CN107282008A - A kind of preparation method of biomass heavy-metal adsorption material - Google Patents
A kind of preparation method of biomass heavy-metal adsorption material Download PDFInfo
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- CN107282008A CN107282008A CN201710424433.3A CN201710424433A CN107282008A CN 107282008 A CN107282008 A CN 107282008A CN 201710424433 A CN201710424433 A CN 201710424433A CN 107282008 A CN107282008 A CN 107282008A
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- 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
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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
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- 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
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Abstract
The present invention relates to a kind of preparation method of biomass heavy-metal adsorption material, belong to technical field of adsorption material preparation.The present invention makes the expansion of pigskin internal void become big by the thermodynamic activity of oil first, form loose porous structure, make pigskin internal void insertion after being pricked again with needle plate pressure, the adsorption site of pig skin surfaces is set fully to expose while cleaning oil stain with methanol solution again, it is modified through the roselle enzymolysis liquid rich in active group and hydroxycitric acid, increase the active group quantity inside porous pigskin and in surface pore and the content of hydroxycitric acid and oxalic acid in the presence of microorganism, microorganism can produce micro- corruption to pigskin simultaneously, formed more to ultramicropore, further increase the absorption property of pigskin, pass through the complexing of citric acid and oxalic acid after pigskin Adsorption of Heavy Metals, tightly pin heavy metal ion, finally sedimentation is removed.Biomass heavy-metal adsorption material absorption produced by the present invention is more thorough, can thoroughly utilize sorbing material, improve utilization rate.
Description
Technical field
The present invention relates to a kind of preparation method of biomass heavy-metal adsorption material, belong to heavy metal processing technology field.
Background technology
With continuing to develop for China's industrial or agricultural, the pollution problem produced therefrom is increasingly serious, a substantial amounts of harmful huge sum of money
Category pollutant is discharged into water, seriously threatens the healthy and ecological environment of the mankind；Therefore, people come up with a variety of absorption
The method of material modification pollution administration thing, generally uses hydrothermal modification, chemical modification method, physical modification method, at present
Maximally effective method of modifying is to change the performance of sorbing material by way of microorganism grows, and is the side grown using fungi
Formula makes the performance of the surface of solids be strengthened, but can not change the internal structure of material, causes sorbing material waste, utilization rate not
Height, so that the raising that absorption property cannot be overall；Can therefore work out on this basis a kind of can not only change thing
The surface property of matter, can also change the method for material internal structure, be the technology development of current microorganism modified absorbing material
Direction.Fried pigskin, i.e., carry out frying using vegetable oil or animal oil by pigskin.Fried pigskin can also pass through bubble with dry-eating
It can be cooked after hair for tune cold dish, burning soup or with other vegetables.The fried pigskin of dry-eating is like to eat dilated food, crisp, food
It can feel fragrant and oiliness, smooth, resilient enoughs of many skies with the fried pigskin after being soaked.And fried pigskin has loose after being soaked
Porous structure, makes it possess high adsorption capacity.
Therefore a kind of heavy-metal adsorption material is invented with the possibility that can be realized using fried pigskin, and provide one kind both
Its internal structure can be changed can improve the method for its surface property again has positive meaning to adsorbent preparation field.
The content of the invention
Present invention mainly solves technical problem, for the current common method of modifying to natural heavy-metal adsorption material
The surface property of material can only be changed, adsorption effect is improved, material internal structure can not be changed, although causing sorbing material table
Face gap enrich, but internal void it is small so that the low defect of adsorbance there is provided a kind of biomass heavy-metal adsorption material
Preparation method.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）Take raw pig skin poured with boiling water scald after scrape off surface impurity, the pigskin after removal of impurities is put into pot and adds clear water, big fire boils
Switch to small fire to after seething with excitement, continue to cook 3~5min, cooking is pulled pigskin out after terminating, eluted with frozen water, then strike off pig with scraper
Intracutaneous side grease, obtains pre-processing pigskin；
（2）Pretreatment pigskin is dried, then the pigskin after drying is put into oil cauldron and is fried to pigskin is fluffy, untill its colour changed into yellow,
Pull the pigskin after frying out and be put into cooking in boiling water, then 5~7h is soaked with deionized water, obtain loose porous fried pigskin；
（3）Pin is inserted in square polystyrene foam plate, needle point is penetrated cystosepiment and exposes 1cm length, is made
Make needle plate by oneself, then with self-control needle plate, pressure is pricked repeatedly on above-mentioned fried pigskin, obtains running through fried pigskin, it is standby；
（4）Weigh and crushed after 2~3kg roselles are eluted with water, obtain crushed material, then will be filled after crushed material and deionized water mixing
Enter in enzymatic vessel, 10~15g cellulases and 5~8g pectases, sealing tank mouth enzymolysis are added into tank；
（5）After above-mentioned enzymolysis terminates, take out enzymolysis product filtering and remove filter residue, obtain enzymolysis liquid, enzymolysis liquid is concentrated, obtain
Concentrate, composite modified liquid is obtained after gained concentrate and oxalic acid solution are mixed；
（6）By step（3）Standby is rinsed through fried pigskin with methanol solution, then will run through fried pigskin and upper after flushing
It is fitted into after stating composite modified liquid mixing in fermentation tank, then addition acetic acid bacteria bacteria suspension, heat-preservation fermentation into fermentation tank；
（7）After after above-mentioned fermentation ends, take out fermentation it is modified run through fried pigskin, freeze-drying is finally crushed and crosses 20
Mesh sieve, biomass heavy-metal adsorption material is produced after collecting sieving powder packaging.
Step（1）Described in the addition of clear water be 8~10 times of pigskin quality, the temperature of frozen water is 2~4 DEG C.
The described square polystyrene foam plate length of side is 10cm, and the contact pin amount of pin is 25/cm2.
Step（4）Described in crushed material and deionized water mass ratio be 1:5, hydrolysis temperature is 45~55 DEG C, enzymolysis
Time is 6~8h.
Step（5）Described in method for concentration be：Enzymolysis liquid is moved into Rotary Evaporators, in 40~50 DEG C of backspin inspissations
The 1/5 of its original volume is reduced to, concentrate is obtained.
Step（5）Described in concentrate and oxalic acid solution volume ratio be 3:1, oxalic acid solution concentration is 0.1mol/L.
Step（6）Described in methanol solution mass fraction be 70%, through fried pigskin and the mass ratio of composite modified liquid
For 1:10, acetic acid bacteria bacteria suspension concentration is 104cfu/mL, and the addition of acetic acid bacteria bacteria suspension is the 5% of fried pigskin quality.
Described freeze-drying temperature is -30~-20 DEG C.
The beneficial effects of the invention are as follows：
（1）The present invention makes the expansion of pigskin internal void become big by the thermodynamic activity of oil first, forms loose porous structure, then
Make pigskin internal void insertion after being pricked with needle plate pressure, make the adsorption site of pig skin surfaces while oil stain is cleaned with methanol solution again
Fully exposure, is modified through the roselle enzymolysis liquid rich in active group and hydroxycitric acid, increases many in the presence of microorganism
Hole pigskin inside and the active group quantity in surface pore and the content of hydroxycitric acid and oxalic acid, while microorganism can be right
Pigskin produces micro- corruption, forms more ultramicropores, not only changes the surface property of porous fried pigskin, also change its internal junction
Structure, further increases the absorption property of pigskin；
（2）By the complexing of citric acid and oxalic acid after pigskin Adsorption of Heavy Metals, heavy metal ion is tightly pinned, is finally settled
Removing, can make absorption more thorough, can thoroughly utilize sorbing material, improve utilization rate.
Embodiment
Take raw pig skin with boiling water pour scald after scrape off surface impurity, the pigskin after removal of impurities is put into pot, then into pot add
The clear water that 8~10 times of pigskin quality, big fire, which is boiled, switchs to small fire to boiling, continues to cook 3~5min, cooking pulls pig out after terminating
Skin, is eluted 3~5 times with 2~4 DEG C of frozen water, then strikes off grease on the inside of pigskin with scraper, obtains pre-processing pigskin；Will pretreatment
Pigskin, which is suspended at shady and cool ventilation, to be dried 5~7 days, then the pigskin after drying is put into oil cauldron fried to pigskin is fluffy, color becomes
Untill Huang, pull the pigskin after frying out and be put into boiling water 3~5min of cooking, then with the deionization water logging of 8~10 times of pigskin quality
5~7h is steeped, loose porous fried pigskin is obtained；By 25/cm2Contact pin amount by pin insert the length of side be 10cm pros
In shape polystyrene foam plate, needle point is penetrated cystosepiment and expose 1cm length, self-control needle plate is made, then existed with self-control needle plate
Pressure is pricked 8~10 times repeatedly on fried pigskin, obtains running through fried pigskin；Weigh after 2~3kg roselles are eluted with water and pour into crushing
20~30min is crushed in machine and obtains crushed material, then by crushed material and deionized water is 1 in mass ratio:Load enzymatic vessel after 5 mixing
In, 6~8h is digested at 45~55 DEG C after 10~15g cellulases and 5~8g pectases, sealing tank mouth are added into tank；Treat
After enzymolysis terminates, take out enzymolysis product filtering and remove filter residue, obtain enzymolysis liquid, enzymolysis liquid is moved into Rotary Evaporators, 40
~50 DEG C of backspin inspissations are reduced to the 1/5 of its original volume, obtain concentrate, are that 0.1mol/L oxalic acid is molten by gained concentrate and concentration
Liquid is 3 by volume:Composite modified liquid is obtained after 1 mixing；Fried pigskin mass fraction is will pass through to rinse for 70% methanol solution
10~15min, then will be 1 in mass ratio through fried pigskin and composite modified liquid after flushing:Load fermentation tank after 10 mixing
In, then it is 10 to add the concentration of fried pigskin quality 5% into fermentation tank4Cfu/mL acetic acid bacteria bacteria suspensions, are protected at 35~40 DEG C
Temperature fermentation 5~7 days；After after fermentation ends, take out fermentation it is modified run through fried pigskin, be put into vacuum freeze-drying machine with -30
~-20 DEG C of temperature freeze-drying, crosses 20 mesh sieves after finally being crushed with pulverizer, biomass is produced after collecting sieving powder packaging
Heavy-metal adsorption material.
Example 1
Take raw pig skin poured with boiling water scald after scrape off surface impurity, the pigskin after removal of impurities is put into pot, then add into pot pigskin
The clear water that 10 times of quality, big fire, which is boiled, switchs to small fire to boiling, continues to cook 5min, cooking pulls pigskin out after terminating, with 4 DEG C
Frozen water is eluted 5 times, then strikes off grease on the inside of pigskin with scraper, obtains pre-processing pigskin；Pretreatment pigskin is suspended on shady and cool logical
Dried at wind 7 days, then the pigskin after drying is put into oil cauldron and fried to pigskin is fluffy, untill its colour changed into yellow, pulled out after frying
Pigskin, which is put into boiling water, cooks 5min, then soaks 7h with the deionized water of 10 times of pigskin quality, obtains loose porous fried pig
Skin；By 25/cm2Contact pin amount by pin insert the length of side for 10cm square polystyrene foam plate in, wear needle point
Saturating cystosepiment simultaneously exposes 1cm length, and self-control needle plate is made, then with self-control needle plate, pressure is pricked 10 times repeatedly on fried pigskin, is obtained
Through fried pigskin；Weigh to pour into after 3kg roselles are eluted with water in pulverizer and crush 30min and obtain crushed material, then will crush
Thing and deionized water are 1 in mass ratio:It is fitted into after 5 mixing in enzymatic vessel, 15g cellulases and 8g pectases is added into tank,
After sealing tank mouth 8h is digested at 55 DEG C；After enzymolysis terminates, take out enzymolysis product filtering and remove filter residue, obtain enzymolysis liquid, will
Enzymolysis liquid is moved into Rotary Evaporators, is reduced to the 1/5 of its original volume in 50 DEG C of backspin inspissations, is obtained concentrate, gained is concentrated
Liquid and concentration are that 0.1mol/L oxalic acid solutions are 3 by volume:Composite modified liquid is obtained after 1 mixing；Fried pigskin is will pass through to use
Mass fraction is that 70% methanol solution rinses 15min, then will be in mass ratio through fried pigskin and composite modified liquid after flushing
1:It is fitted into after 10 mixing in fermentation tank, then it is 10 to add the concentration of fried pigskin quality 5% into fermentation tank4Cfu/mL acetic acid bacterias
Bacteria suspension, heat-preservation fermentation 7 days at 40 DEG C；After after fermentation ends, take out fermentation it is modified run through fried pigskin, be put into vacuum
It is freeze-dried in freeze dryer with -20 DEG C of temperature, 20 mesh sieves is crossed after finally being crushed with pulverizer, is collected after sieving powder packaging i.e.
Obtain biomass heavy-metal adsorption material.
Example 2
Take raw pig skin poured with boiling water scald after scrape off surface impurity, the pigskin after removal of impurities is put into pot, then add into pot pigskin
The clear water that 8 times of quality, big fire, which is boiled, switchs to small fire to boiling, continues to cook 3min, cooking pulls pigskin out after terminating, with 2 DEG C
Frozen water is eluted 3 times, then strikes off grease on the inside of pigskin with scraper, obtains pre-processing pigskin；Pretreatment pigskin is suspended on shady and cool logical
Dried at wind 5 days, then the pigskin after drying is put into oil cauldron and fried to pigskin is fluffy, untill its colour changed into yellow, pulled out after frying
Pigskin, which is put into boiling water, cooks 3min, then soaks 5h with the deionized water of 8 times of pigskin quality, obtains loose porous fried pig
Skin；By 25/cm2Contact pin amount by pin insert the length of side for 10cm square polystyrene foam plate in, wear needle point
Saturating cystosepiment simultaneously exposes 1cm length, and self-control needle plate is made, then with self-control needle plate, pressure is pricked 8 times repeatedly on fried pigskin, is passed through
Wear fried pigskin；Weigh to pour into after 2kg roselles are eluted with water in pulverizer and crush 20min and obtain crushed material, then by crushed material
It is 1 in mass ratio with deionized water:It is fitted into after 5 mixing in enzymatic vessel, 10g cellulases and 5g pectases is added into tank, it is close
After sealed cans mouthful 6h is digested at 45 DEG C；After enzymolysis terminates, take out enzymolysis product filtering and remove filter residue, enzymolysis liquid is obtained, by enzyme
Solve liquid to move into Rotary Evaporators, be reduced to the 1/5 of its original volume in 40 DEG C of backspin inspissations, obtain concentrate, by gained concentrate
It is that 0.1mol/L oxalic acid solutions are 3 by volume with concentration:Composite modified liquid is obtained after 1 mixing；It will pass through fried pigskin matter
It is that 70% methanol solution rinses 10min to measure fraction, then will be 1 in mass ratio through fried pigskin and composite modified liquid after flushing:
It is fitted into after 10 mixing in fermentation tank, then it is 10 to add the concentration of fried pigskin quality 5% into fermentation tank4Cfu/mL acetic acid bacteria bacterium
Suspension, heat-preservation fermentation 5 days at 35 DEG C；After after fermentation ends, take out fermentation it is modified run through fried pigskin, be put into vacuum jelly
It is freeze-dried in dry machine with -30 DEG C of temperature, 20 mesh sieves is crossed after finally being crushed with pulverizer, is produced after collecting sieving powder packaging
Biomass heavy-metal adsorption material.
Example 3
Take raw pig skin poured with boiling water scald after scrape off surface impurity, the pigskin after removal of impurities is put into pot, then add into pot pigskin
The clear water that 9 times of quality, big fire, which is boiled, switchs to small fire to boiling, continues to cook 4min, cooking pulls pigskin out after terminating, with 3 DEG C
Frozen water is eluted 4 times, then strikes off grease on the inside of pigskin with scraper, obtains pre-processing pigskin；Pretreatment pigskin is suspended on shady and cool logical
Dried at wind 6 days, then the pigskin after drying is put into oil cauldron and fried to pigskin is fluffy, untill its colour changed into yellow, pulled out after frying
Pigskin, which is put into boiling water, cooks 4min, then soaks 6h with the deionized water of 9 times of pigskin quality, obtains loose porous fried pig
Skin；By 25/cm2Contact pin amount by pin insert the length of side for 10cm square polystyrene foam plate in, wear needle point
Saturating cystosepiment simultaneously exposes 1cm length, and self-control needle plate is made, then with self-control needle plate, pressure is pricked 9 times repeatedly on fried pigskin, is passed through
Wear fried pigskin；Weigh to pour into after 2kg roselles are eluted with water in pulverizer and crush 25min and obtain crushed material, then by crushed material
It is 1 in mass ratio with deionized water:It is fitted into after 5 mixing in enzymatic vessel, 12g cellulases and 7g pectases is added into tank, it is close
After sealed cans mouthful 7h is digested at 50 DEG C；After enzymolysis terminates, take out enzymolysis product filtering and remove filter residue, enzymolysis liquid is obtained, by enzyme
Solve liquid to move into Rotary Evaporators, be reduced to the 1/5 of its original volume in 45 DEG C of backspin inspissations, obtain concentrate, by gained concentrate
It is that 0.1mol/L oxalic acid solutions are 3 by volume with concentration:Composite modified liquid is obtained after 1 mixing；It will pass through fried pigskin matter
It is that 70% methanol solution rinses 12min to measure fraction, then will be 1 in mass ratio through fried pigskin and composite modified liquid after flushing:
It is fitted into after 10 mixing in fermentation tank, then it is 10 to add the concentration of fried pigskin quality 5% into fermentation tank4Cfu/mL acetic acid bacteria bacterium
Suspension, heat-preservation fermentation 6 days at 37 DEG C；After after fermentation ends, take out fermentation it is modified run through fried pigskin, be put into vacuum jelly
It is freeze-dried in dry machine with -25 DEG C of temperature, 20 mesh sieves is crossed after finally being crushed with pulverizer, is produced after collecting sieving powder packaging
Biomass heavy-metal adsorption material.
Reference examples：Using charcoal as heavy-metal adsorption material,
The heavy-metal adsorption material of example 1 to example 3 and reference examples is added into the same water of content of beary metal respectively, added
Amount 2.0g/L, add after end, it be stirred and stood, take supernatant, detect its content of beary metal, testing result is such as
Table 1.
Table 1
As seen from the above table, the biomass heavy-metal adsorption material that prepared by the present invention greatly reduces the content of beary metal in water, makes
It meets the standard of drinking water.
Claims (8)
1. a kind of preparation method of biomass heavy-metal adsorption material, it is characterised in that specifically preparation process is：
（1）Take raw pig skin poured with boiling water scald after scrape off surface impurity, the pigskin after removal of impurities is put into pot and adds clear water, big fire boils
Switch to small fire to after seething with excitement, continue to cook 3~5min, cooking is pulled pigskin out after terminating, eluted with frozen water, then strike off pig with scraper
Intracutaneous side grease, obtains pre-processing pigskin；
（2）Pretreatment pigskin is dried, then the pigskin after drying is put into oil cauldron and is fried to pigskin is fluffy, untill its colour changed into yellow,
Pull the pigskin after frying out and be put into cooking in boiling water, then 5~7h is soaked with deionized water, obtain loose porous fried pigskin；
（3）Pin is inserted in square polystyrene foam plate, needle point is penetrated cystosepiment and exposes 1cm length, is made
Make needle plate by oneself, then with self-control needle plate, pressure is pricked repeatedly on above-mentioned fried pigskin, obtains running through fried pigskin, it is standby；
（4）Weigh and crushed after 2~3kg roselles are eluted with water, obtain crushed material, then will be filled after crushed material and deionized water mixing
Enter in enzymatic vessel, 10~15g cellulases and 5~8g pectases, sealing tank mouth enzymolysis are added into tank；
（5）After above-mentioned enzymolysis terminates, take out enzymolysis product filtering and remove filter residue, obtain enzymolysis liquid, enzymolysis liquid is concentrated, obtain
Concentrate, composite modified liquid is obtained after gained concentrate and oxalic acid solution are mixed；
（6）By step（3）Standby is rinsed through fried pigskin with methanol solution, then will run through fried pigskin and upper after flushing
It is fitted into after stating composite modified liquid mixing in fermentation tank, then addition acetic acid bacteria bacteria suspension, heat-preservation fermentation into fermentation tank；
（7）After after above-mentioned fermentation ends, take out fermentation it is modified run through fried pigskin, freeze-drying is finally crushed and crosses 20
Mesh sieve, biomass heavy-metal adsorption material is produced after collecting sieving powder packaging.
2. a kind of preparation method of biomass heavy-metal adsorption material according to claim 1, it is characterised in that：Step
（1）Described in the addition of clear water be 8~10 times of pigskin quality, the temperature of frozen water is 2~4 DEG C.
3. a kind of preparation method of biomass heavy-metal adsorption material according to claim 1, it is characterised in that：Described
The square polystyrene foam plate length of side is 10cm, and the contact pin amount of pin is 25/cm2。
4. a kind of preparation method of biomass heavy-metal adsorption material according to claim 1, it is characterised in that：Step
（4）Described in crushed material and deionized water mass ratio be 1:5, hydrolysis temperature is 45~55 DEG C, and enzymolysis time is 6~8h.
5. a kind of preparation method of biomass heavy-metal adsorption material according to claim 1, it is characterised in that：Step
（5）Described in method for concentration be：Enzymolysis liquid is moved into Rotary Evaporators, its original volume is reduced in 40~50 DEG C of backspin inspissations
1/5, obtain concentrate.
6. a kind of preparation method of biomass heavy-metal adsorption material according to claim 1, it is characterised in that：Step
（5）Described in concentrate and oxalic acid solution volume ratio be 3:1, oxalic acid solution concentration is 0.1mol/L.
7. a kind of preparation method of biomass heavy-metal adsorption material according to claim 1, it is characterised in that：Step
（6）Described in methanol solution mass fraction be 70%, through fried pigskin and composite modified liquid mass ratio be 1:10, acetic acid
Bacterium bacteria suspension concentration is 104Cfu/mL, the addition of acetic acid bacteria bacteria suspension is the 5% of fried pigskin quality.
8. a kind of preparation method of biomass heavy-metal adsorption material according to claim 1, it is characterised in that：Described
It is -30~-20 DEG C to be freeze-dried temperature.
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| CN101731640A (en) * | 2008-11-06 | 2010-06-16 | 董四清 | Pig skin sponge body-building food |
| CN101961648A (en) * | 2010-11-05 | 2011-02-02 | 天津森诺过滤技术有限公司 | Membrane adsorbent for removing heavy metal ions from drinking water effectively and preparation method thereof |
| CN102872806A (en) * | 2012-08-28 | 2013-01-16 | 常州大学 | Composite adsorbing material for removing titanium ions in natural water and preparation method thereof |
| CN104971702A (en) * | 2015-05-21 | 2015-10-14 | 四川大学 | Preparation method of collagen-based porous oil-absorbing material |
| CN105217719A (en) * | 2015-11-17 | 2016-01-06 | 梅庆波 | The treatment process of heavy metal chromium in a kind of leather-making waste water |
| CN106179248A (en) * | 2016-08-09 | 2016-12-07 | 吴迪 | A kind of preparation method of mesoporous Herba Potamogetonis Pectinati heavy metal ion adsorbing material |
-
2017
- 2017-06-07 CN CN201710424433.3A patent/CN107282008B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101731640A (en) * | 2008-11-06 | 2010-06-16 | 董四清 | Pig skin sponge body-building food |
| CN101961648A (en) * | 2010-11-05 | 2011-02-02 | 天津森诺过滤技术有限公司 | Membrane adsorbent for removing heavy metal ions from drinking water effectively and preparation method thereof |
| CN102872806A (en) * | 2012-08-28 | 2013-01-16 | 常州大学 | Composite adsorbing material for removing titanium ions in natural water and preparation method thereof |
| CN104971702A (en) * | 2015-05-21 | 2015-10-14 | 四川大学 | Preparation method of collagen-based porous oil-absorbing material |
| CN105217719A (en) * | 2015-11-17 | 2016-01-06 | 梅庆波 | The treatment process of heavy metal chromium in a kind of leather-making waste water |
| CN106179248A (en) * | 2016-08-09 | 2016-12-07 | 吴迪 | A kind of preparation method of mesoporous Herba Potamogetonis Pectinati heavy metal ion adsorbing material |
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