CN114247179A - Grease purifying agent and preparation method and application thereof - Google Patents
Grease purifying agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN114247179A CN114247179A CN202111655043.XA CN202111655043A CN114247179A CN 114247179 A CN114247179 A CN 114247179A CN 202111655043 A CN202111655043 A CN 202111655043A CN 114247179 A CN114247179 A CN 114247179A
- Authority
- CN
- China
- Prior art keywords
- parts
- grease
- purifying agent
- ethyl alcohol
- absolute ethyl
- 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.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Lubricants (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a grease purifying agent, and a preparation method and application thereof, and belongs to the field of food safety detection. The grease purifying agent comprises the following raw materials in parts by weight: 100 parts of silica sol, 15-40 parts of lithium magnesium silicate, 1.5-3.5 parts of organic acid, 9-15 parts of coupling agent, 1-1.8 parts of diamine and 12-50 parts of long-chain alkylamine, wherein the chemical formula of the long-chain alkylamine is (C)nH2n+1)NH2Wherein n is 18-22. The grease purifying agent disclosed by the invention has a good grease purifying effect on animal-derived food, is non-volatile, environment-friendly and safe, does not influence the detection of a target object, and can completely replace an organic solvent to extract and purify grease of animal-derived food.
Description
Technical Field
The invention relates to a grease purifying agent, and a preparation method and application thereof, and belongs to the field of food safety detection.
Background
During the cultivation process, the situation that the fed animals are illegally used by veterinary drugs often occurs. In order to ensure that the animal derived food meets the requirements of national food safety standards, ensure the health of consumers and guarantee the smooth export trade, the animal derived food is necessary to be subjected to the detection and supervision of various conventional veterinary drug residues.
The animal-derived food contains animal oil, and in the detection process of drug residue, the oil is used as a part of the matrix, is extracted in the pretreatment step, and then enters the purification/concentration step. The oil has low solubility in water and common mobile phase solvents (such as methanol and acetonitrile), and has a high melting point and a high boiling point, and if no measures are taken, the oil can be separated out along with the increase of the proportion of water in the mobile phase during the detection of an instrument, or the oil is condensed due to low temperature and is attached to the pipe wall or a separation column, so that the pipeline is polluted or even blocked, the equipment is damaged, and the detection efficiency is seriously influenced.
A large number of documents report the use of non-polar organic solvents as degreasing agents for grease removal in systems. For example: GB/T20366-2006 adopts a formic acid acetonitrile solution as an extraction reagent, and n-hexane as an extraction liquid degreasing reagent to remove grease in animal-derived food. GB/T20751-2006 adopts acetonitrile as an extraction reagent and n-hexane as an extraction liquid degreasing reagent to remove grease in eel. CN102081078A adopts diatomite to absorb water, 8% ammonia water acetonitrile is used for extraction, and n-hexane and ether are used for removing grease in animal derived food. Ultra performance liquid chromatography-tandem mass spectrometry for determining 6 quinolone drug residues in eel muscle tissues (Liu Zheng Cai et al, academic journal of analytical science, 30(6), 2014, 863 and 867) uses a 2% acetonitrile formate solution for extraction, and neutral alumina and n-hexane are used for removing lipid impurities in the eel muscle tissues. Research on a method for detecting multiple pesticide residues in eel (Zhengrenjin, Fujian medical university, 2011) uses Florisil solid phase extraction purification column as a purification column, has a good effect of removing lipid impurities in eel muscle tissues, and has little influence on the recovery rate of multiple residual pesticides. CN111323510A adopts acetonitrile as an extraction reagent, utilizes a three-column two-dimensional liquid chromatography-mass spectrometry method, firstly, through size exclusion of gel chromatography, separation of a target compound from a matrix is realized, and matrix interference is removed; and then the on-line column switching liquid phase-mass spectrum coupling technology is utilized to realize the purpose of on-line purification of the carbostyril drug residues in the chicken.
In the scheme, nonpolar organic solvents such as n-hexane and diethyl ether are generally used as degreasing reagents, and although the purpose can be achieved, the organic solvents such as n-hexane and diethyl ether have low boiling points and high toxicity, and can be absorbed through skin, so that the influence on the body health and the environment of operators is large. In the research on the method for detecting the pesticide residue in the eels, although the Florisil column has a good purification effect, the Florisil column has certain retention on a target object, needs toxic elution solvents such as dichloromethane and the like for elution, cannot avoid the contact of operators with the solvents, and has great influence on the environment. Although the CN111323510A on-line purification can avoid operators from directly contacting organic solvents and has little influence on the environment, the CN111323510A on-line purification needs special equipment, is expensive in manufacturing cost and use and has certain difficulty in large-scale popularization in detection mechanisms.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a grease purifying agent, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
in a first aspect, the grease purifying agent is provided, and comprises the following raw materials in parts by weight: 100 parts of silica sol, 15-40 parts of lithium magnesium silicate, 1.5-3.5 parts of organic acid, 9-15 parts of coupling agent, 1-1.8 parts of diamine and 12-50 parts of long-chain alkylamine, wherein the chemical formula of the long-chain alkylamine is (C)nH2n+1)NH2Wherein n is 18-22.
The grease purifying agent is prepared by in-situ compounding of porous silicon dioxide and long-chain alkylamine modified magnesium lithium silicate, wherein the porous silicon dioxide is used as a hard framework and plays a supporting role; the long-chain alkylamine modified magnesium lithium silicate is an effective part of the grease purifying agent; the long-chain alkylamine modified lithium magnesium silicate is wound in pores and on the surface of the silicon dioxide, the long-chain alkylamine modified part of the lithium magnesium silicate is composed of middle hydrophobic long-chain alkyl and carboxylates at two ends, the lithium magnesium silicate has excellent affinity to grease, and grease emulsified and dissolved by a solvent in a system can be quickly extracted from an extracting solution, so that the aim of purifying the grease is fulfilled. The grease purifying agent can be prepared into a solid-phase extraction column or directly added into a system to be uniformly mixed with a matrix for use, thereby achieving the purpose of purifying grease.
In a preferred embodiment of the fat and oil purifying agent of the present invention, the organic acid is at least one of propionic acid, citric acid and malic acid.
The porous silica is obtained by acidifying silica sol. After the silica sol is mixed with the lithium magnesium silicate, the pH value is adjusted to separate out the silicon dioxide in the silica sol. In the process, organic acid diffusion is utilized to gradually separate out silicon dioxide, and the silicon dioxide and the magnesium silicate lithium gel dispersed in the system form an interpenetrating network structure. The porous silica can adjust the size and structural distribution of pores by the ratio of silica sol to water.
In a preferred embodiment of the grease scavenger of the present invention, the coupling agent is at least one of γ - (2, 3-glycidoxy) propyltrimethoxysilane, γ - (2, 3-glycidoxy) propyltriethoxysilane, and γ - (2, 3-glycidoxy) propylmethyldiethoxysilane.
Gamma- (2, 3-glycidoxy) propyltrimethoxysilane, abbreviated as KH560, CAS No.: 2530-83-8; γ - (2, 3-glycidoxy) propyltriethoxysilane, abbreviated as KH561, CAS number: 2602-34-8; γ - (2, 3-glycidoxy) propylmethyldiethoxysilane, abbreviated KH563, CAS No.: 2897-60-1.
The chemical general formula of the magnesium lithium silicate is Na+ 0.7[(Si8Mg5.5Li0.3)O20(OH)4]-0.7And contains a large number of hydroxyl groups. After adding the silane coupling agent, the silane coupling agent is subjected to hydrolysis reaction with water in a system to generate silanol groups with higher activity, the silanol groups are simultaneously subjected to reaction with hydroxyl on the surface and in pores of the porous silicon dioxide and hydroxyl in the magnesium silicate lithium, and epoxy groups are connected to the surface and in the pores of the porous silicon dioxide and the magnesium silicate lithium; the epoxy groups will react with the subsequently added diamine and long chain amine.
Preferably, the lithium magnesium silicate is BYK
RD and Hemings
One of RD.
In a preferred embodiment of the grease cleaning agent of the present invention, the diamine is one of 1, 4-butanediamine and 1, 6-hexanediamine.
Diamine is used as a cross-linking agent, and mainly has the function of chemically bonding the magnesium lithium silicate with the silicon dioxide and the lamellar structure of the magnesium lithium silicate, so that the magnesium lithium silicate is bonded with the porous silicon dioxide by chemical bonds and is attached to the surface and in pores of the porous silicon dioxide in a physical winding manner, and the magnesium lithium silicate and the porous silicon dioxide are firmly bonded together. The amine-base end of the long-chain amine reacts with epoxy to be connected to the surface of the composite body, and the other end of the long-chain amine provides oleophilic long-chain alkyl which is used as an effective structure for absorbing grease.
In a preferred embodiment of the grease scavenger of the present invention, the long-chain alkylamine is at least one of n-octadecylamine, n-eicosylamine and n-docosamine.
CAS number of n-octadecylamine: 124-30-1; CAS number of n-eicosylamine: 10525-37-8; CAS number of n-icosanediamine: 14130-06-4.
In a preferred embodiment of the fat and oil purifying agent of the present invention, the silica sol is present in an amount of 30% by mass.
The second aspect provides a preparation method of a grease purifying agent, which comprises the following steps:
(1) homogenizing silica sol and lithium magnesium silicate at the rotation speed of 10000-18000rpm for 0.5-1h, standing, adding organic acid, and continuously standing for 10-24h to obtain a translucent gel solid Q1;
(2) dissolving a coupling agent in absolute ethyl alcohol to obtain a transparent aqueous solution, adding the transparent aqueous solution into Q1, stirring for 10-16h at 50-60 ℃, and cooling to obtain a white solid Q2;
(3) adding diamine and long-chain alkylamine into Q2, stirring at the rotation speed of 200-50 ℃ and 500rpm for 3-6h, heating to 60-80 ℃, continuing stirring for 4-8h, cooling to 30-40 ℃, and standing to obtain white suspension Q3;
(4) washing the Q3 with absolute ethyl alcohol, toluene, absolute ethyl alcohol, 40% ethanol solution and absolute ethyl alcohol in sequence, carrying out suction filtration to obtain a white solid, and drying and grinding the white solid to obtain the grease purifying agent.
As a preferred embodiment of the method for preparing the fat and oil purifying agent of the present invention, in the step (4), the volume ratio of Q3, absolute ethyl alcohol, toluene, absolute ethyl alcohol, 40% ethanol solution, and absolute ethyl alcohol is Q3: anhydrous ethanol: toluene: anhydrous ethanol: 40% ethanol solution: anhydrous ethanol is 1:1:2:1:2: 2.
In the step (4), the drying temperature is 30-50 ℃.
In a third aspect, an application of the oil purifying agent in detection of drug residues in animal food is provided.
According to the grease purifying agent, long-chain alkylamine modified magnesium lithium silicate is used as an effective component for grease purification, and long-chain alkyl has a good adsorption effect on animal grease due to the hydrophobic oleophylic performance of the long-chain alkyl. The long-chain amine has unfixed alkyl end, so that the molecular chain of the long-chain amine is expanded in the grease in the using process, and the contact between the alkyl and the grease is increased; because the crosslinked magnesium lithium silicate is in a colloid structure wound inside and on the surface of the silicon dioxide, certain deformation, displacement, diffusion and the like can be generated in the using process, the contact surface is greatly improved, and the oil absorption effect is greatly improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) the grease purifying agent disclosed by the invention is a compound of porous silicon dioxide and long-chain amine modified magnesium lithium silicate generated by an in-situ synthesis method. The porous silica is obtained by acidifying silica sol. The long-chain amine is bonded with the magnesium lithium silicate or the porous silicon dioxide through a silane coupling agent containing an epoxy group, so that the purpose of grease adsorption is achieved. Meanwhile, diamine is added in the reaction process and can react with an epoxy group, and the magnesium lithium silicate or the porous silicon dioxide are tightly combined through chemical crosslinking.
After the silica sol is mixed with the lithium magnesium silicate, the pH value is adjusted to separate out the silicon dioxide in the silica sol. In the process, organic acid diffusion is utilized to gradually separate out silicon dioxide, and the silicon dioxide and the magnesium silicate lithium gel dispersed in the system form an interpenetrating network structure. The porous silica can adjust the size and structural distribution of pores by the ratio of silica sol to water.
The chemical general formula of the magnesium lithium silicate is Na+ 0.7[(Si8Mg5.5Li0.3)O20(OH)4]-0.7And contains a large number of hydroxyl groups. After adding the silane coupling agent, the silane coupling agent is subjected to hydrolysis reaction with water in a system to generate silanol groups with higher activity, the silanol groups are simultaneously subjected to reaction with hydroxyl on the surface and in pores of the porous silicon dioxide and hydroxyl in the magnesium silicate lithium, and epoxy groups are connected to the surface and in the pores of the porous silicon dioxide and the magnesium silicate lithium; the epoxy groups will react with the subsequently added diamine and long chain amine. Diamine is used as a cross-linking agent, and mainly has the function of chemically bonding the magnesium lithium silicate with the silicon dioxide and the lamellar structure of the magnesium lithium silicate, so that the magnesium lithium silicate is bonded with the porous silicon dioxide by chemical bonds and is attached to the surface and in pores of the porous silicon dioxide in a physical winding manner, and the magnesium lithium silicate and the porous silicon dioxide are firmly bonded together. The amine-base end of the long-chain amine reacts with epoxy to be connected to the surface of the composite body, and the other end of the long-chain amine provides oleophilic long-chain alkyl which is used as an effective structure for absorbing grease.
(2) In the grease purifying agent disclosed by the invention, the porous silica is used as a framework to support the structure of the grease purifying agent, so that the problems of low use efficiency of active ingredients or over-high column pressure generated in a column due to the collapse of the structure of the grease purifying agent are prevented in the use process, and meanwhile, because the porous silica contains a large number of hydroxyl groups, a certain amount of hydroxyl groups are modified in the reaction process to form an oleophilic surface which is used as an effective ingredient to adsorb partial grease.
(3) In the grease purifying agent disclosed by the invention, long-chain amine modified magnesium lithium silicate is used as an effective component for grease purification, and long-chain alkyl has a good adsorption effect on animal grease due to the hydrophobic and oleophilic properties of the long-chain alkyl. The long-chain amine has unfixed alkyl end, so that the molecular chain of the long-chain amine is expanded in the grease in the using process, and the contact between the alkyl and the grease is increased; because the crosslinked magnesium lithium silicate is in a colloid structure wound inside and on the surface of the silicon dioxide, certain deformation, displacement, diffusion and the like can be generated in the using process, the contact surface is greatly improved, and the oil absorption effect is greatly improved.
(4) The grease purifying agent disclosed by the invention has a good grease purifying effect on animal-derived food, is non-volatile, environment-friendly and safe, does not influence the detection of a target object, and can completely replace an organic solvent to extract and purify the grease of the animal-derived food.
Drawings
FIG. 1 is a multi-reaction monitoring chromatogram for ciprofloxacin detection in eel.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following detailed description and accompanying drawings.
In the following examples, the magnesium lithium silicate is BYK
RD and Hemings
One of RD; all starting materials are commercially available.
Example 1
The embodiment provides a grease purifying agent, which comprises the following raw materials in parts by weight: 100 parts of silica sol and 40 parts of Hemings
RD, 3.5 parts of citric acid, 15 parts of KH561, 1.8 parts of 1, 4-butanediamine and 50 parts of n-octadecylamine.
The embodiment also provides a preparation method of the grease purifying agent, which comprises the following steps:
(1) 100 parts by weight of silica sol and 40 parts by weight of Hemings
Continuously stirring RD and 200 parts by weight of deionized water on a homogenizer at the rotating speed of 18000rpm for 1 hour, standing for 2 hours, adding 3.5 parts by weight of citric acid, and standing for 10 hours to obtain a translucent gel solid Q1;
(2) dissolving 15 parts by weight of KH561 in 100 parts by weight of absolute ethanol to obtain a transparent aqueous solution, adding the transparent aqueous solution into Q1, stirring for 10 hours at 60 ℃, and cooling to obtain a white solid Q2;
(3) adding 1.8 parts by weight of 1, 4-butanediamine and 50 parts by weight of n-octadecylamine into Q2, stirring at 40 ℃ and 200rpm for 6 hours, heating to 80 ℃, continuing to stir for 4 hours, cooling to 30 ℃, and standing to obtain a white suspension Q3;
(4) adding 100 parts by volume of Q3 into an ion exchange column, washing with 100 parts by volume of absolute ethyl alcohol, 200 parts by volume of toluene, 100 parts by volume of absolute ethyl alcohol, 200 parts by volume of 40% ethanol solution and 200 parts by volume of absolute ethyl alcohol in sequence, and performing suction filtration to obtain a white solid; and (3) drying the white solid in a vacuum drying oven at 50 ℃ overnight to obtain a white loose block solid, and grinding for 1min to obtain the grease purifying agent QQ 1.
Example 2
The embodiment provides a grease purifying agent, which comprises the following raw materials in parts by weight: 100 parts of silica sol and 15 parts of BYK
RD, 1.8 parts of propionic acid, 9 parts of KH561, 1 part of 1, 6-hexamethylene diamine and 12 parts of n-eicosylamine.
The embodiment also provides a preparation method of the grease purifying agent, which comprises the following steps:
(1) 100 parts by weight of silica sol and 15 parts by weight of BYK
RD, continuously stirring for 30min on a homogenizer at the rotating speed of 15000, standing for 2h, adding 1.8 parts by weight of propionic acid, and standing for 24h to obtain a translucent gel solid Q1;
(2) dissolving 9 parts by weight of KH560 in 70 parts by weight of absolute ethanol to obtain a transparent aqueous solution, adding the transparent aqueous solution into Q1, stirring for 16h at 50 ℃, and cooling to obtain white solid Q2;
(3) adding 1 part by weight of 1, 6-hexamethylene diamine and 12 parts by weight of n-eicosylamine into Q2, stirring at 40 ℃ for 6 hours at a rotating speed of 500rpm, heating to 80 ℃, continuing stirring for 4 hours, cooling to 30 ℃, and standing to obtain a white suspension Q3;
(4) adding 100 parts by volume of Q3 into an ion exchange column, washing with 100 parts by volume of absolute ethyl alcohol, 200 parts by volume of toluene, 100 parts by volume of absolute ethyl alcohol, 200 parts by volume of 40% ethanol solution and 200 parts by volume of absolute ethyl alcohol in sequence, and performing suction filtration to obtain a white solid; and (3) drying the white solid overnight at 40 ℃ in a vacuum drying oven to obtain a white loose block solid, and grinding for 1min to obtain the grease purifying agent QQ 2.
Example 3
The embodiment provides a grease purifying agent, which comprises the following raw materials in parts by weight: 100 parts of silica sol and 32 parts of Hemings
RD, 2.1 parts of malic acid, 12 parts of KH563, 1.5 parts of 1, 6-hexanediamine and 32 parts of n-octadecylamine.
The embodiment also provides a preparation method of the grease purifying agent, which comprises the following steps:
(1) 100 parts by weight of silica sol and 32 parts by weight of Hemings
Continuously stirring RD and 150 parts by weight of deionized water on a homogenizer at the rotating speed of 12000rpm for 1h, standing for 2h, adding 2.1 parts by weight of malic acid, and standing for 20h to obtain a translucent gel solid Q1;
(2) dissolving 12 parts by weight of KH563 in 50 parts by weight of absolute ethanol to obtain a transparent aqueous solution, adding into Q1, stirring at 55 deg.C for 12h, and cooling to obtain white solid Q2;
(3) adding 1.5 parts by weight of 1, 6-hexamethylene diamine and 32 parts by weight of n-octadecylamine into Q2, stirring at the rotation speed of 400rpm at the temperature of 45 ℃ for 4 hours, heating to 70 ℃, continuing stirring for 5 hours, cooling to 32 ℃, and standing to obtain a white suspension Q3;
(4) adding 100 parts by volume of Q3 into an ion exchange column, washing with 100 parts by volume of absolute ethyl alcohol, 200 parts by volume of toluene, 100 parts by volume of absolute ethyl alcohol, 200 parts by volume of 40% ethanol solution and 200 parts by volume of absolute ethyl alcohol in sequence, and performing suction filtration to obtain a white solid; and (3) drying the white solid in a vacuum drying oven at 30 ℃ overnight to obtain a white loose block solid, and grinding for 1min to obtain the grease purifying agent QQ 3.
Example 4
The embodiment provides a grease purifying agent, which comprises the following raw materials in parts by weight: 100 parts of silica sol, 17 parts of BYK
RD, 2.6 parts of propionic acid, 14 parts of KH560, 1.3 parts of 1, 4-butanediamine and 40 parts of n-icosaediamine.
The embodiment also provides a preparation method of the grease purifying agent, which comprises the following steps:
(1) 100 parts by weight of silica sol and 17 parts by weight of BYK
Continuously stirring RD and 70 parts by weight of deionized water on a homogenizer at the rotating speed of 10000 for 1h, standing for 2h, adding 2.6 parts by weight of propionic acid, and standing for 16h to obtain a translucent gel solid Q1;
(2) dissolving 14 parts by weight of KH560 in 40 parts by weight of absolute ethanol to obtain a transparent aqueous solution, adding the transparent aqueous solution into Q1, stirring for 14 hours at 55 ℃, and cooling to obtain white solid Q2;
(3) adding 1.3 parts by weight of 1, 4-butanediamine and 40 parts by weight of n-icosane into Q2, stirring at 40 ℃ for 6 hours at the rotating speed of 300rpm, heating to 80 ℃, continuing stirring for 4 hours, cooling to 37 ℃, and standing to obtain white suspension Q3;
(4) adding 100 parts by volume of Q3 into an ion exchange column, washing with 100 parts by volume of absolute ethyl alcohol, 200 parts by volume of toluene, 100 parts by volume of absolute ethyl alcohol, 200 parts by volume of 40% ethanol solution and 200 parts by volume of absolute ethyl alcohol in sequence, and performing suction filtration to obtain a white solid; and (3) drying the white solid in a vacuum drying oven at 35 ℃ overnight to obtain a white loose block solid, and grinding for 1min to obtain the grease purifying agent QQ 4.
Effect example 1
The oil-and-fat purifying agents QQ1 to QQ4 obtained in examples 1 to 4 were compared with the oil-and-fat purifying effect of n-hexane.
The specific method comprises the following steps: taking 12 parts of uniformly mixed pork, chicken, eel, tilapia, egg and minced milk respectively, taking two parts as a parallel, wherein 8 parts of QQ 1-QQ 4 are respectively parallel, 2 parts of blank one parallel and 2 parts of n-hexane purified one parallel are respectively added, and each part is 5.00 +/-0.05 g, and 25 mu L of ciprofloxacin standard solution with the concentration of 1 mu g/mL is respectively added. The experimental conditions of the liquid chromatography-tandem mass spectrometry for determining the residual quantity of fifteen quinolone drugs in GB/T20751 eel and products 2006 eel and products are referred to, and the verification is carried out after the equipment parameters are finely adjusted according to the existing equipment and conditions in a laboratory.
The extraction and purification steps using the grease purifiers QQ1 to QQ4 are described as follows: respectively adding about 5g of grease purifying agent and 25mL of acetonitrile into the paste sample, using a disperser to perform dispersion extraction at 10000rpm for 30 seconds, centrifuging at 4000rpm for 5 minutes, and transferring the supernatant into a 50mL colorimetric tube; adding 15mL of acetonitrile into another 50mL of centrifuge tube, washing a dispersing cutter head for 10 seconds, transferring the washing solution into the first centrifuge tube, stirring residues by using a glass rod, carrying out vortex oscillation extraction for 1 minute, carrying out ultrasonic oscillation extraction for 5 minutes, centrifuging at 4000rpm for 5 minutes, and combining the supernatant into a 50mL colorimetric tube; and adding 10mL of acetonitrile into the residue, performing vortex oscillation extraction for 1min, centrifuging at 4000rpm for 5 min, combining the supernate into a 50mL colorimetric tube, and metering the volume of the acetonitrile to 50.0 mL. Shaking up the colorimetric tube, transferring 10.0mL of acetonitrile extracting solution, blowing nitrogen to be nearly dry at 35 ℃ by using a nitrogen concentrator, adding 3mL of ammonium acetate buffer solution, carrying out vortex oscillation for 30 seconds, then respectively passing through a strong cation exchange column at the flow rate of about 1mL/min, draining, eluting by 1.5mL of methanol and 3mL of ammonia water methanol solution in sequence, combining eluates, blowing nitrogen to be nearly dry at 35 ℃, fixing the volume to 1.00mL by using 10% acidified acetonitrile, passing through a 0.22 mu m filter membrane, and carrying out liquid chromatography-tandem mass spectrometry.
The n-hexane comparison test is completely consistent with the liquid chromatography-tandem mass spectrometry for measuring the residual quantity of fifteen quinolone drugs in GB/T20751 eel and products 2006.
The blank comparison test is consistent with the normal hexane comparison test except that normal hexane is not used for degreasing.
Liquid chromatography conditions: a chromatographic column: c18(5 μm, 150 mm. times.2.1 mm), column temperature 30 ℃, flow rate 200 μ L/min, sample size 10 μ L, gradient elution program as shown in Table 1.
TABLE 1 liquid chromatography gradient elution procedure
| Time, min | Acetonitrile, is% | Methanol, is% | 0.1% formic acid,% |
| 0 | 2 | 20 | 78 |
| 4 | 5 | 20 | 75 |
| 8 | 10 | 20 | 70 |
| 10 | 40 | 20 | 40 |
| 15 | 40 | 20 | 40 |
| 15.5 | 2 | 20 | 78 |
| 22 | 2 | 20 | 78 |
Mass spectrum conditions: electrospray ESI + ion source; the scanning mode is as follows: multiple Reaction Monitoring (MRM); the ion source temperature is 490 ℃; the qualitative ion pair, the quantitative ion pair, the declustering voltage and the energy of the collision gas are shown in Table 2.
TABLE 2 ciprofloxacin Mass Spectrometry parameters
The test results are shown in table 3.
TABLE 3 mean recovery data for ciprofloxacin in each sample
FIG. 1 is a multi-reaction monitoring chromatogram for ciprofloxacin detection in eel. As can be seen from the test data in table 3 and fig. 1, the blank test has a significantly lower ciprofloxacin response value and recovery rate than the others even after purification by the solid phase extraction column because the grease is not removed, and the recovery rate detection result is lower, and the grease is more abundant in eel and pork, which has a greater influence on the detection result. The recovery rate of ciprofloxacin of a sample using the grease purifying agent QQ 1-QQ 4 is 89.34-103.10%, grease is removed by using n-hexane, the recovery rate of ciprofloxacin is 93.99-102.38%, the grease purifying agent has the same purifying effect as the n-hexane, the obtained result meets the requirement of residue detection, the purifying effect is good, no obvious negative influence is caused on a target object, and the grease purifying agent can be used as the grease purifying agent to completely replace the toxic n-hexane in residue detection analysis.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The grease purifying agent is characterized by comprising the following raw materials in parts by weight: 100 parts of silica sol, 15-40 parts of lithium magnesium silicate, 1.5-3.5 parts of organic acid, 9-15 parts of coupling agent, 1-1.8 parts of diamine and 12-50 parts of long-chain alkylamine, wherein the chemical formula of the long-chain alkylamine is (C)nH2n+1)NH2Wherein n is 18-22.
2. The grease purifying agent as claimed in claim 1, wherein the organic acid is at least one of propionic acid, citric acid and malic acid.
3. The grease purifying agent according to claim 1, wherein the coupling agent is at least one of γ - (2, 3-glycidoxy) propyltrimethoxysilane, γ - (2, 3-glycidoxy) propyltriethoxysilane, and γ - (2, 3-glycidoxy) propylmethyldiethoxysilane.
4. The grease purifying agent as claimed in claim 1, wherein the diamine is one of 1, 4-butanediamine and 1, 6-hexanediamine.
5. The grease scavenger according to claim 1, wherein the long-chain alkylamine is at least one of n-octadecylamine, n-eicosylamine and n-docosamine.
6. The grease scavenger according to claim 1, wherein the mass fraction of the silica sol is 30%.
7. A method for preparing the grease purifying agent as defined in any one of claims 1 to 6, which comprises the following steps:
(1) homogenizing silica sol and lithium magnesium silicate at the rotation speed of 10000-18000rpm for 0.5-1h, standing, adding organic acid, and continuously standing for 10-24h to obtain a translucent gel solid Q1;
(2) dissolving a coupling agent in absolute ethyl alcohol to obtain a transparent aqueous solution, adding the transparent aqueous solution into Q1, stirring for 10-16h at 50-60 ℃, and cooling to obtain a white solid Q2;
(3) adding diamine and long-chain alkylamine into Q2, stirring at the rotation speed of 200-50 ℃ and 500rpm for 3-6h, heating to 60-80 ℃, continuing stirring for 4-8h, cooling to 30-40 ℃, and standing to obtain white suspension Q3;
(4) washing the Q3 with absolute ethyl alcohol, toluene, absolute ethyl alcohol, 40% ethanol solution and absolute ethyl alcohol in sequence, carrying out suction filtration to obtain a white solid, and drying and grinding the white solid to obtain the grease purifying agent.
8. The method according to claim 7, wherein in the step (4), the volume ratio of Q3, absolute ethyl alcohol, toluene, absolute ethyl alcohol, 40% ethanol solution and absolute ethyl alcohol is Q3: anhydrous ethanol: toluene: anhydrous ethanol: 40% ethanol solution: anhydrous ethanol is 1:1:2:1:2: 2.
9. The method according to claim 7, wherein the drying temperature in the step (4) is 30 to 50 ℃.
10. Use of the fat purifying agent according to any one of claims 1 to 6 for the detection of drug residues in animal food.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111655043.XA CN114247179B (en) | 2021-12-30 | 2021-12-30 | Grease purifying agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111655043.XA CN114247179B (en) | 2021-12-30 | 2021-12-30 | Grease purifying agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114247179A true CN114247179A (en) | 2022-03-29 |
| CN114247179B CN114247179B (en) | 2022-11-29 |
Family
ID=80798930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111655043.XA Active CN114247179B (en) | 2021-12-30 | 2021-12-30 | Grease purifying agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114247179B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4434076A (en) * | 1981-10-19 | 1984-02-28 | Nl Industries, Inc. | Clay cation complexes and their use to increase viscosity of liquid organic systems |
| WO2002017868A1 (en) * | 2000-09-01 | 2002-03-07 | Cognis Iberia S.L. | Oral and dental hygiene agents |
| US9969680B1 (en) * | 2017-06-28 | 2018-05-15 | Vitaworks Ip, Llc | Process for the separation of long chain amino acids and dibasic acids |
| CN110662525A (en) * | 2017-03-23 | 2020-01-07 | Isp投资有限公司 | Skin care compositions comprising terpolymers, methods of making and methods of using the same |
| CN112607812A (en) * | 2020-12-01 | 2021-04-06 | 中冶焦耐(大连)工程技术有限公司 | Low-loss high-efficiency dephenolizing extraction agent for treating low-rank coal quality-divided conversion phenol-containing wastewater |
| CN113164361A (en) * | 2018-12-06 | 2021-07-23 | 高露洁-棕榄公司 | Personal care compositions |
-
2021
- 2021-12-30 CN CN202111655043.XA patent/CN114247179B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4434076A (en) * | 1981-10-19 | 1984-02-28 | Nl Industries, Inc. | Clay cation complexes and their use to increase viscosity of liquid organic systems |
| WO2002017868A1 (en) * | 2000-09-01 | 2002-03-07 | Cognis Iberia S.L. | Oral and dental hygiene agents |
| CN110662525A (en) * | 2017-03-23 | 2020-01-07 | Isp投资有限公司 | Skin care compositions comprising terpolymers, methods of making and methods of using the same |
| US9969680B1 (en) * | 2017-06-28 | 2018-05-15 | Vitaworks Ip, Llc | Process for the separation of long chain amino acids and dibasic acids |
| CN113164361A (en) * | 2018-12-06 | 2021-07-23 | 高露洁-棕榄公司 | Personal care compositions |
| CN112607812A (en) * | 2020-12-01 | 2021-04-06 | 中冶焦耐(大连)工程技术有限公司 | Low-loss high-efficiency dephenolizing extraction agent for treating low-rank coal quality-divided conversion phenol-containing wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114247179B (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108262019B (en) | Magnetic sulfonic group functionalized COFs material and preparation method and application thereof | |
| CN103816814B (en) | A kind of porous granule MCM-41-ZIF-8/PDMS pervaporation hybrid membrane, preparation and application | |
| CN103028383B (en) | Silica gel chromatography packing and preparation method thereof | |
| CN108276584B (en) | Method for detecting aromatic amine compound in human urine | |
| Yang et al. | Separation and purification of both tea seed polysaccharide and saponin from camellia cake extract using macroporous resin | |
| CN104226262A (en) | Preparing method and application thereof of functional magnetic MOFs (Metal-Organic Frameworks) material | |
| Cai et al. | Use of a novel sol–gel dibenzo-18-crown-6 solid-phase microextraction fiber and a new derivatizing reagent for determination of aliphatic amines in lake water and human urine | |
| CN104475041A (en) | A novel method of preparing agarose magnetic microspheres and uses of the agarose magnetic microspheres in separation and purification of an IgG antibody | |
| CN104857933A (en) | Preparation and application of core-shell type magnetic metal organic framework nano-particles | |
| CN112834642A (en) | Method for determining 191 pesticide residues by combining high-oil complex matrix sample pretreatment technology with UPLC-MSMS (ultra-performance liquid chromatography-Mass Spectrometry) | |
| CN107744799A (en) | Chitosan microball, its preparation method and its application in mineral oil dielectric loss is reduced | |
| CN103399102A (en) | Method for determining total solanesol in tobaccos and tobacco products | |
| CN114247179B (en) | Grease purifying agent and preparation method and application thereof | |
| CN104338512B (en) | A kind of silica aerogel prepared by mixture with alkoxy silane | |
| TWI648253B (en) | Method of purifying kirenol | |
| CN107096509A (en) | The sephadex and preparation method of a kind of succinic acid of amido containing α function base | |
| CN104784972A (en) | Preparation method and application of hesperidin immunoaffinity column | |
| CN104729878A (en) | Novel passive water body sampling technique based on supported ionic liquid | |
| CN102824756A (en) | Method for screening triglyceride enzyme inhibitor from plant extract | |
| CN100496705C (en) | Hydrophilic NPLC, filler and separating method | |
| CN109975085B (en) | Sample pretreatment method for endogenous brassinosteroids in plant sample and pretreatment solid phase material adopted by same | |
| CN107374255B (en) | A kind of catamaran type intelligent filtering cup | |
| CN114994199B (en) | Preparation of MOF@COF core-shell composite material and application of MOF@COF core-shell composite material as solid phase extraction adsorbent | |
| CN105879851B (en) | Graphite oxide ene-type in-line purification Solid Phase Extraction integral post and preparation method and purposes | |
| CN107876025A (en) | Hydroxypropyl chitosan microballoon, its preparation method and its application in mineral oil dielectric loss is reduced |
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 |