CN105688865B - It is a kind of by biological adsorption agent and its preparation method and application made from tea grounds ball milling post-modification - Google Patents
It is a kind of by biological adsorption agent and its preparation method and application made from tea grounds ball milling post-modification Download PDFInfo
- Publication number
- CN105688865B CN105688865B CN201610118975.3A CN201610118975A CN105688865B CN 105688865 B CN105688865 B CN 105688865B CN 201610118975 A CN201610118975 A CN 201610118975A CN 105688865 B CN105688865 B CN 105688865B
- Authority
- CN
- China
- Prior art keywords
- tea grounds
- adsorption agent
- biological adsorption
- tea
- ultra micro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- 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
Abstract
The present invention relates to a kind of by fluorine removal biological adsorption agent and its preparation method and application made from tea grounds ball milling post-modification.The present invention is removed the substances such as the soluble pigment in tea grounds by sulfuric acid and obtains the tea grounds of depigmentaton first, then the tea grounds of depigmentaton progress ball milling is obtained into ultra micro tea grounds, ultra micro tea grounds is immersed in the mixed solution of the metal ions such as zirconium, iron, lanthanum, cerium, titanium again, the hydroxide of generation is made to be carried in tea grounds under alkaline condition, for subsequent high temperature drying to ensure that hydroxide can be fully supported in ultra micro tea grounds, fluorine removal biological adsorption agent is made in last washing and drying.The primary raw material of this biological adsorption agent is tea grounds, it derives from a wealth of sources and cheap, the present invention not only eliminate tea grounds waste and its caused by pollution, and new approach is provided for tea grounds higher value application, solves the problems, such as that tea grounds is intractable in industrial processes.The preparation process reaction condition of this biological adsorption agent is mild, and process route is simple and practicable, is easy to industrial operation.
Description
Technical field
The present invention relates to a kind of preparation methods by biological adsorption agent, the biological adsorption agent made from tea grounds ball milling post-modification
And the biological adsorption agent application in fluorine removal and metal at the same time.
Background technology
Fluorine (Fluoride) as intake micro- necessary to human body, a small amount of can pre- anti-caries, promote bone
Calcium metabolism, but if Excess free enthalpy be more than safe level fluorine can cause fluorine poisoning.World Health Organization's regulation, drinking water
Suitable concentration 0.5mg/L~1.0mg/L of middle content of fluoride.It is reported that have people more than 200,000,000 to drink fluorine content exceeded in the whole world
Water.China is one of country that Water fluorosis prevalence is most wide in the world, harm is most heavy, and there are 1135 drinking water type places in the whole nation
Property fluorine poisoning lesion county, impacted fluorine lesion village's total number of people is up to 8851.7 ten thousand people.And up to the present, endemic fluorosis
Effective therapy is there is no, therefore prevents fluorine poisoning by reducing fluorine content of drinking water, is control Water fluorosis
Main means.
In recent years, since the leachate of waste water caused by industry and solid waste is directly discharged into water body, civilian solid
The unreasonable landfill such as waste and stacking and the application of a large amount of chemical fertilizer, pesticide so that fluorine content is exceeded in drinking-water while a huge sum of money
It is also more serious to belong to pollution.In addition, tea tree is the enriching plant of a kind of fluorine and aluminium, wherein blade is main enrichment positions, special
It is not black tea, ingredient is mainly thick old leaf piece, and fluorine content is up to thousands of a mg/kg, far more than national standard 300mg/kg, aluminium
Content also reaches more than ten of mg/kg, and health risk can not be ignored.
The method of fluorine and metal mainly has absorption method, coagulant sedimentation, ion-exchange, film in processing water both at home and abroad at present
Partition method, electric flocculation method and electroosmose process etc., wherein absorption method be it is the most frequently used be also most efficient method drinking water in it is common
De-fluoridation adsorbent includes agricultural by product, clay, activated bentonite, hydrotalcite, bone black, zeolite and activated alumina etc..Wherein
Activated alumina is one of adsorbent being most widely used in the world, but alumina adsorption capacity it is relatively low and adsorb after have
Residual can cause secondary pollution, and absorption optimal pH range is relatively narrow and only just has preferable adsorption effect in acid condition.Cause
This, it is the key that fluorine removal and metal to develop adsorbent efficient, applied widely.
Tea grounds (tea waste) refer to Tea planting, processing, deep processing and circulation consumption etc. during generate with tealeaves
The general name of waste based on biomass is an important component of agricultural solid residue.Generation in 2013 according to statistics
481.9 ten thousand tons of boundary's tea yield, wherein 1,850,000 tons of Chinese tea yield, these tealeaves can generate greatly during productive consumption
The tea grounds of amount, and as instant tea, tea beverage and tea polyphenol health products etc. have catered to the current living habit of people, tealeaves adds deeply
The a large amount of exploitations and production of chemical product also produce a large amount of tealeaves wastes.And tea grounds offal treatment has become an ecology
Environmental problem.The arbitrary disposition of tea grounds not only causes environmental pollution, but also waste huge living resources.In recent years, such as
What develops and uses tea grounds waste, it has also become research hotspot in recent years.Therefore, how tea grounds is modified, prepared new
The biological adsorption agent of type is ability so as to can not only utilize biomass castoff but also can purify fluorine and the exceeded drinking water of metal
The technical issues of field technique personnel make great efforts to solve always.
Invention content
Against the above deficiency, the present invention provides fluorine removal obtained, metal biology are modified after a kind of ball milling by tea grounds
Adsorbent and its preparation method and application.Preparation method in the present invention is using tea grounds as raw material, and preparation process is few and preparation efficiency
It is high；The biological adsorption agent as made from this method can be widely applied in fluorine and the exceeded drinking water of metal, brick tea and instant tea,
With remarkable advantages such as low cost, high efficiency, the simple, non-secondary pollutions of processing.
Obtained fluorine removal, metal biological adsorption agent are modified after providing a kind of ball milling by tea grounds one of to achieve the above object
Preparation method, present invention employs following technical schemes：
A kind of method that prepared by tea grounds ball milling post-modification biological adsorption agent, includes the following steps：
S1, tea grounds is put into dilution heat of sulfuric acid, 1~3h of water-bath removes the pigment in tea grounds under 70~80 DEG C of warm water；
3~4h is dried after being washed with deionized for several times after water-bath in 70~100 DEG C of baking ovens, obtains treating the tea grounds of ball milling after drying；
S2, the tea grounds for treating ball milling is subjected to ball milling, ultra micro tea grounds to be modified is made；
S3, the metal ion for the one or more mixing being added to ultra micro tea grounds to be modified in zirconium, iron, lanthanum, cerium, titanium
In solution, added in while stirring at 50~80 DEG C alkaline compound solution the pH value of mixed solution adjusted to 4.0~
7.0；0.5~2h of stirring is then proceeded to, taking-up sediment, which is put into dry 2~4h in 70~150 DEG C of baking ovens, makes the hydrogen of metal ion
Oxide is fully supported on tea grounds, obtains modified ultra micro tea grounds；
S4, it modified ultra micro tea grounds is washed with deionized removes soluble-salt for several times, in 70~100 DEG C of baking ovens
Drying can obtain biological adsorption agent.
Preferably, in step S1, a concentration of 0.02M of the dilution heat of sulfuric acid.
Preferably, in step S2, it is less than 76 μm by the ultra micro tea grounds grain size that ball milling obtains
Preferably, in step S3, the total concentration of the metal ion is 0.01~1.0M.
Further, in step S3, the metal ion uses zirconium ion, a concentration of 0.4M of zirconium ion solution.
Meanwhile the present invention provides according to biological adsorption agent made from above-mentioned preparation method.
Also, fluorine removal and gold are gone in drinking water, brick tea, instant tea simultaneously the present invention also provides above-mentioned biological adsorption agent
The application of category.
It preferably, will be biological after inorganic pollution of this biological adsorption agent in absorption drinking water, brick tea, instant tea
Adsorbent is immersed in 1~5h in alkaline compound solution, you can regenerates and reuses.
Further, the alkaline compound solution is the sodium hydroxide solution of 1~5wt%.
The beneficial effects of the present invention are：
1), the present invention is removed the substances such as the soluble pigment in tea grounds by sulfuric acid and obtains the tea grounds of depigmentaton first, so
The tea grounds of depigmentaton progress ball milling is obtained into ultra micro tea grounds afterwards, then by ultra micro tea grounds be immersed in the metals such as zirconium, aluminium, iron, lanthanum, titanium from
In the mixed solution of son, the hydroxide of generation is made to be carried in tea grounds under alkaline condition, subsequent high temperature drying is to ensure hydrogen
Oxide can be fully supported in ultra micro tea grounds, and fluorine removal biological adsorption agent is made in last washing and drying.
This adsorbent primary raw material is tea grounds, is derived from a wealth of sources and cheap, therefore the present invention is discarded eliminating tea grounds
While object and its caused pollution, new approach is provided for tea grounds higher value application, is solved in industrial processes
The intractable problem of tea grounds.
2), the preparation process reaction condition of this biological adsorption agent is mild, and process route is simple and practicable, is easy to industrialization behaviour
Make, therefore have the potentiality of large-scale promotion application.
3), this biological adsorption agent can be widely applied in fluorine and the exceeded drinking water of metal and brick tea, instant tea, have
The advantages that low cost, high efficiency, simple processing.
4), this biological adsorption agent can be continued cycling through by the alkaline compound solution zeolite regeneration of certain mass concentration
It uses, it is environmentally friendly.
Description of the drawings
Fig. 1 a, 1b be respectively amplify 2000 times unmodified tea grounds SEM figures, the ultra micro tea grounds to be modified after ball milling (i.e.
UTP) SEM schemes.
Fig. 1 c are the SEM figures for amplifying 100000 times of lower ultra micro tea grounds.
Fig. 1 d are to amplify the SEM figures through the metal ion-modified UTP-Zr systems of zirconium, modified tea grounds under 100000 times
The hydroxide of middle load zirconium.
Fig. 1 e are that the SEM amplified through the metal ion-modified UTP-Zr systems absorption fluorine of zirconium under 100000 times schemes.
Fig. 1 f are that the SEM amplified through the metal ion-modified UTP-Zr systems absorption fluorine of zirconium and aluminium under 100000 times schemes.
Specific embodiment
In order to which technical characteristic, purpose and the advantageous effect to the present invention are better understood from, below in conjunction with specific embodiment
It is next that the present invention will be further described, but the present invention is not restricted to the present embodiment.
The index that adsorption capacity in embodiment adsorbs fluorine ion in water for biological adsorption agent, wherein fluorine ion is dense in water
Degree is measured by fluoride ion selective electrode, and zirconium ion and aluminum ions concentration use Inductively coupled plasma optical emission spectrometer (ICP)
It measures, caffeine and catechin content are measured using high performance liquid chromatography (HPLC).
Embodiment 1
2.5g ultra micro tea grounds is put into 0.02M (i.e. 0.02mol/L) sulfuric acid solution of 100mL, the water under 70 DEG C of warm water
Bathe pigment in 3h removal tea grounds；3h is dried after being washed with deionized for several times after water-bath in 70 DEG C of baking ovens, ball is carried out after drying
Mill obtains ultra micro tea grounds to be modified；Ultra micro tea grounds to be modified is added in the solution of basic zirconium chloride (0.4M, 100mL),
Sodium hydroxide solution (2M) is added at 60 DEG C while stirring to adjust the pH value of mixed solution to 7.0；It then proceedes to stir
0.5h is mixed, sediment is taken out and is put into 110 DEG C of baking ovens dry 2h, obtain modified ultra micro tea grounds；By modified ultra micro tea
Slag is washed with deionized removes soluble-salt for several times, and drying is that can obtain ultra micro tea grounds biological adsorption agent in 70 DEG C of baking ovens.
The ultra micro tea grounds adsorbent that above-mentioned 0.08g is prepared is taken to be put into equipped with pH is 7.0, fluorinion concentration 10mg/L,
Centrifuge tube in the simulation drinking water that aluminium ion concentration is the 25mL of 2mg/L is 25 ± 2 DEG C in temperature, rotating speed 300r/
After shaking 2h in the constant-temperature table of min, filter after the absorption of survey that fluorine ion and aluminium ion concentration, experiment are parallel three times in solution.
It is 94.1% to the removal rate of fluorine by calculating adsorbent under this condition, remaining fluorine ion in the solution after absorption
A concentration of 0.59mg/L, less than national standard.Adsorbent is 99.5% to the removal rate of aluminium, and the concentration of zirconium is less than in solution
ICP detection limits (LOD；0.01mg/L).
Embodiment 2
2.5g ultra micro tea grounds is put into the 0.02M sulfuric acid solutions of 100mL, water-bath 3h is removed in tea grounds under 70 DEG C of warm water
Pigment；3h is dried after being washed with deionized for several times after water-bath in 70 DEG C of baking ovens, progress ball milling obtains to be modified after drying
Ultra micro tea grounds；Ultra micro tea grounds to be modified is added in the solution of basic zirconium chloride (0.4M, 100mL), is stirred on one side at 60 DEG C
It mixes and adds in sodium hydroxide solution (2M) on one side by the pH value adjusting of mixed solution to 7.0；Stirring 0.5h is then proceeded to, takes out precipitation
Object is put into 110 DEG C of baking ovens dry 2h, obtains modified ultra micro tea grounds；Modified ultra micro tea grounds is washed with deionized
Soluble-salt is removed for several times, and drying is that can obtain ultra micro tea grounds biological adsorption agent in 70 DEG C of baking ovens.
The ultra micro tea grounds adsorbent that above-mentioned 0.08g is prepared is taken to be put into equipped with pH is 6.0, fluorinion concentration 10mg/L,
Centrifuge tube in the simulation drinking water that aluminium ion concentration is the 25mL of 4mg/L is 25 ± 2 DEG C in temperature, rotating speed 300r/
After shaking 2h in the constant-temperature table of min, filter after the absorption of survey that fluorine ion and aluminium ion concentration, experiment are parallel three times in solution.
It is 92.8% to the removal rate of fluorine by calculating adsorbent under this condition, remaining fluorine ion in the solution after absorption
A concentration of 0.72mg/L, less than national standard.Adsorbent is 89.7% to the removal rate of aluminium, and the concentration of zirconium is less than in solution
ICP detection limits (LOD；0.01mg/L).
Embodiment 3
2.5g ultra micro tea grounds is put into the 0.02M sulfuric acid solutions of 100mL, water-bath 3h is removed in tea grounds under 70 DEG C of warm water
Pigment；3h is dried after being washed with deionized for several times after water-bath in 70 DEG C of baking ovens, progress ball milling obtains to be modified after drying
Ultra micro tea grounds；Ultra micro tea grounds to be modified is added in the solution of basic zirconium chloride (0.4M, 100mL), is stirred on one side at 60 DEG C
It mixes and adds in sodium hydroxide solution (2M) on one side by the pH value adjusting of mixed solution to 7.0；Stirring 0.5h is then proceeded to, takes out precipitation
Object is put into 110 DEG C of baking ovens dry 2h, obtains modified ultra micro tea grounds；Modified ultra micro tea grounds is washed with deionized
Soluble-salt is removed for several times, and drying is that can obtain ultra micro tea grounds biological adsorption agent in 70 DEG C of baking ovens.
The ultra micro tea grounds adsorbent that above-mentioned 0.08g is prepared is taken to be put into equipped with pH is 5.0, fluorinion concentration 10mg/L,
Centrifuge tube in the simulation drinking water that aluminium ion concentration is the 25mL of 10mg/L, is 25 ± 2 DEG C in temperature, rotating speed is
After shaking 2h in the constant-temperature table of 300r/min, fluorine ion and aluminium ion concentration in solution are filtered after the absorption of survey, experiment is three times
It is parallel.
It is 91.0% to the removal rate of fluorine by calculating adsorbent under this condition, remaining fluorine ion in the solution after absorption
A concentration of 0.90mg/L, less than national standard.Adsorbent is 50% to the removal rate of aluminium, and the concentration of zirconium is less than ICP in solution
Detection limit (LOD；0.01mg/L).
Embodiment 4
2.5g ultra micro tea grounds is put into the 0.02M sulfuric acid solutions of 100mL, water-bath 3h is removed in tea grounds under 70 DEG C of warm water
Pigment；3h is dried after being washed with deionized for several times after water-bath in 70 DEG C of baking ovens, progress ball milling obtains to be modified after drying
Ultra micro tea grounds；Ultra micro tea grounds to be modified is added in the solution of basic zirconium chloride (0.4M, 100mL), is stirred on one side at 60 DEG C
It mixes and adds in sodium hydroxide solution (2M) on one side by the pH value adjusting of mixed solution to 7.0；Stirring 0.5h is then proceeded to, takes out precipitation
Object is put into 110 DEG C of baking ovens dry 2h, obtains modified ultra micro tea grounds；Modified ultra micro tea grounds is washed with deionized
Soluble-salt is removed for several times, and drying is that can obtain ultra micro tea grounds biological adsorption agent in 70 DEG C of baking ovens.
The biological adsorption agent that above-mentioned 0.05g is prepared is taken to be put into the Fu equipped with the 25mL that pH is 5.3, a concentration of 9.4mg/L
Brick tea millet paste (1:It is prepared by 50m/v) centrifuge tube, after temperature cooks 30min for 30 ± 1 DEG C, filter after the absorption of survey in solution
Fluorinion concentration, aluminium ion concentration, caffeine, catechin and pH value, experiment are parallel three times.
It is 28% to the removal rate of fluorine by calculating adsorbent under this condition, the removal rate to aluminium is 15%, tea after absorption
Caffeine content and pH in soup do not change substantially, and catechin loss only 5%, millet paste color and luster does not have substantially before and after the processing
Variation.
Embodiment 5
2.5g ultra micro tea grounds is put into the 0.02M sulfuric acid solutions of 100mL, water-bath 3h is removed in tea grounds under 70 DEG C of warm water
Pigment；3h is dried after being washed with deionized for several times after water-bath in 70 DEG C of baking ovens, progress ball milling obtains to be modified after drying
Ultra micro tea grounds；Ultra micro tea grounds to be modified is added in the solution of basic zirconium chloride (0.4M, 100mL), is stirred on one side at 60 DEG C
It mixes and adds in sodium hydroxide solution (2M) on one side by the pH value adjusting of mixed solution to 7.0；Stirring 0.5h is then proceeded to, takes out precipitation
Object is put into 110 DEG C of baking ovens dry 2h, obtains modified ultra micro tea grounds；Modified ultra micro tea grounds is washed with deionized
Soluble-salt is removed for several times, and drying is that can obtain ultra micro tea grounds biological adsorption agent in 70 DEG C of baking ovens.
The biological adsorption agent that above-mentioned 0.05g is prepared is taken to be put into the speed equipped with the 25mL that pH is 5.2, a concentration of 52.4mg/L
Molten tea millet paste (1:It is prepared by 50m/v) centrifuge tube, after temperature cooks 30min for 30 ± 1 DEG C, filter after the absorption of survey in solution
Fluorinion concentration, aluminium ion concentration, caffeine, catechin and pH value, experiment are parallel three times.
It is 43% to the removal rate of fluorine by calculating adsorbent under this condition, the removal rate to aluminium is 25%, tea after absorption
Caffeine content and pH in soup do not change substantially, and catechin loss only 8%, millet paste color and luster does not have substantially before and after the processing
Variation.
Claims (6)
- A kind of 1. method that tea grounds ball milling post-modification is prepared into biological adsorption agent, it is characterised in that include the following steps：S1, tea grounds is put into dilution heat of sulfuric acid, 1~3h of water-bath removes the pigment in tea grounds under 70~80 DEG C of warm water；Water-bath After be washed with deionized for several times after in 70~100 DEG C of baking ovens dry 3~4h, obtain treating the tea grounds of ball milling after drying；S2, the tea grounds for treating ball milling is subjected to ball milling, ultra micro tea grounds to be modified is made；S3, the metal ion solution for the one or more mixing being added to ultra micro tea grounds to be modified in zirconium, iron, lanthanum, cerium, titanium In, alkaline compound solution is added in by the pH value adjusting of mixed solution to 4.0~7.0 while stirring at 50~80 DEG C； 0.5~2h of stirring is then proceeded to, taking-up sediment, which is put into dry 2~4h in 70~150 DEG C of baking ovens, makes the hydroxide of metal ion Object is fully supported on tea grounds, obtains modified ultra micro tea grounds；S4, it modified ultra micro tea grounds is washed with deionized removes soluble-salt for several times, dried in 70~100 DEG C of baking ovens It can obtain biological adsorption agent；In step S2, it is less than 76 μm by the ultra micro tea grounds grain size that ball milling obtains；In step S3, the metal ion uses zirconium ion, a concentration of 0.4M of zirconium ion solution.
- 2. a kind of method that tea grounds ball milling post-modification is prepared into biological adsorption agent according to claim 1, it is characterised in that： In step S1, a concentration of 0.02M of the dilution heat of sulfuric acid.
- 3. according to biological adsorption agent made from any one of claim 1~2 preparation method.
- 4. biological adsorption agent according to claim 3 goes the application of fluorine removal and metal in drinking water, brick tea, instant tea.
- 5. the application of biological adsorption agent according to claim 4, it is characterised in that：This biological adsorption agent is drunk in absorption After inorganic pollution in water, brick tea and instant tea, biological adsorption agent is immersed in 1~5h in alkaline compound solution, i.e., It is renewable and reuse.
- 6. the application of biological adsorption agent according to claim 5, it is characterised in that：The alkaline compound solution for 1~ The sodium hydroxide solution of 5wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118975.3A CN105688865B (en) | 2016-03-02 | 2016-03-02 | It is a kind of by biological adsorption agent and its preparation method and application made from tea grounds ball milling post-modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118975.3A CN105688865B (en) | 2016-03-02 | 2016-03-02 | It is a kind of by biological adsorption agent and its preparation method and application made from tea grounds ball milling post-modification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105688865A CN105688865A (en) | 2016-06-22 |
| CN105688865B true CN105688865B (en) | 2018-07-06 |
Family
ID=56223873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610118975.3A Active CN105688865B (en) | 2016-03-02 | 2016-03-02 | It is a kind of by biological adsorption agent and its preparation method and application made from tea grounds ball milling post-modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105688865B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114392722B (en) * | 2022-01-28 | 2023-07-14 | 湖南烯富环保科技有限公司 | Biochar@five-membered metal oxide composite defluorination material as well as preparation and application thereof |
| CN114653341A (en) * | 2022-04-12 | 2022-06-24 | 四川文理学院 | Modified tea residue biochar, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507913A (en) * | 2009-02-10 | 2009-08-19 | 浙江大学 | Preparation method of tea-leaf power capable of cleaning organic waste gas and use method thereof |
| CN103506087A (en) * | 2013-09-27 | 2014-01-15 | 华南农业大学 | Method for preparing heavy metal ion adsorbent using maleic acylation wood fibers at room temperature |
| CN104525137A (en) * | 2014-12-04 | 2015-04-22 | 安徽农业大学 | Defluorination biological adsorbent made by tea residue modification, preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6790363B2 (en) * | 2001-07-24 | 2004-09-14 | Chk Group, Inc. | Method of treating arsenic-contaminated waters |
-
2016
- 2016-03-02 CN CN201610118975.3A patent/CN105688865B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507913A (en) * | 2009-02-10 | 2009-08-19 | 浙江大学 | Preparation method of tea-leaf power capable of cleaning organic waste gas and use method thereof |
| CN103506087A (en) * | 2013-09-27 | 2014-01-15 | 华南农业大学 | Method for preparing heavy metal ion adsorbent using maleic acylation wood fibers at room temperature |
| CN104525137A (en) * | 2014-12-04 | 2015-04-22 | 安徽农业大学 | Defluorination biological adsorbent made by tea residue modification, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105688865A (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107298477B (en) | Method for degrading organic pollutants in wastewater by catalyzing persulfate | |
| CN104098166B (en) | A kind of agricultural chemicals waste water dephosphorization agent | |
| CN105013435B (en) | A kind of metal composite oxide dephosphorization adsorbent and preparation method thereof | |
| CN109554549A (en) | The method that high temperature and pressure leaches rare earth in recycling neodymium iron boron waste material | |
| CN105289562B (en) | Heavy metal wastewater thereby recoverying and utilizing method | |
| CN106111055B (en) | A kind of synchronous denitrification dephosphorizing adsorbent and its preparation method and application | |
| CN108002472A (en) | A kind of preparation method of domestic sewage treating compound | |
| CN104226259A (en) | Threonine modified attapulgite adsorbent and application thereof | |
| CN109608021A (en) | Deep dehydration method for sludge | |
| CN102513108B (en) | TiO2-carrying photoelectric catalyst for photoelectrocatalytic advanced treatment on sludge and method and device for TiO2-carrying photoelectric catalyst-based photoelectrocatalytic advanced treatment on sludge | |
| CN106186441A (en) | A kind of processing method of heavy metal-containing waste water | |
| CN105668856A (en) | Treatment method for heavy-metal-containing wastewater | |
| CN104525137A (en) | Defluorination biological adsorbent made by tea residue modification, preparation method and application thereof | |
| CN109012565A (en) | A kind of method of the magnetic carbon material Adsorption heavy metal ions in wastewater of nitrating | |
| CN104998618A (en) | Method for preparing hydrothermal biomass charcoal from pecan shells | |
| CN106904705A (en) | A kind of efficiently recyclable acidity contains As (V) method of wastewater treatment | |
| CN105688865B (en) | It is a kind of by biological adsorption agent and its preparation method and application made from tea grounds ball milling post-modification | |
| CN106929679A (en) | A kind of method that sulfuric acid neutrality leaching-reducing process processes chromium slag | |
| CN106745591A (en) | A kind of preparation method of heavy metal ion adsorbed type composite flocculation agent and products thereof | |
| CN102580666B (en) | Modified pumice for purifying heavy metal sewage and preparation method and application of modified pumice | |
| CN104193061B (en) | A kind of processing method of paraquat agricultural chemicals waste water | |
| CN107879415A (en) | A kind of domestic sewage treating compound | |
| CN106396308A (en) | Excess activated sludge recycling method | |
| CN103585978B (en) | Remove chromic adsorbent and preparation method thereof and application in Drinking w ater | |
| CN106881062A (en) | A kind of preparation method of the magnesium hydroxide-flyash built agent for processing fluoride waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |