CN110368905A - A kind of sulfydryl amine type functional silica gel material and its application - Google Patents
A kind of sulfydryl amine type functional silica gel material and its application Download PDFInfo
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- CN110368905A CN110368905A CN201910561912.9A CN201910561912A CN110368905A CN 110368905 A CN110368905 A CN 110368905A CN 201910561912 A CN201910561912 A CN 201910561912A CN 110368905 A CN110368905 A CN 110368905A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of sulfydryl amine type functional silica gel material and its applications.The present invention provides application of the sulfydryl amine type functional silica gel material as adsorbent selective absorption noble metal in the liquid phase.Of the invention can parse such as oxidation acid leaching method hereinafter, in addition can carry out being desorbed by strong oxidizer for precious metal adsorption present in liquid phase to 0.5ppm, resolution factor is up to 95% or more to the noble metal of concentration 1000ppm by adsorption concentration 0.5 in the liquid phase.
Description
Technical field
The present invention relates to technical field of organic chemistry, it is related to a kind of sulfydryl amine type functional silica gel material and its application.
Background technique
Noble metal based on its own value and have many unique physics, chemical property, alloy and chemicals
With more comprehensive physicochemical characteristics, it has also become the important materials of modern industry and national defense construction.Precious metal chemical complex and match
Object is closed to play in homogeneous complex catalysis, fine chemical industry and the energy for cancer, in petro chemical industry and bioengineering
Important function, therefore it is known as " vitamin in modern industry ".In the catalysis for being used as pollutant purification such as purifying vehicle exhaust
In terms of agent, more there are other metal material irreplaceable roles, and be known as " SafeClean Utilities ".Noble metal is in new and high technology
Status becomes more and more important in development, is classified as strategic materials by many countries, has special significance in national economy.As
Most of noble metal relies on for the China of import, in the manufacturing process in electronic equipment and the technique with precious metal electroplating, produces
It all may include noble metal in the waste liquid of product cleaning solution, it is many that the material containing noble metal scrapped was used arbitrarily to abandon, from
For economic benefit and environmental protection angle, recycling noble metal is required.
Due to noble metal physics, the particularity of chemical property, so as to cause the complexity of its extraction process.At present
In industrialized noble metal extraction process, in addition to part is by solvent extraction, considerable enterprise is still using classics such as precipitatings
Method, not only process is tediously long, yield is low, at high cost, and environmental pollution is more serious, large labor intensity.For general waste liquid, make
It can solve these problems with absorption resin, but for the waste liquid of process conditions harshness, such as multiple heavy noble metal process waste liquor,
Precipitating displacement is carried out to noble metal through common lye-active metal system in depositing technology, lye and active metal can introduce
High salt impurity, this itself proposes the demand of high salt tolerance interference, high-selectivity adsorption, and resin currently on the market to adsorbent
These requirements are unable to satisfy, and since absorption resin is based on macromolecular scaffold, the highest method of analyzing efficiency is desorbed at present is
Roasting ashing, roasting ashing can cause serious pollution to atmosphere.
Therefore, precious metal element high-efficiency and economic, short route, environmental-friendly, high salt tolerance interference, highly selective absorption are explored
Material, adsorption method and desorption method are imperative.
Summary of the invention
The problem to be solved by the present invention is that in view of the deficiencies of the prior art, providing a kind of sulfydryl amine type functional silica gel
Material and its application.
To solve above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
First aspect present invention provides a kind of sulfydryl amine type functional silica gel material, structural formula are as follows: [(O3/2)Si(CH2)xS(CH2)yNH(CH2CH2NH)zH]a[Si(O4/2)]b[(CH2)uWSi(O3/2)]c, wherein x is the integer from 2 to 12；Y be from 3 to
12 integer；Z is 0 to 100 integer；U is the integer from 2 to 12；W is SH or S (CH2)vSH, v are 2 to 6 integers；A, b, c
It is integer, and the ratio of a+c:b exists always between 0.000001 to 100, a and b, when c is greater than zero, the ratio of c and a+b are situated between
In 0.000001 to 10.
Technical solution of the present invention, the preferred value of the z are 1-9.
There is provided a kind of synthetic method of above-mentioned sulfydryl amine type functional silica gel material, comprising the following steps: (1) (CH3O)3Si
(CH2)xS(CH2)yCl, x are the integers from 2 to 12, and y is the integer and polyethylene polyamine NH from 3 to 122(CH2CH2NH)zH, z
Value is 0-100, and back flow reaction obtains polyamines silane coupling agent；It (2), will be more then in dicyandiamide solution with silica gel back flow reaction
Amine silane coupling agent loads on silica gel, finally adds mercaptosilane coupling agents (CH3O)3Si(CH2)uW, u are from 2 to 12
Integer；W is SH or S (CH2)vSH continues back flow reaction, loads mercaptosilane coupling agents, obtains sulfydryl amine type functional silica gel material
Material.
Technical solution of the present invention, 90-150 DEG C of the back flow reaction temperature of step (1), reaction time 0.5-5h.
Technical solution of the present invention, 0-160 DEG C of the back flow reaction temperature of step (2), reaction time 0.5-24h.
Technical solution of the present invention, polyamines silane coupling agent are with the ratio between mercaptosilane coupling agents and the amount of substance of silica gel
0.05~20:0.05~20:1.
Technical solution of the present invention, polyamines silane coupling agent are with the ratio between mercaptosilane coupling agents and the amount of substance of silica gel
0.05~5:0.05~5:1, preferably 1.5~3:1.5~3:1.
Technical solution of the present invention, used silica gel are amorphous pellets and form of spherical particles.
The granular size of technical solution of the present invention, used silica gel is 10nm-30mm, and pore size is
The coupling reaction of currently preferred technical solution, the step (2) carries out in organic solvent, described organic molten
The requirement of agent is that boiling point is higher than 90 DEG C and does not react with mercaptosilane coupling agents or polyamines silane coupling agent, such as toluene, dimethylbenzene,
Heptane, water etc..
Currently preferred technical solution, in the step (2): quantitative polyamines silane coupling agent is dissolved in organic solvent
In, 2h-12h is reacted under 120-160 DEG C of temperature, normal pressure, and mercaptosilane coupling agents the reaction was continued 2-6h is then added, uses polarity
Stirring solvent washing is filtered several times, is dried overnight to obtain sulfydryl amine type functional silica gel material.
Second aspect of the present invention provides above-mentioned sulfydryl amine type silica gel material as adsorbent selective absorption in the liquid phase
The application of noble metal.
Technical solution of the present invention, the application is to expensive in the system of waste liquid containing inorganic salts of middle strong acidity (pH < 6)
Metal carries out selective absorption.
In technical solution of the present invention, the salt anionic in the inorganic salts waste liquid system includes but is not limited to Cl-,
Br-, NO3 -, SO4 2-, S2O4 2-。
Technical solution of the present invention, the application system are strong acid, contain high concentration Na, K, Mg, Ca salt system；Or it is strong
Acid contains the metal such as Cu, Ni, Zn that complex anion can be formed with part complexing power, Fe salt system；Or strong acid, containing height
Concentration Na, K, Mg, Ca salt system, and the metal such as Cu, Ni, Zn of complex anion, Fe salt can be formed with part complexing power
System.
Technical solution of the present invention, the strong acid are the hydrochloric acid of 0-12M, sulfuric acid, nitric acid etc.；It is described it is with high salt be inorganic
Salinity reaches the system of 10000ppm or more.
Technical solution of the present invention, the application is to the noble metal progress in multiple heavy noble metal acid system with high salt
Selective absorption.Repeatedly heavy noble metal process waste liquor needs to carry out precipitating displacement to noble metal using lye-active metal system,
Since lye and active metal can introduce base metal with high salt such as Cu, Ni, Zn, Fe, Na, K, Mg, Ca etc. impurity, so to suction
Attached dose itself proposes high salt tolerance interference, high-selectivity adsorption demand, using the present invention have sulfydryl amine type silica gel material make
It can highly selective, orientation recycling noble metal for adsorbent.
Technical solution of the present invention, the adsorbent is in room temperature to 200 DEG C of uses.
Technical solution of the present invention, the noble metal include but is not limited to platinum, palladium, rhodium, iridium, ruthenium, osmium.
Technical solution of the present invention, the concentration 0.5ppm to 1000ppm of noble metal in liquid-phase system to be removed.
The present invention also provides a kind of desorption analytic method, the sulfydryl amine type silica gel material after the absorption noble metal passes through strong
Oxidant destroys the structure of functional groups of sulfydryl amine type silica gel material, makes the noble metal adsorbed on sulfydryl amine type silica gel material from sulfydryl
Removing forms the aqueous solution of noble metal on amine type silica gel material, achievees the purpose that desorption parsing.
Currently preferred technical solution, the strong oxidizer are concentrated nitric acid, and concentrated hydrochloric acid (concentration 9-12M), chloroazotic acid is (dense
Nitric acid: concentrated hydrochloric acid volume ratio=1:3), inverse chloroazotic acid (concentrated nitric acid: concentrated hydrochloric acid volume ratio=3:1), the desorption parsing are as follows: add
Enter strong oxidizer, heated oxide, then room temperature washes pickling, collects washing lotion.
In technical solution of the present invention, the strong oxidizer is chlorine, and the gases such as ozone, the desorption resolves to, draw
Enter strong oxidizer, after heated oxide, is then rinsed under room temperature with acid such as hydrochloric acid, collection washing lotion.
Beneficial effects of the present invention:
In middle acid salt-containing system, noble metal exists in the form of complex anion, other base metal impurities such as Cu, Ni, Zn,
Fe etc. exists in the form of cationic, cooperate sulfydryl amine type functional silica gel material provided by the invention in acid condition with proton
In conjunction with forming ammonium salt structure, and mercapto-amine can further with noble metal chela and, keep its not easily to fall off, form stable cyclic annular tie
Structure, thus can realize in strong acid salt-containing system noble metal high-selectivity adsorption, and sulfydryl amine type function provided by the invention
SiClx glue material adsorbent is in strong acid high salt as your gold can be achieved in 12M concentrated hydrochloric acid, saturated sodium-chloride high salt
The selective absorption of category.Including the waste liquid to process conditions harshness such as multiple heavy noble metal acid system with high salt, precious metal smelting
Residual noble metal in factory's hydrochloride waste system etc. carries out selective absorption.
Silica gel material containing mercapto-amine of the invention is not necessarily to pre-treatment, can be directly used for the selective absorption of noble metal, technique
It is simple and convenient.
The adsorbent of silica gel material containing mercapto-amine of the invention in the liquid phase adsorption concentration 0.5 to concentration 1000ppm your gold
Belong to, it can be by precious metal adsorption present in liquid phase to 0.5ppm hereinafter, being taken off additionally by strong oxidizer to the adsorbent
The recycling for realizing noble metal is smelted in attached parsing such as oxidation acid leaching method, concentration, and resolution factor is up to 95% or more.
Specific embodiment
In order to make it easy to understand, the present invention will be described in detail by specific embodiment below.It needs to refer in particular to
Out, these descriptions are only exemplary description, and are not meant to limit the scope of the invention.Opinion according to this specification
It states, many variations of the invention, change will be apparent from for those skilled in the art.
Embodiment 1
In the 500mL three-necked flask for being equipped with glass stopper and condensation reflux unit be added diethylenetriamine (0.4mol) and
3- (3- chloropropyl) thiopropyl trimethoxy silane (0.4mol) flows back at 130 DEG C is cooled to 70 DEG C after 2.5h, and methanol is added
(40mL) flows back 1 hour afterwards, after cooling, put into dimethylbenzene (125ml) and amorphous silica gel (90g, 147-500 μm,Makall mixed solution) at 125 DEG C after reflux 2h, then puts into 3- mercaptopropyl trimethoxysilane
(0.2mol) is cooling after continuous heating 5 hours afterwards.Filtering dry product M after washing 5 times with methanol, wherein x=3, y=3, z
=2, u=3, W SH.
Embodiment 2
In the 500mL three-necked flask for being equipped with glass stopper and condensation reflux unit be added polyethylene polyamine (0.4mol) and
3- (3- chloropropyl) thiopropyl trimethoxy silane (0.4mol) flows back at 130 DEG C is cooled to 70 DEG C after 2.5h, and methanol is added
(40mL) flows back 1 hour afterwards, after cooling, put into dimethylbenzene (125ml) and spherical silica gel (90g, 147-500 μm,Makall mixed solution) at 125 DEG C after reflux 2h, then puts into 3- mercaptopropyl trimethoxysilane
(0.2mol) is cooling after continuous heating 5 hours afterwards.Filtering dry product M after washing 5 times with methanol, wherein wherein x=3, y=
3, z=9, u=3, W SH.
Embodiment 3
Rhodium to 300ml containing 300-400ppm, iridium, 400ppm iron, 1000ppm zinc are saturated certain precious metal smelting of sodium salt
10g embodiment 1 is added in secondary heavy palladium process of acidic (3M hydrochloric acid) waste liquid of factory, the adsorbent implemented in 2 stirs 8- at 40 DEG C
Filtering is separated by solid-liquid separation after 20 hours, carries out inductive coupling plasma emission spectrograph (ICP-OES) detection to filtrate,
Middle rhodium, iridium content < 1ppm, the equal concentration of iron, zinc is unchanged compared with stoste, and solution realizes high and low metal efficient selective separation.
Embodiment 4
Contain 100ppm palladium, platinum, rhodium, 50000ppm iron, to 1000ml solution in certain precious metal smelting factory 2M hydrochloride waste
Middle addition 12g embodiment 1, the adsorbent in embodiment 2 is filtered after stirring at normal temperature 6-16 hours and is separated by solid-liquid separation, to filter
Liquid carries out inductive coupling plasma emission spectrograph (ICP-OES) detection, and concentration of iron is substantially unchanged, wherein palladium, platinum content
It is limited lower than detection, rhodium content < 1ppm.
Embodiment 5
By embodiment 3, the adsorbent in embodiment 4 takes 10g to be added in the 63% concentrated nitric acid liquid of 32ml, at 120 DEG C
Lower stirring 6 hours, filtering carry out inductive coupling plasma emission spectrograph (ICP-OES) to filtrate and detect bullion content,
Resolution factor is 98% or more.
Embodiment 6
By embodiment 3, the adsorbent in embodiment 4 takes 10g to be added in the 63% inverse chloroazotic acid liquid of 32ml, at 120 DEG C
Lower stirring 6 hours, filtering carry out inductive coupling plasma emission spectrograph (ICP-OES) to filtrate and detect bullion content,
Resolution factor is 98% or more.
Embodiment 7
By embodiment 3, the 12M concentrated hydrochloric acid that the adsorbent in embodiment 4 takes 10g that 32ml is added leads to chlorine at 120 DEG C and stirs
It mixes 6 hours, filters, inductive coupling plasma emission spectrograph (ICP-OES) is carried out to filtrate and detects bullion content, parsing
Rate is 95% or more.
The above examples are only for illustrating the technical concept and characteristics of the present invention, and its object is to allow person skilled in the art to be
It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.
Claims (13)
1. a kind of sulfydryl amine type functional silica gel material, it is characterised in that: structural formula are as follows: [(O3/2)Si(CH2)xS(CH2)yNH
(CH2CH2NH)zH]a[Si(O4/2)]b[(CH2)uWSi(O3/2)]c, wherein x is the integer from 2 to 12；Y is the integer from 3 to 12；
Z is 0 to 100 integer；U is the integer from 2 to 12；W is SH or S (CH2)vSH, v are 2 to 6 integers；A, b, c are integer,
And the ratio of a+c:b exists always between 0.000001 to 100, a and b, when c is greater than zero, the ratio of c and a+b between
0.000001 to 10.
2. sulfydryl amine type functional silica gel material according to claim 1, it is characterised in that: the z value is 1-9.
3. the synthetic method of sulfydryl amine type functional silica gel material described in claim 1, it is characterised in that: including following step
It is rapid: (1) (CH3O)3Si(CH2)xS(CH2)yCl, x are the integers from 2 to 12, and y is the integer and polyethylene polyamine from 3 to 12
NH2(CH2CH2NH)zH, z value are 0-100, and back flow reaction obtains polyamines silane coupling agent；(2) then in dicyandiamide solution and
Silica gel back flow reaction on silica gel by the load of polyamines silane coupling agent finally adds mercaptosilane coupling agents (CH3O)3Si
(CH2)uW, u are the integers from 2 to 12；W is SH or S (CH2)vSH continues back flow reaction, loads mercaptosilane coupling agents, obtains
Sulfydryl amine type silica gel material.
4. the synthetic method of sulfydryl amine type functional silica gel material according to claim 3, it is characterised in that: used silica gel
For amorphous pellets and form of spherical particles；The granular size of used silica gel is 10nm-30mm, and pore size is
5. sulfydryl amine type silica gel material described in claim 1 is as adsorbent, selective absorption noble metal is answered in the liquid phase
With.
6. application according to claim 5, it is characterised in that: the application is inorganic to containing for middle strong acidity (pH < 6)
Noble metal in bisulfate waste liquor system carries out selective absorption.
7. application according to claim 6, it is characterised in that: the salt anionic in the inorganic salts waste liquid system includes
But it is not limited to Cl-, Br-, NO3 -, SO4 2-, S2O4 2-。
8. application according to claim 5, it is characterised in that: the application system is strong acid, contains high concentration Na, K,
Mg, Ca salt system；Or strong acid, contain the Ni metal with part complexing power, Ni, Zn, Fe salt system；Or strong acid, containing height
Concentration Na, K, Mg, Ca salt system, and the Ni metal with part complexing power, Ni, Zn, Fe salt system.
9. application according to claim 8, it is characterised in that: the strong acid is the acid of 0-12M；Described is with high salt for nothing
Machine salinity reaches the system of 10000ppm or more.
10. application according to claim 5, it is characterised in that: the application is salt acidic to multiple heavy noble metal height
Noble metal in system carries out selective absorption.
11. application according to claim 5, it is characterised in that: the adsorption temp is in room temperature to 200 DEG C of uses；It is described
Noble metal includes but is not limited to platinum, palladium, rhodium, iridium, ruthenium, osmium；The concentration 0.5ppm of noble metal is extremely in liquid-phase system to be removed
1000ppm。
12. application according to claim 6, it is characterised in that: the application includes: by the sulfydryl after absorption noble metal
Amine type silica gel material destroys the structure of functional groups of sulfydryl amine type silica gel material by strong oxidizer, makes on sulfydryl amine type silica gel material
The noble metal of absorption removes the aqueous solution for forming noble metal from sulfydryl amine type silica gel material, achievees the purpose that desorption parsing.
13. application according to claim 6, it is characterised in that: the strong oxidizer be concentrated nitric acid, concentrated hydrochloric acid, chloroazotic acid,
Inverse chloroazotic acid, the desorption parsing are as follows: strong oxidizer is added, heated oxide, then room temperature washes pickling, collects washing lotion；
The strong oxidizer is chlorine, and ozone gas, the desorption resolves to, introducing strong oxidizer, after heated oxide, then
It is rinsed under room temperature with acid, collects washing lotion.
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| CN111939875A (en) * | 2020-07-20 | 2020-11-17 | 杨南超 | Targeted silica gel material adsorbent and application thereof |
| CN112694529A (en) * | 2021-02-05 | 2021-04-23 | 无锡定象改性硅胶材料有限公司 | High-purity phycocyanin and method for extracting phycocyanin from spirulina |
| CN113106252A (en) * | 2021-02-20 | 2021-07-13 | 苏州硒诺唯新新材料科技有限公司 | Method for removing palladium from silver electrolyte by using multifunctional silica gel adsorbent |
| CN113893886A (en) * | 2021-09-30 | 2022-01-07 | 苏州硒诺唯新新材料科技有限公司 | Sulfamic acid type functionalized silica gel material and application thereof in water purification |
| CN113952942A (en) * | 2021-12-22 | 2022-01-21 | 苏州硒诺唯新新材料科技有限公司 | Modified functional silica gel material and preparation method and application thereof |
| CN114042433A (en) * | 2021-09-30 | 2022-02-15 | 苏州硒诺唯新新材料科技有限公司 | Quaternary ammonium base type functional silica gel material and application thereof in water purification |
| CN115624957A (en) * | 2022-12-06 | 2023-01-20 | 苏州硒诺唯新新材料科技有限公司 | Modified functional silica gel material and preparation method and application thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111939875A (en) * | 2020-07-20 | 2020-11-17 | 杨南超 | Targeted silica gel material adsorbent and application thereof |
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| CN112694529B (en) * | 2021-02-05 | 2022-12-20 | 无锡定象改性硅胶材料有限公司 | High-purity phycocyanin and method for extracting phycocyanin from spirulina |
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| CN113893886A (en) * | 2021-09-30 | 2022-01-07 | 苏州硒诺唯新新材料科技有限公司 | Sulfamic acid type functionalized silica gel material and application thereof in water purification |
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