103529148A (en) * | 2013-10-21 | 2014-01-22 | 福建出入境检验检疫局检验检疫技术中心 | Method for detecting residual quantity of glyphosate and aminomethyl phosphonic acid metabolite of glyphosate in food |
| CN104474739B (en) * | 2014-12-04 | 2016-08-31 | 上海绿强新材料有限公司 | The application in removing traditional Chinese medicine heavy metal of a kind of molecular sieve adsorption material |
| CN104758323A (en) * | 2015-04-14 | 2015-07-08 | 江苏贝斯康药业有限公司 | Method for removing residual pesticide in ginkgol biloba extract |
Non-Patent Citations (1)
| Title |
|---|
| "Removal of Pesticides from Aqueous Solutions by Adsorption on Zeolites as Solid Adsorbents";C. De Smedt et.al;《Adsorption Science & Technology》;20151231;第33卷(第5期);摘要，结论，表7 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107335401A (en) | 2017-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107335401B (en) | Method for removing pesticide residues in traditional Chinese medicine ointment formula by using inorganic adsorbent | |
| CN104982599A (en) | Botanic herbal tea concentrate and low-sugar botanic herbal tea beverage | |
| CN113521232B (en) | A Chinese medicinal composition containing Atractylodis rhizoma | |
| CN106362020B (en) | A kind of pine pollen composition and preparation method thereof with improvement defecating feces excretion | |
| JP2002154979A (en) | Medicine composition for i type allergy and method for producing the same | |
| CN104984210A (en) | Amomum kravanh and galangal alcohol effect dispelling honey and preparing method thereof | |
| CN101940642A (en) | Chinese medicinal composition and application thereof | |
| CN106109521A (en) | A kind of Radix Notoginseng oral liquid | |
| CN114099609B (en) | Pharmaceutical composition for treating cough and preparation method thereof | |
| CN106309736B (en) | Anti-fatigue Chinese medicinal composition and its preparation method and application | |
| CN113995074A (en) | Molecular essence solid beverage with blood glucose reducing function and preparation method thereof | |
| CN100500174C (en) | Medicine composition used for lowering blood-sugar, preparation method and use thereof | |
| CN102580042A (en) | Traditional Chinese medicine composition for treating wind-cold type of common cold and preparation method of traditional Chinese medicine composition | |
| CN100355440C (en) | Compound Chinese medicinal preparation for treating type II diabetes and lowering blood sugar and its preparation method | |
| CN105663079B (en) | A method of it prepares and subtracts taste antiphlogistic bezoar capsule | |
| CN104352717A (en) | Traditional Chinese medicine preparation for treating spleen-qi weakness type hemafecia and preparation method thereof | |
| CN1060663C (en) | Compound Tibet capillary artemisia patent medicine | |
| CN115252729B (en) | Traditional Chinese medicine composition for treating diabetes and application thereof | |
| CN106491747B (en) | Preparation of cordyceps sinensis-astragalus-ginseng capsule and quality standard detection method | |
| CN111588771B (en) | Application of traditional Chinese medicine composition in preparation of medicine for treating vertigo | |
| CN102949496A (en) | Dispersible tablet of traditional Chinese medicine used for treating allergic rhinitis and preparation method thereof | |
| CN101926907B (en) | Method for preparing Kang'ai body resistance-strengthening tablets for treating tumors | |
| CN102755519A (en) | Kudzuvine root-kudzuvine flower anti-canker sore particle and preparation method thereof | |
| CN1672703A (en) | Medicine xinqin tablet for treating allergic rhintis and its prepn | |
| CN109394968B (en) | Composition with auxiliary blood sugar reducing function and application thereof |
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 |