CN109092268A - A kind of renewable dicyandiamide modified tannin adsorbent and preparation method thereof and production system - Google Patents
A kind of renewable dicyandiamide modified tannin adsorbent and preparation method thereof and production system Download PDFInfo
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- CN109092268A CN109092268A CN201811162977.8A CN201811162977A CN109092268A CN 109092268 A CN109092268 A CN 109092268A CN 201811162977 A CN201811162977 A CN 201811162977A CN 109092268 A CN109092268 A CN 109092268A
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The present invention relates to a kind of renewable dicyandiamide modified tannin adsorbent and preparation method thereof and production system, the structural formula of above-mentioned renewable dicyandiamide modified tannin adsorbent are as follows:In preparation method provided by the invention, pass through optimization reaction mixing speed and the rate of addition of dicyandiamide, obtain a kind of uniform particle diameter and the good renewable dicyandiamide modified tannin adsorbent of consistency, above-mentioned renewable dicyandiamide modified tannin adsorbent reaches 70mg/g or more to the adsorbance of Co and Ni within the scope of pH 3.5-7.5,60% or more is improved than existing tannin adsorbent, is 2-5 times or more of other biological adsorbent.
Description
Technical field
The present invention relates to field of material technology more particularly to a kind of renewable dicyandiamide modified tannin adsorbent and its preparations
Method and production system.
Background technique
Vegatable tannin abundance, it is at low cost, rich in phenolic hydroxyl group, be easy be modified, be a kind of biology having a extensive future
Adsorbent material.Tannin can dissolve in water, it is therefore desirable to which being prepared into the insoluble adsorbent material of water could use.Currently, containing tannin
It is novel that adsorbent is roughly divided into tannin phenolic resin, modified tannin resin, scion grafting macromolecule substrate solidified tannin, tannin foam etc.
4 seed type such as adsorbent material.1993, Nakajima etc. be reported in for the first time it is sodium hydroxide catalyzed under the conditions of formaldehyde and persimmon tannin hand over
Connection solidification prepares adsorbent, Au (III) in the adsorbent energy efficient absorption aqueous solution of chloraurate.There is researcher to make tannin modification
Its area load is nitrogenous or sulfur-containing group small molecule such as dimethylamine, bis-thiourea, N- aminoguanidine etc., improves its energy for adsorbing noble metal
Power, but such method of modifying utilizes the reagents such as paraformaldehyde or concentrated acid more, and needs pyroreaction condition, and preparation cost is higher and easy
Generate pollution.Existing research and technology mainly consider adsorption capacity is high, selectivity is strong etc. in terms of adsorbent preparation, can not accomplish
Partial size and morphology controllable there is no to form batch preparation process.
Summary of the invention
For the above problem present in existing adsorbent, now provide a kind of renewable dicyandiamide modified tannin adsorbent and
Preparation method and production system, it is desirable to provide the preparation method provided through the invention prepare a kind of adsorption capacity it is high and
The renewable dicyandiamide modified tannin adsorbent of partial size, morphology controllable.
Specific technical solution is as follows
The first aspect of the invention is to provide a kind of renewable dicyandiamide modified tannin adsorbent, has such spy
Sign, structural formula are shown below:
Wherein, n 30-50.
The second aspect of the invention is to provide a kind of preparation method of above-mentioned renewable dicyandiamide modified tannin adsorbent,
It has the feature that, includes the following steps:
1) ammonia spirit, is added into the reaction kettle for fill tanning solution, stir and first is added thereto after mixing
Aldehyde solution reacts 2-5h under the conditions of speed of agitator is 40-300r/min, reaction temperature is 40-85 DEG C, then with 0.1-0.5L/
Dicyandiamide solution is added dropwise in the reaction kettle by min rate of addition, in speed of agitator is 40-300r/min, reaction temperature is
2-5h is reacted under the conditions of 40-85 DEG C, wherein the ratio between amount of substance of tannin, ammonia, formaldehyde, dicyandiamide is 20-35:5-6:1-
1.5:1-1.2；
2), the reaction solution of end of reaction in step 1) is crystallized under the conditions of 20-40 DEG C, Crystallization Separation, Crystallization Separation obtains
The supernatant liquor obtained, which is pumped into the reaction kettle, continues to participate in reaction, and the sediment that Crystallization Separation obtains is centrifuged described
Renewable dicyandiamide modified tannin adsorbent, the mother liquor for being centrifugated acquisition is tested through content of formaldehyde, if content of formaldehyde is greater than
5mg/L is then pumped into the reaction kettle and continues to participate in reaction, if content of formaldehyde is less than 5mg/L, direct outlet.
Above-mentioned solution is using water as solvent in the present invention.
The third aspect of the invention is to provide a kind of renewable dicyandiamide modified tannin suction using above-mentioned preparation method
Attached dose of production system, has the feature that, comprising: for store tanning solution the first storage tank, for storing ammonium hydroxide
Two storage tanks, the third storage tank for storing formalin, the 4th storage tank for storing dicyandiamide solution, reaction kettle, thickener,
Whizzer, formaldehyde on-line detector, electronic three-way valve, the first storage tank, the second storage tank, third storage tank and the 4th storage tank difference
It is connected to by pipeline with reaction kettle, the arrival end of thickener is connected to by pipeline with the outlet end of reaction kettle, the outlet of thickener
End is connected to by pipeline with the arrival end of whizzer, and the top of thickener is connected to by pipeline with reaction kettle, is centrifugated
The outlet end of device is connected to by pipeline with the arrival end of formaldehyde on-line detector, and the outlet end of formaldehyde on-line detector passes through pipeline
It is connected to the arrival end of electronic three-way valve, one of outlet end of electronic three-way valve is connected to by pipeline with reaction kettle, electronics
Another outlet end of triple valve is connected to by pipeline with outer comb, and formaldehyde on-line detector is electrically connected with electronic three-way valve.
The beneficial effect of above scheme is:
In preparation method provided by the invention, by optimization reaction mixing speed and the rate of addition of dicyandiamide, obtain
A kind of uniform particle diameter and good renewable dicyandiamide modified tannin adsorbent of consistency, above-mentioned renewable dicyandiamide modified tannin are inhaled
Attached dose reaches 70mg/g or more to the maximal absorptive capacity of Co and Ni within the scope of pH 3.5-7.5, improves than existing tannin adsorbent
60% or more, it is 2-5 times or more of other biological adsorbent.
Detailed description of the invention
Fig. 1 is that the SEM test of the renewable dicyandiamide modified tannin adsorbent prepared in the embodiment of the present invention 1 is shown
It is intended to.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art without creative labor it is obtained it is all its
His embodiment, shall fall within the protection scope of the present invention.
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
The present invention will be further explained below with reference to the attached drawings and specific examples, but not as the limitation of the invention.
Embodiment 1
A kind of renewable dicyandiamide modified tannin adsorbent, preparation method are as follows:
Ammonium hydroxide in tanning solution and the second storage tank in first storage tank is successively pumped into reaction kettle, stir and is mixed
Formalin in third storage tank is pumped into reaction kettle after even, in speed of agitator is 40r/min, reaction temperature is 40 DEG C of conditions
Lower reaction 2h, then with 0.1L/min rate of addition by dicyandiamide solution (tannin, ammonia, the first in above-mentioned reaction in the 4th storage tank
The ratio between amount of substance of aldehyde, dicyandiamide is 20:5:1:1) it is added dropwise in the reaction kettle, it is 40r/min, reacts in speed of agitator
Temperature reacts 2h under the conditions of being 40 DEG C, and reacting rear material, which is pumped into thickener, carries out condensing crystallizing, and condensing crystallizing temperature is 20 DEG C,
Upper layer overflow clear liquid after condensing crystallizing is pumped into reaction kettle, and lower layer's magma after condensing crystallizing, which is pumped into whizzer, to carry out
Centrifuge separation, the solid for being centrifugated acquisition is renewable dicyandiamide modified tannin adsorbent, is centrifugated the clear liquid of acquisition
It is detected through formaldehyde on-line detector, if content of formaldehyde is greater than 5mg/L, is pumped into reaction kettle and continues to participate in reaction, if formaldehyde contains
Amount is less than 5mg/L, then direct outlet；
Fig. 1 is the SEM test schematic diagram of the renewable dicyandiamide modified tannin adsorbent provided in the present embodiment, can by figure
Know renewable dicyandiamide modified tannin adsorbent uniform particle sizes provided by the invention and consistency is good.
The characterization of adsorption of renewable dicyandiamide modified tannin adsorbent is as shown in the table in the present invention:
| C (wt%) | 56.6 |
| H (wt%) | 4.6 |
| N (wt%) | 5.4 |
| O (wt%) | 33.4 |
| Specific surface area (m2/g) | 2.38 |
| Pore volume (m3/g) | 0.156 |
Adsorption test is carried out in the present invention, test result is as follows:
As seen from the above table, renewable dicyandiamide modified tannin adsorbent provided by the invention is to Co2+And Ni2+Removal rate
It is 100%, adsorbance is respectively 61.7mg/L and 66.1mg/L；Meanwhile it can also Adsorption Mn2+、Zn2+、Mg2+、Pb2+、
Cu2+、Cd2+、Cr3+Equal metal ions, show higher adsorption recovery ability and anti-ion interference sexuality.
Embodiment 2
A kind of renewable dicyandiamide modified tannin adsorbent, preparation method are as follows:
Ammonium hydroxide in tanning solution and the second storage tank in first storage tank is successively pumped into reaction kettle, stir and is mixed
Formalin in third storage tank is pumped into reaction kettle after even, in speed of agitator is 200r/min, reaction temperature is 60 DEG C of items
React 3.5h under part, then with 0.3L/min rate of addition by dicyandiamide solution (tannin, ammonia in above-mentioned reaction in the 4th storage tank
The ratio between amount of substance of gas, formaldehyde, dicyandiamide is 27:5.5:1.3:1.1) it is added dropwise in the reaction kettle, be in speed of agitator
200r/min, reaction temperature react 3h under the conditions of being 60 DEG C, and reacting rear material, which is pumped into thickener, carries out condensing crystallizing, concentration knot
Brilliant temperature be 30 DEG C, the upper layer overflow clear liquid after condensing crystallizing is pumped into reaction kettle, lower layer's magma after condensing crystallizing be pumped into from
It is centrifuged in centrifugal separator, the solid for being centrifugated acquisition is renewable dicyandiamide modified tannin adsorbent, centrifugation
The clear liquid that separation obtains is detected through formaldehyde on-line detector, if content of formaldehyde is greater than 5mg/L, is pumped into reaction kettle and is continued to participate in
Reaction, if content of formaldehyde is less than 5mg/L, direct outlet；
The characterization of adsorption of renewable dicyandiamide modified tannin adsorbent is as shown in the table in the present invention:
| C (wt%) | 57.1 |
| H (wt%) | 4.4 |
| N (wt%) | 5.2 |
| O (wt%) | 33.3 |
| Specific surface area (m2/g) | 2.36 |
| Pore volume (m3/g) | 0.149 |
Adsorption test is carried out in the present invention, test result is as follows:
As seen from the above table, renewable dicyandiamide modified tannin adsorbent provided by the invention is to Co2+And Ni2+Removal rate
Close to 100%, adsorbance is respectively 74.2mg/L and 63.3mg/L；Meanwhile it can also Adsorption Mn2+、Zn2+、Mg2+、
Pb2+、Cu2+、Cd2+、Cr3+Equal metal ions, show higher adsorption recovery ability and anti-ion interference sexuality.
Embodiment 3
A kind of renewable dicyandiamide modified tannin adsorbent, preparation method are as follows:
Ammonium hydroxide in tanning solution and the second storage tank in first storage tank is successively pumped into reaction kettle, stir and is mixed
Formalin in third storage tank is pumped into reaction kettle after even, in speed of agitator is 300r/min, reaction temperature is 85 DEG C of items
React 5h under part, then with 0.5L/min rate of addition by dicyandiamide solution drop (tannin, ammonia in above-mentioned reaction in the 4th storage tank
The ratio between amount of substance of gas, formaldehyde, dicyandiamide be 35:6:1.5:1.2) add in the reaction kettle, in speed of agitator be 300r/
Min, reaction temperature react 5h under the conditions of being 85 DEG C, and reacting rear material, which is pumped into thickener, carries out condensing crystallizing, condensing crystallizing temperature
Degree is 40 DEG C, and the upper layer overflow clear liquid after condensing crystallizing is pumped into reaction kettle, and lower layer's magma after condensing crystallizing is pumped into centrifugation point
From being centrifuged in device, the solid for being centrifugated acquisition is renewable dicyandiamide modified tannin adsorbent, centrifuge separation
The clear liquid of acquisition is detected through formaldehyde on-line detector, if content of formaldehyde is greater than 5mg/L, is pumped into reaction kettle and is continued to participate in instead
It answers, if content of formaldehyde is less than 5mg/L, direct outlet；
The characterization of adsorption of renewable dicyandiamide modified tannin adsorbent is as shown in the table in the present invention:
Adsorption test is carried out in the present invention, test result is as follows:
As seen from the above table, renewable dicyandiamide modified tannin adsorbent provided by the invention is to Co2+And Ni2+Removal rate
Close to 100%, adsorbance is respectively 56.4mg/L and 71.8mg/L；Meanwhile it can also Adsorption Mn2+、Zn2+、Mg2+、
Pb2+、Cu2+、Cd2+、Cr3+Equal metal ions, show higher adsorption recovery ability and anti-ion interference sexuality.
The renewable dicyandiamide modified tannin adsorbent after absorption heavy metal can be filtered out in the present invention and use 0.1-
The dilution heat of sulfuric acid of 0.5mol/L impregnates 3-5h at room temperature, so that it is regenerated, the renewable dicyandiamide modified tannin after regeneration
Adsorbent can be applied to above-mentioned adsorption test again, and five regenerative adsorption test datas are as follows in the present invention:
The foregoing is merely preferred embodiments of the present invention, are not intended to limit embodiments of the present invention and protection model
It encloses, to those skilled in the art, should can appreciate that all with made by description of the invention and diagramatic content
Equivalent replacement and obviously change obtained scheme, should all be included within the scope of the present invention.
Claims (3)
1. a kind of renewable dicyandiamide modified tannin adsorbent, which is characterized in that its structural formula is shown below:
Wherein, n 30-50.
2. the preparation method of renewable dicyandiamide modified tannin adsorbent described in a kind of claim 1, which is characterized in that including such as
Lower step:
1) ammonia spirit, is added into the reaction kettle for fill tanning solution, stir and formaldehyde is added thereto after mixing is molten
Liquid reacts 2-5h under the conditions of speed of agitator is 40-300r/min, reaction temperature is 40-85 DEG C, then with 0.1-0.5L/min drop
Dicyandiamide solution is added dropwise in the reaction kettle by acceleration, in speed of agitator be 40-300r/min, reaction temperature 40-85
2-5h is reacted under the conditions of DEG C, wherein the ratio between amount of substance of tannin, ammonia, formaldehyde, dicyandiamide is 20-35:5-6:1-1.5:1-
1.2；
2), the reaction solution of end of reaction in step 1) is crystallized under the conditions of 20-40 DEG C, Crystallization Separation, what Crystallization Separation obtained
Supernatant liquor, which is pumped into the reaction kettle, continues to participate in reaction, the sediment that Crystallization Separation obtains be centrifuged it is described can be again
Raw dicyandiamide modified tannin adsorbent, the mother liquor for being centrifugated acquisition are tested through content of formaldehyde, if content of formaldehyde is greater than 5mg/L,
It is then pumped into the reaction kettle and continues to participate in reaction, if content of formaldehyde is less than 5mg/L, direct outlet.
3. a kind of production system of renewable dicyandiamide modified tannin adsorbent characterized by comprising molten for storing tannin
First storage tank of liquid, the second storage tank for storing ammonium hydroxide, the third storage tank for storing formalin, for storing dicyandiamide
The 4th storage tank, reaction kettle, thickener, whizzer, the formaldehyde on-line detector, electronic three-way valve of solution, first storage
Tank, second storage tank, the third storage tank and the 4th storage tank pass through pipeline respectively and are connected to the reaction kettle, described thick
The arrival end of thick device is connected to by pipeline with the outlet end of the reaction kettle, the outlet end of the thickener pass through pipeline with it is described
The arrival end of whizzer is connected to, and the top of the thickener is connected to by pipeline with the reaction kettle, the centrifuge separation
The outlet end of device is connected to by pipeline with the arrival end of the formaldehyde on-line detector, the outlet end of the formaldehyde on-line detector
Be connected to by pipeline with the arrival end of the electronic three-way valve, one of outlet end of the electronic three-way valve by pipeline with
The reaction kettle connection, another outlet end of the electronic three-way valve are connected to by pipeline with outer comb, and the formaldehyde is online
Detector is electrically connected with the electronic three-way valve.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112355318A (en) * | 2020-10-21 | 2021-02-12 | 荆楚理工学院 | Large-particle-size porous spherical nickel powder and preparation method thereof |
| CN113881065A (en) * | 2021-11-05 | 2022-01-04 | 内江师范学院 | Novel tannin-based heavy metal flocculant, preparation method and application thereof |
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| CN104148022A (en) * | 2014-08-12 | 2014-11-19 | 辽宁大学 | Amine-modified persimmon tannin adsorbent, and preparation method and application thereof |
| CN107744801A (en) * | 2017-11-23 | 2018-03-02 | 齐鲁工业大学 | A kind of poly- phenol amine sorbing material of new lignin-base and preparation method |
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| CN104148022A (en) * | 2014-08-12 | 2014-11-19 | 辽宁大学 | Amine-modified persimmon tannin adsorbent, and preparation method and application thereof |
| CN107744801A (en) * | 2017-11-23 | 2018-03-02 | 齐鲁工业大学 | A kind of poly- phenol amine sorbing material of new lignin-base and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112355318A (en) * | 2020-10-21 | 2021-02-12 | 荆楚理工学院 | Large-particle-size porous spherical nickel powder and preparation method thereof |
| CN113881065A (en) * | 2021-11-05 | 2022-01-04 | 内江师范学院 | Novel tannin-based heavy metal flocculant, preparation method and application thereof |
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