CN101822970B - Silicon rubber compound and preparation method and application thereof - Google Patents
Silicon rubber compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a silicon rubber compound. The structure of the silicon rubber compound is shown in the general formula (I), wherein X is oxygen atoms, nitrogen atoms or sulfur atoms, and Y is aryl, heteroaryl or heterocyclyl. The invention also provides a method for preparing the silicon rubber compound and application of the silicon rubber compound in removing heavy metals in Chinese medicament extract or electroplating effluent and other liquid. The silicon rubber compound has the advantages of readily available raw materials, low cost, simple and convenient preparation method, simple using method, capacity of efficiently, rapidly and conveniently removing heavy metal elements contained in the Chinese medicament extract or the electroplating effluent and other liquid, obvious removal effect, environmental friendliness and good industrialized prospect.
Description
Technical field
The present invention relates to a kind of silica gel compound, specifically, relate to a kind of chemical modification bonded silica gel, its preparation method and application thereof.
Background technology
Over nearly 30 years, in the economic fast development of China, problem of environmental pollution is also serious day by day, and particularly heavy-metal residual is one of the most serious pollution form of China.Heavy metal contamination is meant the environmental pollution that is caused by heavy metal or its compound, mainly is because due to the human factors such as mining, exhaust gas emission, sewage irrigation and use heavy metal goods.Heavy metal can get into food chain after contaminated soil, atmosphere and water body, and finally gets into human body.And because biological amplification, food chain from rudimentary to the high-grade progression, the enrichment gradually of objectionable impuritiess such as heavy metal, its content in vivo is with increasing.If heavy metal ion is accumulated, will bring the damage that is difficult to repair to human body, when dosage is big even can directly cause death in human body.In " world's ten big pollution incidents ", " minamata disease " incident is caused by heavy metal Hg and cadmium respectively with " itai-itai " incident.The significant damage that heavy-metal residual causes has made people have to face its existence and has striven to find terms of settlement.
Heavy metal in the Chinese medicine is mainly derived from soil pollution, the metabolic needs of Chinese medicine self and to the pollution of pollution, agricultural chemicals and the fertilizer of the accumulation ability of certain metallic element, industry " liquid, waste gas, waste residue " and the pollution in storage, processing, concocting process etc.Too high heavy-metal residual has been a undisputable fact in the Chinese medicine, this not only heavy damage the image of Chinese medicine, also caused great financial loss to China.Current, the countries and regions of import Chinese medicinal materials and Chinese patent medicine have all proposed strict demand to the heavy metal content of Chinese medicinal materials, Chinese patent medicine in the world.Limit index to heavy metal in " medicinal plant and preparation are imported and exported green industry standard " of Ministry of Foreign Trade and Economic Cooperation appearance of China country and enforcement is: total metals is answered≤20.0mg/kg; Plumbous (Pb)≤5.0mg/kg; Cadmium (Cd)≤0.3mg/kg; Mercury (Hg)≤0.2mg/kg, copper (Cu)≤20.0mg/kg, arsenic (As)≤2.0mg/kg.Therefore, the effective constituent in guaranteeing Chinese medicine is not destroyed, keeps to reduce as much as possible under the prerequisite of drug effect the focus that heavy metal content in the Chinese medicine has become the traditional Chinese medicine research field.
The method of heavy metal has following several kinds in the liquid such as removal Chinese medicine extract of using always at present, or electroplating effluent: membrane separation process, ion exchange treatment method, solvent extraction and separation method, absorption method and resin removal method etc.
But all there are many shortcomings in aforesaid method, these drawbacks limit they promotion and application in actual production.For example:
Membrane separation process; Because its separation function relies on film to realize; The pollution of film and the decay of flux in use always take place; Therefore need often to clean and safeguard, this big limitations the promotion and application of membrane separation process, the composition of the unusual complicacy of Chinese medicine extract has increased the contaminated probability of film simultaneously.
The employed ionite of ion exchange treatment method generally all demonstrates certain acid-basicity, and this has certain destruction to the effective ingredient in the Chinese medicine extract; Simultaneously, the electric charge that carries of ionite itself also might exert an influence to the effective ingredient in the Chinese medicine extract.This has just limited the application of the heavy metal ions of ion exchange method in removing Chinese medicine.
The loss of solvent takes place in solvent extraction and separation method easily in extraction process; And in complexing agent and solvent reclamation process, need to consume a large amount of energy; Simultaneously, must use organic solvent in the solvent extraction and separation method, it can extract the effective constituent in the Chinese medicine extract; Have a strong impact on the drug effect of Chinese medicine, so the application of solvent extraction and separation method receives very big restriction.
Effective ingredient in the absorption method Yin Qiyi absorption Chinese medicine extract, and be difficult to Adsorption of Heavy Metal Ions, make the application of absorption method receive very big restriction.Simultaneously, the reprocessing cycle of sorbent material is difficult for realizing.
The selectivity of resin method is single; This is because lead, cadmium, mercury and copper in the Chinese medicine extract generally exist with cationic form, but arsenic element then can exist with cationic form, also can exist with anionic form; The existence form of heavy metal relative complex makes to unite uses multiple resin; Not only increase cost, prolonged the running time, also made the reprocessing cycle of resin to realize easily.
The research of removing heavy metal ion with supercritical fluid extraction is just at the early-stage; And the supercritical fluid extraction method is relatively stricter to the requirement of equipment, equipment manufacturing cost is higher, so should still not have industrialized instance aspect the heavy metal of technology in removing Chinese medicine extract at present.
In sum, the method novel, efficient, that rapidly, easily remove heavy metal ion in liquid such as Chinese medicine extract or electroplating effluent of development with industrial prospect has very important significance.
Summary of the invention
The purpose of this invention is to provide a kind of silica gel compound that can remove the heavy metal ion that contains in the liquid such as Chinese medicine extract or electroplating effluent efficiently, fast, easily.
In order to realize the object of the invention, a kind of silica gel compound of the present invention, its structure is shown in general formula (I):
Wherein, X is Sauerstoffatom, nitrogen-atoms or sulphur atom; Y is aryl, heteroaryl or heterocyclic radical.
Y is (C in the aforesaid silica gel compound, general formula (I)
2-C
9) heteroaryl, (C
2-C
9) heteroaryl (C
1-C
6) alkyl, (C
2-C
9) heterocyclic radical, (C
2-C
9) heterocyclic radical (C
1-C
6) alkyl, (C
2-C
9) heteroaryl (C
6-C
10) aryl, (C
2-C
9) heteroaryl (C
6-C
10) aryl (C
6-C
10) aryl, (C
2-C
9) heteroaryl (C
6-C
10) aryl (C
2-C
9) heteroaryl, (C
2-C
9) heteroaryl (C
2-C
9) heteroaryl, (C
6-C
10) aryl (C
2-C
9) heteroaryl or (C
6-C
10) aryl (C
6-C
10) aryl (C
2-C
9) heteroaryl.
The ring carbon atom of Y is replaced by one or more following substituting groups in the aforesaid silica gel compound, general formula (I), and said substituting group is fluorine, chlorine, bromine, sulfydryl, hydroxyl, nitro, amino, substituted amido, (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, perfluoro (C
1-C
3) alkyl, perfluoro (C
1-C
3) alkoxyl group.
The aryl of Y comprises phenyl or naphthyl etc. in the aforesaid silica gel compound, general formula (I), and wherein the ring carbon atom of phenyl or naphthyl is replaced by 1 to 3 following substituting group, and said substituting group is fluorine, chlorine, bromine, sulfydryl, hydroxyl, nitro, amino, substituted amido, (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, perfluoro (C
1-C
3) alkyl, perfluoro (C
1-C
3) alkoxyl group.
Aforesaid silica gel compound; The heteroaryl of Y comprises pyridyl, furyl, pyrryl, thienyl, different thienyl, imidazolyl, pyrazinyl, pyrimidyl, quinolyl, isoquinolyl, pyrazolyl, thiazolyl 、 oxazolyl etc. in the general formula (I), and said heteroaryl is preferably imidazolyl, thiazolyl 、 oxazolyl, pyrazinyl.
Aforesaid silica gel compound, the ring carbon atom of said heteroaryl is replaced by 1 to 2 following substituting group, and said substituting group is fluorine, chlorine, bromine, sulfydryl, hydroxyl, nitro, amino, substituted amido, (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, perfluoro (C
1-C
3) alkyl, perfluoro (C
1-C
3) alkoxyl group.
Aforesaid silica gel compound; The heterocyclic radical of Y comprises tetrahydrofuran base, Pyrrolidine base, tetrahydro-thienyl, the different thienyl of tetrahydrochysene, imidazolidine base, tetrahydric quinoline group, tetrahydro isoquinolyl, pyrazolinyl, thiazolinyl 、 oxazolinyl etc. in the general formula (I), and said heterocyclic radical is preferably thiazolinyl, imidazolinyl.
Aforesaid silica gel compound, the ring carbon atom of said heterocyclic radical is replaced by 1 to 2 following substituting group, and said substituting group is fluorine, chlorine, bromine, sulfydryl, hydroxyl, nitro, amino, substituted amido, (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, perfluoro (C
1-C
3) alkyl, perfluoro (C
1-C
3) alkoxyl group.
The preparation method of silica gel compound of the present invention comprises the steps:
1) with silica gel in 120 ℃ of-140 ℃ of baking ovens after activation 4-6 hour, at the moisture eliminator internal cooling;
2) with activatory silica gel and chlorination reagent reaction, will obtain chlorination silica gel then and be dried to Powdered; Adopting the chlorination degree of hydrolysis-determination of acid-basetitration silica gel is n mmole/gram;
Wherein, said chlorination reagent is sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride or oxalyl chloride;
3) get the silica gel m gram that the chlorination degree is n mmole/gram; The low polar solvent, the H-X-Y of nm mmole and the organic bases of 0.5m milliliter that add the 4m-6m milliliter; Stir after 24-48 hour, filter, filter cake washs 3-5 time respectively with low polar solvent and zero(ppm) water; With the acetonitrile washing, obtain the silica gel compound shown in general formula (I) after the vacuum-drying at last;
Wherein, said low polar solvent is ETHYLE ACETATE, MTBE, THF or dioxane; Described organic bases is triethylamine, pyridine, 4,4 '-dimethylamino pyridine or diisopropyl ethyl amine.
The building-up process of said silica gel compound is:
The application of silica gel compound of the present invention heavy metal ion in removing liquid such as Chinese medicine extract, electroplating effluent, it is realized through following method:
Take by weighing an amount of silica gel compound of the present invention, join in the waste water such as Chinese medicine extract that need to handle or electroplating effluent, vigorous stirring 30～90min filters and obtains treated Chinese medicine extract or electroplate liquid.
In the present invention, because heavy metal ion is generally positively charged ion, its unoccupied orbital that has is equivalent to Lewis acid, and it can form co-ordination bond with the Lewis alkali that lone-pair electron are provided, so heavy metal ion can be removed from solution with the form of inner complex.The silicon hydroxyl on silica gel surface has adsorptivity, and a large amount of hydroxyl that the silica gel surface exists can be replaced by the heavy metal ion in the solution, demonstrates the function of cationic exchange.But directly use silica gel as sorbent material separation and concentration heavy metal element, its adsorption efficiency and selectivity are difficult to reach gratifying effect; Be incorporated in the silica gel if will contain the functional group of ligating atoms such as S, N, O, will form inner complex with heavy metal element, improved the efficient of removing heavy metal element significantly through the silica gel after the modification.
In sum, the present invention adopts the functional group that simple method will contain ligating atoms such as S, N, O to be incorporated in the silica gel from basic Organic Chemicals silica gel, prepares silica gel compound of the present invention.This silica gel compound can be removed the heavy metal ion that contains in the liquid such as Chinese medicine extract, electroplating effluent, and removal effect is obvious, and clearance is high.
The invention has the advantages that, silica gel compound of the present invention, its raw material be easy to get and cost lower; The preparation method is easy; Method of use is simple, and can remove the heavy metal ion that contains in the liquid such as Chinese medicine extract, electroplating effluent efficiently, fast, easily, and removal effect is obvious; Reach " medicinal plant and preparation are imported and exported green industry standard " and discharging standards, environmentally friendly and have an industrial prospect.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
The preparation of embodiment 1 mercaptobenzothiazole base silica gel compound
The activation in 120 ℃ of baking ovens of a certain amount of silica gel was placed on brown bottle at the moisture eliminator internal cooling and preserves after 6 hours.Get 100 gram activatory silica gel, added 60 milliliters of sulfur oxychloride reflux 48 hours.Sulfur oxychloride is revolved the dried pearl silicon chlorides rubber powder end that obtains on Rotary Evaporators, pour nitrogen, sealing is preserved.The silicon chlorides rubber powder that takes a morsel is last, adopts the method for hydrolysis-acid base titration to confirm that the chlorination degree of silica gel is 1.5 mmole/grams.
Getting the chlorination degree is silica gel 20 grams of 1.5 mmole/grams, adds 100 milliliters of ETHYLE ACETATE, 30 mmoles (5.0 gram) 2-mercaptobenzothiazole and 10 milliliters of triethylamines.After the vigorous stirring 48 hours, filter, filter cake washs respectively 5 times with ETHYLE ACETATE and zero(ppm) water, at last with the acetonitrile washing, obtains mercaptobenzothiazole base silica gel compound 23 grams after the vacuum-drying, and the building-up process of said silica gel compound is:
Detect through micro ft-ir spectroscopy, find that this silica gel compound is at 1640cm
-1(characteristic absorbance of C=N in the 2-mercaptobenzothiazole) has tangible absorption peak, shows that C=N is not destroyed in the bonding process; Simultaneously, 2600cm
-1Near the charateristic avsorption band of S-H key does not appear, show that 2-mercaptobenzothiazole is bonded on the silica gel through sulfydryl.
The preparation of embodiment 2 sulfydryl pyrazinyl silica gel compounds
The activation in 130 ℃ of baking ovens of a certain amount of silica gel was placed on brown bottle at the moisture eliminator internal cooling and preserves after 5 hours.Get 100 gram activatory silica gel, added 40 milliliters of phosphorus trichloride reflux 24 hours.Phosphorus trichloride is revolved the dried pearl silicon chlorides rubber powder end that obtains on Rotary Evaporators, pour nitrogen, sealing is preserved.The silicon chlorides rubber powder that takes a morsel is last, adopts the method for hydrolysis-acid base titration to confirm that the chlorination degree of silica gel is 1.6 mmole/grams.
Getting the chlorination degree is silica gel 40 grams of 1.6 mmole/grams, adds 240 milliliters of THFs, 64 mmoles (7.2 gram) 2-sulfydryl pyrazine and 20 milliliters of triethylamines.After the vigorous stirring 36 hours, filter, filter cake washs respectively 5 times with THF and zero(ppm) water, at last with the acetonitrile washing, obtains bonded silica gel 45 grams of sulfydryl pyrazinyl modification after the vacuum-drying, and the building-up process of said silica gel compound is:
The preparation of embodiment 3 mercaptoimidazoline base silica gel compounds
The activation in 140 ℃ of baking ovens of a certain amount of silica gel was placed on brown bottle at the moisture eliminator internal cooling and preserves after 4 hours.Get 500 gram activatory silica gel, added 300 milliliters of oxalyl chloride reflux 48 hours.Oxalyl chloride is revolved the dried pearl silicon chlorides rubber powder end that obtains on Rotary Evaporators, pour nitrogen, sealing is preserved.The silicon chlorides rubber powder that takes a morsel is last, adopts the method for hydrolysis-acid base titration to confirm that the chlorination degree of silica gel is 1.2 mmole/grams.
Getting the chlorination degree is silica gel 300 grams of 1.2 mmole/grams, adds 1200 milliliters of ETHYLE ACETATE, 360 mmoles (36.8 gram) 2-mercaptoimidazoline and 150 milliliters of diisopropyl ethyl amines.After the vigorous stirring 48 hours, filter, filter cake washs respectively 3 times with ETHYLE ACETATE and zero(ppm) water, at last with the acetonitrile washing, obtains bonded silica gel 330 grams of mercaptoimidazoline base modification after the vacuum-drying, and the building-up process of said silica gel compound is:
The preparation of embodiment 4 hydroxybenzothiazole base silica gel compounds
The activation in 130 ℃ of baking ovens of a certain amount of silica gel was placed on brown bottle at the moisture eliminator internal cooling and preserves after 5 hours.Get 100 gram activatory silica gel, added 40 milliliters of sulfur oxychloride reflux 48 hours.Oxalyl chloride is revolved the dried pearl silicon chlorides rubber powder end that obtains on Rotary Evaporators, pour nitrogen, sealing is preserved.The silicon chlorides rubber powder that takes a morsel is last, adopts the method for hydrolysis-acid base titration to confirm that the chlorination degree of silica gel is 1.3 mmole/grams.
Getting the chlorination degree is silica gel 40 grams of 1.3 mmole/grams, adds 200 milliliters of MTBEs, 52 mmoles (8.6 gram) 2-hydroxy-5-methyl base benzothiazole and 20 milliliters of diisopropyl ethyl amines.After the vigorous stirring 36 hours, filter, filter cake washs respectively 3 times with MTBE and zero(ppm) water, at last with the acetonitrile washing, obtains bonded silica gel 46 grams of hydroxybenzothiazole base modification after the vacuum-drying, and the building-up process of said silica gel compound is:
The preparation of embodiment 5 Basedol base silica gel compounds
With a certain amount of silica gel in 130 ℃ of baking ovens during activation 5 after, be placed on brown bottle at the moisture eliminator internal cooling and preserve.Get 250 gram activatory silica gel, added 150 milliliters of sulfur oxychloride reflux 48 hours.Oxalyl chloride is revolved the dried pearl silicon chlorides rubber powder end that obtains on Rotary Evaporators, pour nitrogen, sealing is preserved.The silicon chlorides rubber powder that takes a morsel is last, adopts the method for hydrolysis-acid base titration to confirm that the chlorination degree of silica gel is 1.4 mmole/grams.
Getting the chlorination degree is silica gel 100 grams of 1.4 mmole/grams, adds 400 milliliters of MTBEs, 140 mmoles (14 gram) thiazolamine and 50 milliliters of diisopropyl ethyl amines.After the vigorous stirring 48 hours, filter, filter cake washs respectively 3 times with MTBE and zero(ppm) water, at last with the acetonitrile washing, obtains bonded silica gel 110 grams of Basedol base modification after the vacuum-drying, and the building-up process of said silica gel compound is:
The preparation method of employing silica gel compound of the present invention can also obtain the modified silica-gel compound of following structural formula:
Below remove the experiment of heavy metal in the liquid such as Chinese medicine extract, electroplating effluent, further specify the present invention through silica gel compound of the present invention.
Embodiment 6 uses mercaptobenzothiazole base silica gel compound and removes the heavy metal ion in the glycyrrhizic aqueous solution
Get commercially available Radix Glycyrrhizae extractum powder 20 grams, it is dissolved with 100 ml waters.The silica gel compound that in glycyrrhizic aqueous solution, adds 10 gram embodiment 1, vigorous stirring filtered after 60 minutes, collected filtrating.
Measure the content of lead, cadmium, copper, mercury and arsenic in the glycyrrhizic aqueous solution of handling front and back with Varian 700 type inductively coupled plasma emission spectrographies (ICP-AES), result such as table 1:
Table 1
| The heavy metal element of being measured | Before handling (mg/Kg) | Handle back (mg/Kg) |
| Plumbous | 3.0 | Do not detect |
| Cadmium | 1.2 | Do not detect |
| Copper | 1.7 | Do not detect |
| Mercury | 0.0 | Do not detect |
| Arsenic | 235.2 | Do not detect |
This shows that the heavy metal ion content in the Radix Glycyrrhizae solution after mercaptobenzothiazole base silica gel compound is handled reaches " medicinal plant and preparation are imported and exported green industry standard ".
Embodiment 7 uses sulfydryl pyrazinyl silica gel compound and removes the heavy metal ion in the Root of Indigowoad aqueous solution
Get commercially available Radix Isatidis extractum powder 100 grams, it is dissolved with 500 ml waters.The silica gel compound that in the Root of Indigowoad aqueous solution, adds 45 gram embodiment 2, vigorous stirring filtered after 75 minutes, collected filtrating.
Measure the content of lead, cadmium, copper, mercury and arsenic in the Root of Indigowoad aqueous solution of handling front and back with Varian 700 type inductively coupled plasma emission spectrographies (ICP-AES), result such as table 2:
Table 2
| The heavy metal element of being measured | Before handling (mg/Kg) | Handle back (mg/Kg) |
| Plumbous | 8.0 | Do not detect |
| Cadmium | 1.4 | Do not detect |
| Copper | 6.8 | Do not detect |
| Mercury | 0.0 | Do not detect |
| Arsenic | 274.6 | Do not detect |
This shows that the heavy metal ion content in the Root of Indigowoad aqueous solution after sulfydryl pyrazinyl silica gel compound is handled reaches " medicinal plant and preparation are imported and exported green industry standard ".
Embodiment 8 uses mercaptoimidazoline base silica gel compound and removes the heavy metal ion in the Chinese medicine compound prescription
Chinese medicine compound prescription: mulberry leaf 18 grams, chrysanthemum 18 grams, northern almond 15 grams, Loquat Leaf 18 grams, the root of kudzu vine 22.5 grams, Semen Coicis 22.5 grams, reed rhizome 22.5 grams, balloonflower root 18 grams, the capsule of weeping forsythia 18 grams, Leaf of Indigowoad 22.5 grams, honeysuckle flower 18 grams, Radix Glycyrrhizae 9 grams.
Each composition in the above-mentioned compound is poured in 2.5 liters of glasswares, and each composition that adds water in the compound is not had by water logging fully, soaks after 30 minutes, is heated to boiling, boils elimination medicine after 20 minutes, collects filtrating; In filter cake, add zero(ppm) water (water yield is with suitable for the first time) again, ebuillition of heated boils after 20 minutes and leaches liquid.Merge filtrating twice, steam most water under the decompression, obtain the paste solid.After this compound is fried in shallow oil 10 pairs, the paste solid is merged, obtain about 300 gram solid pastes.
Get these paste solid 300 grams and be dissolved in 1800 ml waters, add the silica gel compound of 100 gram embodiment 3,90 minutes after-filtration of vigorous stirring are collected filtrating.
Measure the content of lead, cadmium, copper, mercury and arsenic in the Chinese medicine compound prescription of handling front and back with Varian 700 type inductively coupled plasma emission spectrographies (ICP-AES), result such as table 3:
Table 3
| The heavy metal element of being measured | Before handling (mg/Kg) | Handle back (mg/Kg) |
| Plumbous | 8.2 | Do not detect |
| Cadmium | 2.6 | Do not detect |
| Copper | 50.7 | Do not detect |
| Mercury | 3.0 | Do not detect |
| Arsenic | 180.9 | Do not detect |
This shows that the heavy metal ion content in the Chinese medicine compound prescription solution after mercaptoimidazoline base silica gel compound is handled can't detect with inductively coupled plasma emission spectrography.
Embodiment 9 uses hydroxybenzothiazole base silica gel compound and removes the heavy metal ion in the root of kudzu vine solution
Get the commercially available Chinese medicine root of kudzu vine 250 grams, obtain 50-100 purpose powder after pulverizing with the microphyte kibbler.This powder poured in 2 liters the beaker, add 1 liter of zero(ppm) water, soak after 30 minutes, be heated to boiling under the vigorous stirring, boil 20 minutes after-filtration, collect filtrating; Filter cake adds 1 liter of zero(ppm) water again, and ebuillition of heated boils after 20 minutes and leaches liquid.Merge filtrating twice, remove most water under the decompression, obtain about 20 grams of paste solid.
Get these paste solid 20 grams and be dissolved in 100 ml waters, add the silica gel compound of 10 gram embodiment 4,30 minutes after-filtration of vigorous stirring are collected filtrating.
Measure the content of lead, cadmium, copper, mercury and arsenic in the root of kudzu vine solution of handling front and back with Varian 700 type inductively coupled plasma emission spectrographies (ICP-AES), result such as table 4:
Table 4
| The heavy metal element of being measured | Before handling (mg/Kg) | Handle back (mg/Kg) |
| Plumbous | 3.0 | Do not detect |
| Cadmium | 0.9 | Do not detect |
| Copper | 15.5 | Do not detect |
| Mercury | 0.5 | Do not detect |
| Arsenic | 50.6 | Do not detect |
This shows that the heavy metal ion content in the root of kudzu vine solution after hydroxybenzothiazole base silica gel compound is handled can't detect with inductively coupled plasma emission spectrography.
Embodiment 10 uses Basedol base silica gel compound and removes the heavy metal ion in the electroplating effluent
Get 500 milliliters of the electroplating wastewaters (the pH value is 6) of certain Electroplate Factory, add the silica gel compound of 50 gram embodiment 5, vigorous stirring was filtered after 60 minutes, collected filtrating.
Measure the content of nickel in the electroplating wastewater solution of handling front and back with Varian 700 type inductively coupled plasma emission spectrographies (ICP-AES), the result is as shown in table 5:
Table 5
| The heavy metal element of being measured | Before handling (mg/Kg) | After the processing |
| Nickel | 35.8 | Do not detect |
This shows that the heavy metal nickel ion content in the electroplating wastewater after Basedol base silica gel compound is handled can not detect, reaches discharging standards.
Though, the present invention has been done detailed description in the preceding text with general explanation and specific embodiments, on basis of the present invention, can to some modifications of do or improvement, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (11)
1. a silica gel compound is characterized in that, its structure is shown in general formula (I):
Wherein, X is Sauerstoffatom, nitrogen-atoms or sulphur atom; Y is (C
2-C
9) heteroaryl, (C
2-C
9) heteroaryl (C
1-C
6) alkyl, (C
2-C
9) heterocyclic radical, (C
2-C
9) heterocyclic radical (C
1-C
6) alkyl, (C
2-C
9) heteroaryl (C
6-C
10) aryl, (C
2-C
9) heteroaryl (C
6-C
10) aryl (C
6-C
10) aryl, (C
2-C
9) heteroaryl (C
6-C
10) aryl (C
2-C
9) heteroaryl, (C
2-C
9) heteroaryl (C
2-C
9) heteroaryl, (C
6-C
10) aryl (C
2-C
9) heteroaryl or (C
6-C
10) aryl (C
6-C
10) aryl (C
2-C
9) heteroaryl, and the ring carbon atom of Y replaced by one or more following substituting groups, and said substituting group is fluorine, chlorine, bromine, sulfydryl, hydroxyl, nitro, amino, substituted amido, (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, perfluoro (C
1-C
3) alkyl or perfluoro (C
1-C
3) alkoxyl group.
2. silica gel compound according to claim 1 is characterized in that, the aryl of Y comprises phenyl or naphthyl in the general formula (I).
3. silica gel compound according to claim 2 is characterized in that, the ring carbon atom of phenyl or naphthyl is replaced by 1 to 3 following substituting group, and said substituting group is fluorine, chlorine, bromine, sulfydryl, hydroxyl, nitro, amino, substituted amido, (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, perfluoro (C
1-C
3) alkyl or perfluoro (C
1-C
3) alkoxyl group.
4. silica gel compound according to claim 1; It is characterized in that the heteroaryl of Y comprises pyridyl, furyl, pyrryl, thienyl, different thienyl, imidazolyl, pyrazinyl, pyrimidyl, quinolyl, isoquinolyl, pyrazolyl, thiazolyl Huo oxazolyl in the general formula (I).
5. silica gel compound according to claim 4 is characterized in that, said heteroaryl is imidazolyl, thiazolyl 、 oxazolyl or pyrazinyl.
6. silica gel compound according to claim 4 is characterized in that, the ring carbon atom of said heteroaryl is replaced by 1 to 2 following substituting group, and said substituting group is fluorine, chlorine, bromine, sulfydryl, hydroxyl, nitro, amino, substituted amido, (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, perfluoro (C
1-C
3) alkyl or perfluoro (C
1-C
3) alkoxyl group.
7. silica gel compound according to claim 1; It is characterized in that the heterocyclic radical of Y comprises tetrahydrofuran base, Pyrrolidine base, tetrahydro-thienyl, the different thienyl of tetrahydrochysene, imidazolidine base, tetrahydric quinoline group, tetrahydro isoquinolyl, pyrazolinyl, thiazolinyl Huo oxazolinyl in the general formula (I).
8. silica gel compound according to claim 7 is characterized in that, said heterocyclic radical is thiazolinyl or imidazolinyl.
9. silica gel compound according to claim 7 is characterized in that, the ring carbon atom of said heterocyclic radical is replaced by 1 to 2 following substituting group, and said substituting group is fluorine, chlorine, bromine, sulfydryl, hydroxyl, nitro, amino, substituted amido, (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, perfluoro (C
1-C
3) alkyl or perfluoro (C
1-C
3) alkoxyl group.
10. prepare the method for any described silica gel compound of claim 1-9, it is characterized in that, comprise the steps:
1) with silica gel in 120 ℃ of-140 ℃ of baking ovens after activation 4-6 hour, at the moisture eliminator internal cooling;
2) with activatory silica gel and chlorination reagent reaction, be dried to the chlorination silica gel that obtains Powdered then; The chlorination degree of measuring silica gel is n mmole/gram;
Wherein, said chlorination reagent is sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride or oxalyl chloride;
3) get the silica gel m gram that the chlorination degree is n mmole/gram; The low polar solvent, the H-X-Y of nm mmole and the organic bases of 0.5m milliliter that add the 4m-6m milliliter; Stir after 24-48 hour, filter, filter cake washs 3-5 time respectively with low polar solvent and zero(ppm) water; With the acetonitrile washing, obtain the silica gel compound shown in general formula (I) after the vacuum-drying at last;
Wherein, the X among the H-X-Y is Sauerstoffatom, nitrogen-atoms or sulphur atom; Y is (C
2-C
9) heteroaryl, (C
2-C
9) heteroaryl (C
1-C
6) alkyl, (C
2-C
9) heterocyclic radical, (C
2-C
9) heterocyclic radical (C
1-C
6) alkyl, (C
2-C
9) heteroaryl (C
6-C
10) aryl, (C
2-C
9) heteroaryl (C
6-C
10) aryl (C
6-C
10) aryl, (C
2-C
9) heteroaryl (C
6-C
10) aryl (C
2-C
9) heteroaryl, (C
2-C
9) heteroaryl (C
2-C
9) heteroaryl, (C
6-C
10) aryl (C
2-C
9) heteroaryl or (C
6-C
10) aryl (C
6-C
10) aryl (C
2-C
9) heteroaryl, and the ring carbon atom of Y replaced by one or more following substituting groups, and said substituting group is fluorine, chlorine, bromine, sulfydryl, hydroxyl, nitro, amino, substituted amido, (C
1-C
6) alkyl, (C
1-C
6) alkoxyl group, perfluoro (C
1-C
3) alkyl or perfluoro (C
1-C
3) alkoxyl group; Said low polar solvent is ETHYLE ACETATE, MTBE, THF or dioxane; Described organic bases is triethylamine, pyridine, 4,4 '-dimethylamino pyridine or diisopropyl ethyl amine.
11. the application of any described silica gel compound of claim 1-9 heavy metal ion in removing Chinese medicine extract, electroplating effluent.
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