CN104784969A - Method for removing metal ions in solution by sulfydryl-containing quinoline functionalized mesoporous silica - Google Patents
Method for removing metal ions in solution by sulfydryl-containing quinoline functionalized mesoporous silica Download PDFInfo
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Abstract
The invention discloses a method for removing metal ions in solution by sulfydryl-containing quinoline functionalized mesoporous silica. Mesoporous silica is used as a carrier and a skeleton and reacts with a sulfydryl-containing quinoline compound to form the sulfydryl-containing quinoline functionalized mesoporous silica with a high chelating ability; the sulfydryl-containing quinoline functionalized mesoporous silica is used as an adsorbent and the metal ions in medicine solution are adsorbed on mesoporous silica solid so as to separate the metal ions from medicine. According to the method, the metal ions in the solution can be efficiently and selectively adsorbed; the method adopts a simple process, is low in cost, has a high metal adsorption rate, is environmental-friendly and cannot cause pollution to the medicine or an intermediate of the medicine when effectively removing heavy metal.
Description
Technical field
The present invention relates to a kind of use removes metal ion in solution method containing the functional mesoporous silica of mercaptoquinoline class.
Background technology
In recent years, how metallic catalyst is more next is incorporated in pharmaceutical synthesis process, as reactions such as hydrogenation, carbonylation synthesis, coupling and isomerization, in these technical process, the metal residue inevitably having certain content is retained in product, in view of the potential impact of metal pair health, on February 21st, 2008, EMEA/CHMP promulgated the policy paper that metallic catalyst or metal reagent residual quantity limit specify, and formally will implement on September 1st, 2008 in European Union.This directive document is divided three classes according to the harm of metal residual to human body, wherein, platinum, palladium, ruthenium, rhodium, iridium, osmium and molybdenum, nickel, chromium, vanadium, plumbous about ten kinds of metals are listed in the highest has remarkable safety concerns (carcinogenic) list, middle traditional Chinese medicines prison department more and more payes attention to the control problem of residual metal level in medicine, China is as global drug consumption and manufacture big country, metal residual in the production and consumption of effective management and control medicine for the health of the people and the competitiveness of pharmaceutical industry all significant, in medicine, the removal of metal has become a study hotspot in recent years.
As needed rhodium caprylate to need triphenylphosphine radium chloride to elect hydrogenation catalyst, palladium as coupling catalyst etc. as cyclization catalyst, ivermectin building-up process in berkelium south class pharmaceutical synthesis process.These catalyst often include the metal ion of tens ppm after inactivation is separated at medicine or its intermediate.
Summary of the invention
A kind of use is the object of the present invention is to provide to remove the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, can metal ion efficiently, selectively in adsorbent solution, technique is simple, cost is low, metal adsorption rate is high, environmental friendliness, and while effective removal heavy metal, can not pollute medicine or its intermediate.
For achieving the above object, technical scheme of the present invention is that a kind of use of design removes the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, take mesopore silicon oxide as carrier and skeleton, mesopore silicon oxide is reacted with containing mercaptoquinoline compounds, what form strong sequestering power contains the functional mesoporous silica of mercaptoquinoline class, the functional mesoporous silica of mercaptoquinoline class is contained for adsorbent with this, by the adsorption of metal ions in drug solution on mesopore silicon oxide solid, make metal ion and medical separation.
Preferably, described metal ion comprises platinum group metal ion and gold, silver, nickel, mercury, lead ion; Described solution is the aqueous solution or organic solution.
Preferably, above-mentioned use removes the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, specifically comprises the steps:
A) preparation of mesopore silicon oxide:
Take a certain amount of template and ethyl orthosilicate is placed in reactor, in water-bath, 70 DEG C are stirred to whole dissolving, a small amount of watery hydrochloric acid is added under fast stirring to system, after clear colloidal sol to be formed, on the glass sheet, under room temperature, drying forms gel to uniform application, dry 10 hours are continued in 70 DEG C, slowly be warming up to 450 DEG C again, heat treatment 6 hours, obtains mesopore silicon oxide;
B) containing the preparation of the functional mesoporous silica of mercaptoquinoline class:
By prepared mesopore silicon oxide in 120 DEG C of dryings 8 hours, take a small amount of, add in the xylene solution containing 10% mercaptoquinoline compounds, in 70 DEG C of stirring and refluxing 24 hours, place and be chilled to room temperature, filter, 4 hours are washed with dimethylbenzene, to remove unreacted mercaptoquinoline compounds, in 70 DEG C of dryings 12 hours, obtain containing the functional mesoporous silica of mercaptoquinoline class; Wherein, the mass ratio of described mercaptoquinoline and mesopore silicon oxide is 1: 5-10;
C) metal biosorption:
First its adsorption capacity is calculated according to the gauge of mercaptoquinoline in change mesopore silicon oxide, the theoretical amount containing the functional mesoporous silica of mercaptoquinoline class is calculated with adsorption capacity, doubly will add in medicine (or pharmaceutical intermediate) solution upon adsorption containing the functional mesoporous silica of mercaptoquinoline class by the 3-10 of theoretical amount, soak absorption 0.5-24hr; Filter, measure the tenor in the rear solution of absorption, calculate adsorption rate.
Preferably, described step a) in, mesopore silicon oxide being ground to specific surface is 400-600m
2/ g, average pore size is not less than 6nm.
Preferably, described steps d) in, the temperature of solution upon adsorption controls at 0-70 DEG C.
Preferably, described steps d) in, first will load in fixed leg containing the functional mesoporous silica of mercaptoquinoline class, solution upon adsorption is adsorbed by fixed leg with the speed of 0.2-5L/hr, adsorption time is 0.5-24hr, until the concentration of metal ions in solution no longer reduces.
Preferably, described steps d) in, the consumption containing the functional mesoporous silica of mercaptoquinoline class is 5-60 grams per liter.
Advantage of the present invention and beneficial effect are: provide a kind of use to remove the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, can metal ion efficiently, selectively in adsorbent solution, technique is simple, cost is low, metal adsorption rate is high, environmental friendliness, and while effective removal heavy metal, can not pollute medicine or its intermediate.
Functional mesoporous silica absorption method has the high strength silica of certain pore size and specific surface for skeleton and carrier, be connected with the active function compound of ad hoc structure, can be combined by the metal ion efficiently, selectively in drug solution, form stable chelate, reach the object with medical separation.
Containing the sulfydryl in the functional mesoporous silica of mercaptoquinoline class, there is extremely strong chelating ligands effect, stable hexatomic ring configuration chelate can be formed with many metal ions, significantly improve mesopore silicon oxide to the coordination of metal ion, adsorption capacity, obtain the functional mesoporous silica that absorption property is good.
Adsorbent in the present invention--have containing the functional mesoporous silica of mercaptoquinoline class that adsorption rate is fast, adsorption rate high, advantage is while effective removal heavy metal, can not pollute medicine or its intermediate, reset procedure is applicable to the aqueous solution and all organic solution systems, and can react under normal temperature; Adsorbent material is easy to get, and preparation technology is simple and direct, is easy in midget plant's large-scale production.
Adsorbent is to the adsorption rate of platinum-group noble metals ion all more than 95%, and what have reaches 99.9%.To concentration be not more than 0.01ppm metallic solution still have good adsorption effect.
Detailed description of the invention
Below in conjunction with embodiment, the specific embodiment of the present invention is further described.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
The technical scheme that the present invention specifically implements is:
Embodiment 1
A) preparation of mesopore silicon oxide: take 4g template P123 and 3.5ml ethyl orthosilicate in reactor, be stirred to whole dissolving at 70 DEG C in water-bath, under rapid stirring, add the watery hydrochloric acid 2ml of 0.1N to system, after clear colloidal sol to be formed, uniform application on the glass sheet, under room temperature, dry formation gel, continues dry 10 hours at 70 DEG C, is more slowly warming up to 450 DEG C, heat treatment 6 hours, obtain mesopore silicon oxide, be ground to required order number, for subsequent use.
B) containing the preparation of the functional mesoporous silica of mercaptoquinoline class: by above-mentioned mesopore silicon oxide at 120 DEG C dry 8 hours, take 10g, add in the 100ml xylene solution containing 1g8-mercaptoquinoline, stirring and refluxing 24 hours at 70 DEG C, places cold room temperature processed, filters, 4 hours are washed with dimethylbenzene, to remove unreacted mercaptoquinoline compounds, at 70 DEG C, drying 12 hours, obtains the functional mesoporous silica of thiooxine.
C) metal biosorption: accurate weighing 0.5g triphenylphosphine radium chloride (rhodium content 11%) and ivermectin 20g, adding volume is in the volumetric flask of 1L, add toluene to scale, obtain the toluene solution that rhodium-containing is 550ppm, in this solution, rhodium total content is 0.53mmol, calculating its adsorption capacity according to the gauge of thiooxine on silica is 3-7mmol/g, known 0.1g modified silica-gel just can palladium completely in adsorbent solution, be adopted as and add adsorbent by more than ten times of theoretical amount, actual addition is 1 gram (following this example of example reference).Added in above-mentioned solution by functional mesoporous for 1g8-mercaptoquinoline silica, fully stir half an hour, filter, measuring rhodium content in solution is 6ppm, and adsorption rate is 98.9%.
Embodiment 2
On the basis of embodiment 1, described step c) change into: accurate weighing 0.6g chloroplatinic acid (platinum content 37%) and the former medicine 20g of tetracycline, adding volume is in the volumetric flask of 1L, add toluene to scale, obtain the toluene solution that platiniferous is 2220ppm, in this solution, platinum total content is 1.2mmol, calculating its adsorption capacity according to the gauge of thiooxine on mesopore silicon oxide is 5-8mmol/g, known 0.5g modified silica-gel just can platinum completely in adsorbent solution, be adopted as and add adsorbent by more than ten times of theoretical amount, actual addition is 5 grams.Functional mesoporous for 5g8-mercaptoquinoline silica is loaded about 60 centimetres, internal diameter is in the glass tube of 2 centimetres, add in above-mentioned solution from glass tube top, be that 1000ml/hr slowly flows through adsorbent with flow velocity, measuring platinum content in the rear solution of absorption after absorption is 17ppm, and adsorption rate is 99.2%.
Embodiment 3
A) preparation of mesopore silicon oxide: take 4g template P123 and 3.5ml ethyl orthosilicate in reactor, be stirred to whole dissolving at 70 DEG C in water-bath, under rapid stirring, add the watery hydrochloric acid 2ml of 0.1N to system, after clear colloidal sol to be formed, uniform application on the glass sheet, under room temperature, dry formation gel, continues dry 10 hours at 70 DEG C, is more slowly warming up to 450 DEG C, heat treatment 6 hours, obtain mesopore silicon oxide, be ground to required order number, for subsequent use.
B) containing the preparation of the functional mesoporous silica of mercaptoquinoline class: by above-mentioned mesopore silicon oxide at 120 DEG C dry 8 hours, take 20g, add in the 120ml xylene solution containing 4g5-amido-thiooxine, stirring and refluxing 24 hours at 70 DEG C, places cold room temperature processed, filters, 4 hours are washed with dimethylbenzene, to remove unreacted mercaptoquinoline compounds, at 70 DEG C, drying 12 hours, obtains the functional mesoporous silica of 5-amido-thiooxine.
C) metal biosorption: accurate weighing 0.5g rhodium caprylate (rhodium content 26%) and Meropenem 20g, adding volume is in the volumetric flask of 1L, add methyl alcohol to scale, obtain the 1L methanol solution that rhodium-containing is 1300ppm, in this solution, rhodium total content is 1.26mmol, calculating its adsorption capacity according to 5-amido-thiooxine at the gauge of mesopore silicon oxide is 5-8mmol/g, known 1g modified silica-gel just can rhodium completely in adsorbent solution, adopt more than ten times of theoretical amount to add adsorbent, actual addition is 10 grams.Added in above-mentioned solution by the functional mesoporous silica of 10g5-amido-thiooxine, fully stir half an hour, filter, measuring rhodium content in solution is 11ppm, and adsorption rate is 99.2%.
Embodiment 4
On the basis of embodiment 3, described step c) change into: accurate weighing 0.5g nickel nitrate (nickel content 20%), adding volume is in the volumetric flask of 1L, add absolute ethyl alcohol to scale, obtain the nickeliferous ethanolic solution for 1000ppm, in this solution, nickel total content is 1.7mmol, calculating its adsorption capacity according to the gauge of 5-amido-thiooxine on mesopore silicon oxide is 5-8mmol/g, known 0.4g modified silica-gel just can nickel completely in adsorbent solution, be adopted as and add adsorbent by more than ten times of theoretical amount, actual addition is 4 grams.Functional mesoporous for 4g5-amido-thiooxine silica is loaded about 60 centimetres, internal diameter is in the glass tube of 2 centimetres, add in above-mentioned solution from glass tube top, be that 1000ml/hr slowly flows through adsorbent with flow velocity, measuring nickel content in the rear solution of absorption after absorption is 13ppm, and adsorption rate is 98.7%.
Embodiment 5
A) preparation of mesopore silicon oxide: take 4g template P123 and 3.5ml ethyl orthosilicate in reactor, be stirred to whole dissolving at 70 DEG C in water-bath, under rapid stirring, add the watery hydrochloric acid 2ml of 0.1N to system, after clear colloidal sol to be formed, uniform application on the glass sheet, under room temperature, dry formation gel, continues dry 10 hours at 70 DEG C, is more slowly warming up to 450 DEG C, heat treatment 6 hours, obtain mesopore silicon oxide, be ground to required order number, for subsequent use.
B) containing the preparation of the functional mesoporous silica of mercaptoquinoline class: by above-mentioned mesopore silicon oxide at 120 DEG C dry 8 hours, take 25g, add in the 100ml xylene solution containing 3g5-methyl-thiooxine, stirring and refluxing 24 hours at 70 DEG C, places cold room temperature processed, filters, 4 hours are washed with dimethylbenzene, to remove unreacted mercaptoquinoline compounds, at 70 DEG C, drying 12 hours, obtains the functional mesoporous silica of 5-methyl-thiooxine.
C) metal biosorption: accurate weighing 0.5g palladium (palladium content 47%) and the former medicine 20g of Tamiflu, adding volume is in the volumetric flask of 1L, add toluene to scale, obtain containing the 1L toluene solution that palladium is 2350ppm, in this solution, palladium total content is 2.2mmol, calculating its adsorption capacity according to the gauge of 5-methyl-thiooxine on mesopore silicon oxide is 5-8mmol/g, known 1g modified silica-gel just can palladium completely in adsorbent solution, adopt more than ten times of theoretical amount to add adsorbent, actual addition is 12 grams.Added in above-mentioned solution by the functional mesoporous silica of 12g5-methyl-thiooxine, fully stir half an hour, filter, measuring palladium content in solution is 39ppm, and adsorption rate is 98.3%.
Embodiment 6
A) preparation of mesopore silicon oxide: take 4g template P123 and 3.5ml ethyl orthosilicate in reactor, be stirred to whole dissolving at 70 DEG C in water-bath, under rapid stirring, add the watery hydrochloric acid 2ml of 0.1N to system, after clear colloidal sol to be formed, uniform application on the glass sheet, under room temperature, dry formation gel, continues dry 10 hours at 70 DEG C, is more slowly warming up to 450 DEG C, heat treatment 6 hours, obtain mesopore silicon oxide, be ground to required order number, for subsequent use.
B) containing the preparation of the functional mesoporous silica of mercaptoquinoline class: by above-mentioned mesopore silicon oxide at 120 DEG C dry 8 hours, take 10g, add in the 100ml xylene solution containing 1.5g5-hydroxyl-thiooxine, stirring and refluxing 24 hours at 70 DEG C, places cold room temperature processed, filters, 4 hours are washed with dimethylbenzene, to remove unreacted mercaptoquinoline compounds, at 70 DEG C, drying 12 hours, obtains the functional mesoporous silica of 5-hydroxyl-thiooxine.
C) metal biosorption: accurate weighing 0.5g iridous chloride (iridium content 58%) and the former medicine 20g of first dimension rhzomorph, adding volume is in the volumetric flask of 1L, add the hydrochloric acid of 1N to scale, obtaining containing iridium is the aqueous solution of 2900ppm, in this solution, iridium total content is 1.5mmol, calculating its adsorption capacity according to the gauge of 5-hydroxyl-thiooxine on mesopore silicon oxide is 5-8mmol/g, known 1g modified silica-gel just can iridium completely in adsorbent solution, be adopted as and add adsorbent by more than ten times of theoretical amount, actual addition is 10 grams.Added in above-mentioned solution by the functional mesoporous silica of 10g5-hydroxyl-thiooxine, fully stir half an hour, filter, measuring iridium content in solution is 27ppm, and adsorption rate is 99.1%.
Embodiment 7
On the basis of embodiment 6, described step c) change into:
Accurate weighing 0.5g ruthenium trichloride (ruthenium content 35%) and the former medicine 20g of erythromycin, adding volume is in the volumetric flask of 1L, add absolute ethyl alcohol to scale, obtaining containing ruthenium is the ethanolic solution of 1750ppm, in this solution, ruthenium total content is 1.7mmol, calculating its adsorption capacity according to the gauge of 5-hydroxyl-thiooxine on mesopore silicon oxide is 5-8mmol/g, known 0.4g modified silica-gel just can ruthenium completely in adsorbent solution, be adopted as and add adsorbent by more than ten times of theoretical amount, actual addition is 4 grams.Functional mesoporous for 4g5-hydroxyl-thiooxine silica is loaded about 60 centimetres, internal diameter is in the glass tube of 2 centimetres, add in above-mentioned solution from glass tube top, be that 1000ml/hr slowly flows through adsorbent with flow velocity, measuring ruthenium content in the rear solution of absorption after absorption is 29ppm, and adsorption rate is 98.3%.
Embodiment 8
On the basis of embodiment 6, described step c) change into: accurate weighing 0.5g rhodium dicarbonyl acetylacetonate (rhodium content 40%) and the former medicine 20g of erythromycin, adding volume is in the volumetric flask of 1L, add chloroform to scale, obtain the aqueous solution that rhodium-containing is 2000ppm, in this solution, rhodium total content is 2.9mmol, calculating its adsorption capacity according to the gauge of 5-hydroxyl-thiooxine on mesopore silicon oxide is 5-8mmol/g, known 1g modified silica-gel just can platinum completely in adsorbent solution, be adopted as and add adsorbent by more than ten times of theoretical amount, actual addition is 10 grams.10g5-hydroxyl-thiooxine is loaded about 60 centimetres at mesopore silicon oxide, internal diameter is in the glass tube of 2 centimetres, add in above-mentioned solution from glass tube top, be that 1000ml/hr slowly flows through adsorbent with flow velocity, measuring rhodium content in the rear solution of absorption after absorption is 9ppm, and adsorption rate is 99.6%.
In the various embodiments described above, silica gel be milled to specific surface be 400-600m
2/ g, average pore size is not less than 6nm.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. by the method removing metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, it is characterized in that, take mesopore silicon oxide as carrier and skeleton, mesopore silicon oxide is reacted with containing mercaptoquinoline compounds, what form strong sequestering power contains the functional mesoporous silica of mercaptoquinoline class, contain the functional mesoporous silica of mercaptoquinoline class for adsorbent with this, by the adsorption of metal ions in drug solution on mesopore silicon oxide solid, make metal ion and medical separation.
2. use according to claim 1 removes the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, and it is characterized in that, described metal ion comprises platinum group metal ion and gold, silver, nickel, mercury, lead ion; Described solution is the aqueous solution or organic solution.
3. use according to claim 1 and 2 removes the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, it is characterized in that, specifically comprises the steps:
A) preparation of mesopore silicon oxide:
Take a certain amount of template and ethyl orthosilicate is placed in reactor, in water-bath, 70 DEG C are stirred to whole dissolving, a small amount of watery hydrochloric acid is added under fast stirring to system, after clear colloidal sol to be formed, on the glass sheet, under room temperature, drying forms gel to uniform application, dry 10 hours are continued in 70 DEG C, slowly be warming up to 450 DEG C again, heat treatment 6 hours, obtains mesopore silicon oxide;
B) containing the preparation of the functional mesoporous silica of mercaptoquinoline class:
By prepared mesopore silicon oxide in 120 DEG C of dryings 8 hours, take a small amount of, add in the xylene solution containing 10% mercaptoquinoline compounds, in 70 DEG C of stirring and refluxing 24 hours, place and be chilled to room temperature, filter, 4 hours are washed with dimethylbenzene, to remove unreacted mercaptoquinoline compounds, in 70 DEG C of dryings 12 hours, obtain containing the functional mesoporous silica of mercaptoquinoline class; Wherein, the mass ratio of described mercaptoquinoline and mesopore silicon oxide is 1: 5-10;
C) metal biosorption:
First its adsorption capacity is calculated according to the gauge of mercaptoquinoline in change mesopore silicon oxide, the theoretical amount containing the functional mesoporous silica of mercaptoquinoline class is calculated with adsorption capacity, doubly will add in solution upon adsorption containing the functional mesoporous silica of mercaptoquinoline class by the 3-10 of theoretical amount, soak absorption 0.5-24hr.
4. use according to claim 3 removes the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, it is characterized in that, described step a) in, mesopore silicon oxide being ground to specific surface is 400-600m
2/ g, average pore size is not less than 6nm.
5. use according to claim 4 removes the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, it is characterized in that, described steps d) in, the temperature of solution upon adsorption controls at 0-70 DEG C.
6. use according to claim 5 removes the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, it is characterized in that, described steps d) in, first will load in fixed leg containing the functional mesoporous silica of mercaptoquinoline class, solution upon adsorption is adsorbed by fixed leg with the speed of 0.2-5L/hr, adsorption time is 0.5-24hr, until the concentration of metal ions in solution no longer reduces.
7. use according to claim 6 removes the method for metal ion in solution containing the functional mesoporous silica of mercaptoquinoline class, it is characterized in that, described steps d) in, the consumption containing the functional mesoporous silica of mercaptoquinoline class is 5-60 grams per liter.
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