CN104784969B - With the method for the functional mesoporous silica removal metal ion in solution of class containing mercaptoquinoline - Google Patents
With the method for the functional mesoporous silica removal metal ion in solution of class containing mercaptoquinoline Download PDFInfo
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Abstract
The invention discloses a kind of methods with the functional mesoporous silica removal metal ion in solution of class containing mercaptoquinoline, using mesopore silicon oxide as carrier and skeleton, mesopore silicon oxide and the compound of class containing mercaptoquinoline are reacted, form the functional mesoporous silica of class containing mercaptoquinoline of strong sequestering power, using the functional mesoporous silica of the class containing mercaptoquinoline as adsorbent, by the adsorption of metal ions in drug solution on mesopore silicon oxide solid, make metal ion and medical separation.The present invention can efficiently, the selectively metal ion in adsorbent solution, it is simple for process, at low cost, metal adsorption rate is high, environmental-friendly, and while heavy metal is effectively removed, will not be to drug or wherein mesosome pollutes.
Description
Technical field
The present invention relates to a kind of methods with the functional mesoporous silica removal metal ion in solution of class containing mercaptoquinoline.
Background technology
In recent years, metallic catalyst is more next mostly is incorporated in pharmaceutical synthesis process, such as hydrogenation, carbonylation synthesis, coupling and different
The reactions such as structure, in these technical process, the metal residue for inevitably having certain content is retained in product,
In view of potential impact of the metal to health, EMEA/CHMP has promulgated metallic catalyst or metal reagent on 2 21st, 2008
Policy paper as defined in residual quantity limit, and will formally implement in European Union within 1st in Septembers in 2008.The directive document is according to gold
Belong to residual to be divided into three classes to the harm of human body, wherein, about ten kinds of metal quilts of platinum, palladium, ruthenium, rhodium, iridium, osmium and molybdenum, nickel, chromium, vanadium, lead
Be classified as it is highest have notable safety concerns (carcinogenic) list, Chinese drug administration department is to the control problem of residual metal level in drug
Increasingly pay attention to, China is as global drug consumption and manufactures big country, the metal in effective management and control drug production and consumption
Residual be all of great significance for the health of the people and the competitiveness of pharmaceutical industry, in drug the removal of metal become
A research hotspot in recent years.
Such as in berkelium south, class pharmaceutical synthesis process needs rhodium caprylate to need triphenyl as cyclization catalyst, ivermectin building-up process
Phosphine radium chloride elects hydrogenation catalyst, palladium as coupling catalyst etc..These catalyst inactivation separate after often
In drug or the in-between metal ion in vivo containing tens ppm.
The content of the invention
It is an object of the invention to provide a kind of with the functional mesoporous silica removal GOLD FROM PLATING SOLUTION category of class containing mercaptoquinoline
The method of ion, can efficiently, the selectively metal ion in adsorbent solution, it is simple for process, at low cost, metal adsorption rate is high, ring
Border is friendly, and while heavy metal is effectively removed, will not be to drug or wherein mesosome pollutes.
To achieve the above object, the technical scheme is that design is a kind of to use the functional mesoporous oxidation of class containing mercaptoquinoline
The method that silicon removes metal ion in solution, using mesopore silicon oxide as carrier and skeleton, by mesopore silicon oxide with containing mercaptoquinoline
Class compound is reacted, and forms the functional mesoporous silica of class containing mercaptoquinoline of strong sequestering power, contains mercaptoquinoline with this
The functional mesoporous silica of class is adsorbent, by the adsorption of metal ions in drug solution on mesopore silicon oxide solid, makes gold
Belong to ion and medical separation.
Preferably, the metal ion includes platinum group metal ion and gold, silver, nickel, mercury, lead ion；The solution is water
Solution or organic solution.
Preferably, the above-mentioned method with the functional mesoporous silica removal metal ion in solution of class containing mercaptoquinoline,
Specifically comprise the following steps：
A) preparation of mesopore silicon oxide：
It weighs a certain amount of template and ethyl orthosilicate is placed in reactor, stirred in water-bath to whole dissolvings for 70 DEG C,
A small amount of dilute hydrochloric acid is added in system, after clear colloidal sol to be formed, uniformly smear on the glass sheet, room temperature under fast stirring
Lower drying forms gel, in 70 DEG C continue dry 10 it is small when, then be slowly warming up to 450 DEG C, when heat treatment 6 is small, obtain mesoporous oxygen
SiClx；
B) preparation of the functional mesoporous silica of class containing mercaptoquinoline：
By prepared mesopore silicon oxide when 120 DEG C of dryings 8 are small, weigh on a small quantity, add in containing 10% mercaptoquinoline class
Close object xylene solution in, in 70 DEG C be stirred at reflux 24 it is small when, placement be cooled to room temperature, filter, with dimethylbenzene wash 4 it is small when,
To remove unreacted mercaptoquinoline class compound, when 70 DEG C of dryings 12 are small, the functional mesoporous oxygen of class containing mercaptoquinoline is obtained
SiClx；Wherein, the mass ratio of the mercaptoquinoline and mesopore silicon oxide is 1: 5-10；
C) absorption of metal ion：
Its adsorption capacity is calculated according to gauge of the mercaptoquinoline in mesopore silicon oxide is changed first, is calculated with adsorption capacity
The theoretical amount of the functional mesoporous silica of class containing mercaptoquinoline will contain mercaptoquinoline class functionalization by 3-10 times of theoretical amount
Mesopore silicon oxide is added in drug (or pharmaceutical intermediate) solution to be adsorbed, impregnates absorption 0.5-24hr；Filtering measures absorption
Tenor in solution afterwards calculates adsorption rate.
Preferably, in the step a), mesopore silicon oxide is ground to specific surface as 400-600m2/ g, average pore size is not
Less than 6nm.
Preferably, in the step d), the temperature of solution to be adsorbed is controlled at 0-70 DEG C.
Preferably, in the step d), it will first contain the functional mesoporous silica of mercaptoquinoline class and be fitted into fixed column, and make to treat
The solution of absorption is adsorbed with the speed of 0.2-5L/hr by fixed column, adsorption time 0.5-24hr, until in solution
Concentration of metal ions no longer reduces.
Preferably, in the step d), the dosage of the functional mesoporous silica of class containing mercaptoquinoline is 5-60 g/l.
The advantages of the present invention are：A kind of functional mesoporous silica removal of class containing mercaptoquinoline is provided
The method of metal ion in solution, can efficiently, selectively the metal ion in adsorbent solution, simple for process, at low cost, metal be inhaled
Attached rate is high, environmental-friendly, and while heavy metal is effectively removed, will not be to drug or wherein mesosome pollutes.
Functional mesoporous silica absorption method is using the high intensity silica with certain pore size and specific surface as skeleton
And carrier, be connected with the active function compound of specific structure, can efficiently, selectively with the metal ion knot in drug solution
It closes, forms stable chelate, achieve the purpose that and medical separation.
Sulfydryl in the functional mesoporous silica of class containing mercaptoquinoline has extremely strong chelating ligands effect, can be with many
Metal ion forms stable hexa-atomic ring configuration chelate, greatly improves coordination of the mesopore silicon oxide to metal ion, adsorption energy
Power obtains the good functional mesoporous silica of absorption property.
The functional mesoporous silica of adsorbent in the present invention -- class containing mercaptoquinoline has that adsorption rate is fast, adsorption rate is high
The features such as, advantage is while heavy metal is effectively removed, will not be to drug or wherein mesosome pollutes, and reset procedure can
Suitable for aqueous solution and all organic solution systems, and can be reacted under room temperature；Adsorbent material is easy to get, and preparation process is simple and direct,
It is easy in midget plant's large-scale production.
Adsorbent is to the adsorption rate of platinum-group noble metals ion more than 95%, and some is up to 99.9%.It is little to concentration
Still there is good adsorption effect in the metallic solution of 0.01ppm.
Specific embodiment
With reference to embodiment, the specific embodiment of the present invention is further described.Following embodiment is only used for more
Add and clearly demonstrate technical scheme, and be not intended to limit the protection scope of the present invention and limit the scope of the invention.
The technical solution that the present invention is embodied is：
Embodiment 1
A) preparation of mesopore silicon oxide：4g template P123 and 3.5ml ethyl orthosilicates are weighed in reactor, in water-bath
Stirring is to whole dissolvings at 70 DEG C, to the dilute hydrochloric acid 2ml of system addition 0.1N, clear colloidal sol to be formed under quick stirring
Afterwards, uniformly smear on the glass sheet, drying at room temperature forms gel, continue at 70 DEG C dry 10 it is small when, then be slowly warming up to 450
DEG C, when heat treatment 6 is small, mesopore silicon oxide is obtained, is ground to required mesh number, it is spare.
B) preparation of the functional mesoporous silica of class containing mercaptoquinoline：By above-mentioned mesopore silicon oxide, drying 8 is small at 120 DEG C
When, weigh 10g, add in the 100ml xylene solutions of the mercaptoquinoline containing 1g8-, be stirred at reflux at 70 DEG C 24 it is small when, place it is cold
Room temperature processed, filtering, with dimethylbenzene wash 4 it is small when, it is small that 12 are dried to remove unreacted mercaptoquinoline class compound, at 70 DEG C
When, obtain the functional mesoporous silica of thiooxine.
C) absorption of metal ion：Accurate weighing 0.5g triphenylphosphines radium chloride (rhodium content 11%) and ivermectin 20g,
It adds in the volumetric flask that volume is 1L, adds in toluene to scale, obtain the toluene solution that rhodium-containing is 550ppm, rhodium is total in the solution
Content is 0.53mmol, its adsorption capacity is calculated as 3-7mmol/g according to gauge of the thiooxine on silica, it is known that
0.1g modified silica-gels can be completely in adsorbent solution palladium, be adopted as adding in adsorbent by ten times or more of theoretical amount, it is real
Border additive amount is 1 gram (following example reference this example).The functional mesoporous silica of 1g8- mercaptoquinolines is added in into above-mentioned solution
In, be sufficiently stirred half an hour, filter, measure solution in rhodium content be 6ppm, adsorption rate 98.9%.
Embodiment 2
On the basis of embodiment 1, the step c) is changed to：Accurate weighing 0.6g chloroplatinic acids (platinum content 37%) and Fourth Ring
Plain active compound 20g is added in the volumetric flask that volume is 1L, addition toluene to scale, obtains the toluene solution that platiniferous is 2220ppm,
Platinum total content is 1.2mmol in the solution, and calculating its adsorption capacity according to gauge of the thiooxine on mesopore silicon oxide is
5-8mmol/g, it is known that the platinum that 0.5g modified silica-gels can be completely in adsorbent solution is adopted as ten times or more by theoretical amount
Adsorbent is added in, actual interpolation amount is 5 grams.The functional mesoporous silica of 5g8- mercaptoquinolines is packed into about 60 centimetres, internal diameter 2
Centimetre glass tube in, will in above-mentioned solution from glass tube top add in, slowly flow through adsorbent by 1000ml/hr of flow velocity,
It is 17ppm that platinum content in solution is measured after absorption after absorption, adsorption rate 99.2%.
Embodiment 3
A) preparation of mesopore silicon oxide：4g template P123 and 3.5ml ethyl orthosilicates are weighed in reactor, in water-bath
Stirring is to whole dissolvings at 70 DEG C, to the dilute hydrochloric acid 2ml of system addition 0.1N, clear colloidal sol to be formed under quick stirring
Afterwards, uniformly smear on the glass sheet, drying at room temperature forms gel, continue at 70 DEG C dry 10 it is small when, then be slowly warming up to 450
DEG C, when heat treatment 6 is small, mesopore silicon oxide is obtained, is ground to required mesh number, it is spare.
B) preparation of the functional mesoporous silica of class containing mercaptoquinoline：By above-mentioned mesopore silicon oxide, drying 8 is small at 120 DEG C
When, weigh 20g, add in the 120ml xylene solutions of amido containing 4g5--thiooxine, be stirred at reflux at 70 DEG C 24 it is small when,
Place cold room temperature processed, filter, with dimethylbenzene wash 4 it is small when, to remove unreacted mercaptoquinoline class compound, dried at 70 DEG C
12 it is small when, obtain 5- amidos-functional mesoporous silica of thiooxine.
C) absorption of metal ion：Accurate weighing 0.5g rhodium caprylates (rhodium content 26%) and Meropenem 20g add in volume
For in the volumetric flask of 1L, methanol is added in scale, obtains the 1L methanol solutions that rhodium-containing is 1300ppm, rhodium total content in the solution
For 1.26mmol, its adsorption capacity is calculated as 5-8mmol/g in the gauge of mesopore silicon oxide according to 5- amidos-thiooxine,
It understands the rhodium that 1g modified silica-gels can be completely in adsorbent solution, adds in adsorbent using ten times or more of theoretical amount, actually
Additive amount is 10 grams.The functional mesoporous silica of 10g5- amidos-thiooxine is added in above-mentioned solution, is sufficiently stirred half
Hour, filtering, measure solution in rhodium content be 11ppm, adsorption rate 99.2%.
Embodiment 4
On the basis of embodiment 3, the step c) is changed to：Accurate weighing 0.5g nickel nitrates (nickel content 20%) add in
Volume is in the volumetric flask of 1L, adds in absolute ethyl alcohol to scale, obtains the nickeliferous ethanol solution for 1000ppm, nickel in the solution
Total content is 1.7mmol, its adsorption capacity is calculated as 5- according to 5- amidos-gauge of the thiooxine on mesopore silicon oxide
8mmol/g, it is known that the nickel that 0.4g modified silica-gels can be completely in adsorbent solution, be adopted as by ten times or more of theoretical amount plus
Enter adsorbent, actual interpolation amount is 4 grams.It is interior by functional mesoporous about 60 centimetres of the silica loading of 4g5- amidos-thiooxine
Footpath is in 2 centimetres of glass tube, will be added in above-mentioned solution from glass tube top, suction is slowly flowed through as 1000ml/hr using flow velocity
Attached dose, it is 13ppm that nickel content in solution is measured after absorption after absorption, adsorption rate 98.7%.
Embodiment 5
A) preparation of mesopore silicon oxide：4g template P123 and 3.5ml ethyl orthosilicates are weighed in reactor, in water-bath
Stirring is to whole dissolvings at 70 DEG C, to the dilute hydrochloric acid 2ml of system addition 0.1N, clear colloidal sol to be formed under quick stirring
Afterwards, uniformly smear on the glass sheet, drying at room temperature forms gel, continue at 70 DEG C dry 10 it is small when, then be slowly warming up to 450
DEG C, when heat treatment 6 is small, mesopore silicon oxide is obtained, is ground to required mesh number, it is spare.
B) preparation of the functional mesoporous silica of class containing mercaptoquinoline：By above-mentioned mesopore silicon oxide, drying 8 is small at 120 DEG C
When, weigh 25g, add in the 100ml xylene solutions of methyl containing 3g5--thiooxine, be stirred at reflux at 70 DEG C 24 it is small when,
Place cold room temperature processed, filter, with dimethylbenzene wash 4 it is small when, to remove unreacted mercaptoquinoline class compound, dried at 70 DEG C
12 it is small when, obtain 5- methyl-functional mesoporous silica of thiooxine.
C) absorption of metal ion：Accurate weighing 0.5g palladiums (palladium content 47%) and Tamiflu active compound 20g add in volume
For in the volumetric flask of 1L, toluene is added in scale, is obtained containing the 1L toluene solutions that palladium is 2350ppm, palladium total content in the solution
For 2.2mmol, its adsorption capacity is calculated as 5-8mmol/g according to 5- methyl-gauge of the thiooxine on mesopore silicon oxide,
It understands the palladium that 1g modified silica-gels can be completely in adsorbent solution, adds in adsorbent using ten times or more of theoretical amount, actually
Additive amount is 12 grams.The functional mesoporous silica of 12g5- methyl-thiooxine is added in above-mentioned solution, is sufficiently stirred half
Hour, filtering, measure solution in palladium content be 39ppm, adsorption rate 98.3%.
Embodiment 6
A) preparation of mesopore silicon oxide：4g template P123 and 3.5ml ethyl orthosilicates are weighed in reactor, in water-bath
Stirring is to whole dissolvings at 70 DEG C, to the dilute hydrochloric acid 2ml of system addition 0.1N, clear colloidal sol to be formed under quick stirring
Afterwards, uniformly smear on the glass sheet, drying at room temperature forms gel, continue at 70 DEG C dry 10 it is small when, then be slowly warming up to 450
DEG C, when heat treatment 6 is small, mesopore silicon oxide is obtained, is ground to required mesh number, it is spare.
B) preparation of the functional mesoporous silica of class containing mercaptoquinoline：By above-mentioned mesopore silicon oxide, drying 8 is small at 120 DEG C
When, 10g is weighed, is added in the 100ml xylene solutions of hydroxyl containing 1.5g5--thiooxine, it is small to be stirred at reflux 24 at 70 DEG C
When, place cold room temperature processed, filtering, with dimethylbenzene wash 4 it is small when, to remove unreacted mercaptoquinoline class compound, at 70 DEG C
When drying 12 is small, 5- hydroxyls-functional mesoporous silica of thiooxine is obtained.
C) absorption of metal ion：Accurate weighing 0.5g iridous chlorides (iridium content 58%) and first dimension rhzomorph active compound 20g, add
Enter in the volumetric flask that volume is 1L, add in the hydrochloric acid of 1N to scale, obtain containing the aqueous solution that iridium is 2900ppm, iridium in the solution
Total content is 1.5mmol, its adsorption capacity is calculated as 5- according to 5- hydroxyls-gauge of the thiooxine on mesopore silicon oxide
8mmol/g, it is known that the iridium that 1g modified silica-gels can be completely in adsorbent solution is adopted as adding in by ten times or more of theoretical amount
Adsorbent, actual interpolation amount are 10 grams.The functional mesoporous silica of 10g5- hydroxyls-thiooxine is added in above-mentioned solution,
Be sufficiently stirred half an hour, filter, measure solution in iridium content be 27ppm, adsorption rate 99.1%.
Embodiment 7
On the basis of embodiment 6, the step c) is changed to：
Accurate weighing 0.5g ruthenium trichlorides (ruthenium content 35%) and erythromycin active compound 20g add in the volumetric flask that volume is 1L
In, addition absolute ethyl alcohol to scale obtains the ethanol solution for 1750ppm containing ruthenium, and ruthenium total content is 1.7mmol in the solution,
Its adsorption capacity is calculated as 5-8mmol/g according to 5- hydroxyls-gauge of the thiooxine on mesopore silicon oxide, it is known that 0.4g changes
Property silica gel can be completely in adsorbent solution ruthenium, be adopted as adding in adsorbent by ten times or more of theoretical amount, actual interpolation
It measures as 4 grams.The functional mesoporous silica of 4g5- hydroxyls-thiooxine is packed into about 60 centimetres, internal diameter is 2 centimetres of glass tube
In, it will be added in above-mentioned solution from glass tube top, slowly flow through adsorbent by 1000ml/hr of flow velocity, surveyed after absorption
Ruthenium content is 29ppm in solution after fixed absorption, adsorption rate 98.3%.
Embodiment 8
On the basis of embodiment 6, the step c) is changed to：Accurate weighing 0.5g rhodium dicarbonyl acetylacetonate (rhodium contents
40%) and erythromycin active compound 20g, addition volume are in the volumetric flask of 1L, add in chloroform to scale, obtain rhodium-containing as 2000ppm
Aqueous solution, rhodium total content is 2.9mmol in the solution, according to 5- hydroxyls-gauge of the thiooxine on mesopore silicon oxide
Its adsorption capacity is calculated as 5-8mmol/g, it is known that the platinum that 1g modified silica-gels can be completely in adsorbent solution is adopted as by theory
Ten times or more of dosage add in adsorbent, and actual interpolation amount is 10 grams.By 10g5- hydroxyls-thiooxine in mesopore silicon oxide
Be packed into about 60 centimetres, internal diameter is in 2 centimetres of glass tube, will be added in above-mentioned solution from glass tube top, using flow velocity as
1000ml/hr slowly flows through adsorbent, and rhodium content is 9ppm in solution after measure absorption after absorption, and adsorption rate is
99.6%.
In the various embodiments described above, it is 400-600m that silica gel, which has been milled to specific surface,2/ g, average pore size are not less than 6nm.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (2)
1. with the method for the functional mesoporous silica removal metal ion in solution of class containing mercaptoquinoline, which is characterized in that be situated between
Hole silica is carrier and skeleton, and mesopore silicon oxide and the compound of class containing mercaptoquinoline are reacted, form strong sequestering power
The functional mesoporous silica of class containing mercaptoquinoline, using the functional mesoporous silica of the class containing mercaptoquinoline as adsorbent, by medicine
Adsorption of metal ions in object solution makes metal ion and medical separation on mesopore silicon oxide solid；
The metal ion includes platinum group metal ion and gold, silver, nickel, mercury, lead ion；The solution is aqueous solution or organic matter
Solution.
2. the side according to claim 1 with the functional mesoporous silica removal metal ion in solution of class containing mercaptoquinoline
Method, which is characterized in that specifically comprise the following steps：
A) preparation of mesopore silicon oxide：
It weighs a certain amount of template and ethyl orthosilicate is placed in reactor, 70 DEG C of stirrings are to whole dissolvings in water-bath, fast
A small amount of dilute hydrochloric acid is added in system, after clear colloidal sol to be formed, uniformly smear on the glass sheet, do at room temperature under speed stirring
Dry formation gel, in 70 DEG C continue dry 10 it is small when, then be slowly warming up to 450 DEG C, when heat treatment 6 is small, obtain mesopore silicon oxide；
B) preparation of the functional mesoporous silica of class containing mercaptoquinoline：
By prepared mesopore silicon oxide when 120 DEG C of dryings 8 are small, weigh on a small quantity, add in containing 10% mercaptoquinoline class compound
Xylene solution in, in 70 DEG C be stirred at reflux 24 it is small when, placement be cooled to room temperature, filter, with dimethylbenzene wash 4 it is small when, to remove
Unreacted mercaptoquinoline class compound is gone, when 70 DEG C of dryings 12 are small, obtains the functional mesoporous silica of class containing mercaptoquinoline；
Wherein, the mass ratio of the mercaptoquinoline and mesopore silicon oxide is 1: 5-10；
C) absorption of metal ion：
Its adsorption capacity is calculated according to gauge of the mercaptoquinoline in functional mesoporous silica first, is calculated with adsorption capacity
The theoretical amount of the functional mesoporous silica of class containing mercaptoquinoline will contain mercaptoquinoline class functionalization by 3-10 times of theoretical amount
Mesopore silicon oxide is added in solution to be adsorbed, impregnates absorption 0.5-24hr；
In the step a), mesopore silicon oxide is ground to specific surface as 400-600m2/ g, average pore size are not less than 6nm；
In the step c), the temperature of solution to be adsorbed is controlled at 0-70 DEG C；
In the step c), it will first contain the functional mesoporous silica of mercaptoquinoline class and be fitted into fixed column, and make solution to be adsorbed
It is adsorbed with the speed of 0.2-5L/hr by fixed column, adsorption time 0.5-24hr, until the metal ion in solution is dense
Degree no longer reduces；
In the step c), the dosage of the functional mesoporous silica of class containing mercaptoquinoline is 5-60 g/l.
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