CN110038512A - A kind of attapulgite adsorbent and its application - Google Patents
A kind of attapulgite adsorbent and its application Download PDFInfo
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- CN110038512A CN110038512A CN201910344649.8A CN201910344649A CN110038512A CN 110038512 A CN110038512 A CN 110038512A CN 201910344649 A CN201910344649 A CN 201910344649A CN 110038512 A CN110038512 A CN 110038512A
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- attapulgite
- adsorbent
- spherolite
- heat treatment
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 59
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 59
- 239000003463 adsorbent Substances 0.000 title claims abstract description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000004575 stone Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000009287 sand filtration Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000006115 defluorination reaction Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 206010016818 Fluorosis Diseases 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 208000004042 dental fluorosis Diseases 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002366 mineral element Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018085 Al-F Inorganic materials 0.000 description 1
- 229910018179 Al—F Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019077 Mg—F Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910008284 Si—F Inorganic materials 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- -1 agricultural Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention relates to a kind of attapulgite adsorbents; it is prepared by the following method: concave and convex rod stone powder being taken to be added in pelletizer; water is added to be granulated; obtaining diameter is 2-4mm attapulgite spherolite; after drying, attapulgite spherolite is placed in Muffle furnace, 100-600 DEG C of heat treatment 3-6h; it then cools to room temperature, i.e. attapulgite adsorbent.The attapulgite adsorbent can be used for handling fluoride waste, and method is simple, and attapulgite adsorbent is added into fluoride waste, be greater than 6 with sodium hydroxide tune pH after mixing, settle sand filtration after 15-20min.Attapulgite adsorbent preparation of the invention is simple, and heat treatment temperature is not high, and heat treatment modification can be obviously improved the performance of attapulgite, under the conditions of especially neutral with alkaline water.
Description
Technical field
The present invention relates to a kind of attapulgite adsorbents, belong to environment remediation technical field.
Background technique
Current fluoride pollution underground water has become a global environmental problem, and endemic fluorosis also becomes a kind of generation
The endemic disease of the serious harm human health of boundary's range.The whole world has more than 30 countries and regions, is faced with more than 200,000,000 populations
The threat of Water related fluorosis, most of these countries and regions concentrate on developing country.China is that fluoride pollution endangers most
One of serious country has more than 28 provinces and cities, there are Fluorine of Drinking Water over-standard phenomenons for autonomous region.Drunk high-fluorine water harm in China
More serious area is Henan, Hebei, Anhui and the Inner Mongol, and drinking population is respectively 1,270,000,7,490,000,4,360,000 and 365
Ten thousand, the population for drinking high-fluorine water is all located at national first place in absolute quantity and ratio.And in Xuzhou City of Jiangsu Province some areas
Underground water fluoride content up to 13mg/L, considerably beyond the drinking water standard of safety, therefore, probe into technology of Fluoride Removal and principle, seek
It is most important to find most suitable defluorination material.
Existing artificial defluorination method mainly includes absorption method, coagulant sedimentation, electrochemical method, membrane separation process etc..It is mixed
The solidifying precipitation method limit its application due to that can introduce other ions when handling fluoride waste significantly；Electrochemical method not only consumes
A large amount of electric energy, and some mineral elements in water can be removed, thus limit its application；Ion-exchange is handed over using ion
A kind of method of resin fluorine removal is changed, easy to operate, defluorination effect is stablized, but also eliminates water Mineral Elements simultaneously and introduce
Amine and be restricted；Membrane separation process is a kind of clean defluorination method, and expensive film cost is to limit its popularity
An important factor for.The advantages such as wherein for absorption method with its simple process, operation cost is low, and application conditions are wide are most popular.Matter attachment
Aggregation is mutually known as adsorbent.Absorption is when two are in contact, and one of one of phase or various ingredients are in another phase
Surface there is a phenomenon where opposite aggregation, mostly occur in solid-liquid or solid gas two-phase interface.The component being adsorbed is known as adsorbate, inhales
Attached absorption method is by adding porosu solid, and when it is contacted with fluid, a certain component or multiple components in fluid are in solid
Surface generates savings, to separate a kind of method of certain component in fluid.Adsorbing separation is widely used in chemical industry, petroleum, food
The departments such as product, light industry and environmental protection.
It is when previous research hotspot by absorption method fluorine removal.Its most important work is to find one kind efficiently, inexpensively
The adsorbent being easy to get again.In the industry or drinking water often uses Defluorination of Formation Mater By Adsorption On Activated Alumina.Defluorination of Formation Mater By Adsorption On Activated Alumina agent is white spherolite,
Fluorine removal capacity is big, through the purified water of the defluorinating agent, can reach the sanitary standard of drinking water of national regulation, defluorination effect is significant.But
The synthesis cost of activated alumina is higher, and pollution is easy to produce in manufacture craft.Attapulgite is a kind of naturally occurring viscous
Native mineral, not only relative inexpensiveness, and also it is with unique micropore and microchannel configurations, so that it possesses excellent absorption
Property, big specific surface area and stronger ion-exchange capacity.Currently, attapulgite petroleum, chemical industry, building materials, agricultural, medicine,
The industries such as papermaking are widely used.With the development of industry, water pollution is very serious, pollution of the fluorine ion to water quality
It is very serious, great threat is caused to human health, leading to common attapulgite clay adsorbent has the suction-operated of fluorine ion
Limit, needs to be modified it, to further increase the absorption property to fluorine ion.
Summary of the invention
The purpose of the present invention is overcoming the defect of the above-mentioned prior art, a kind of attapulgite adsorbent is provided.
The technical scheme is that
A kind of attapulgite adsorbent, is prepared by the following method: concave and convex rod stone powder being taken to be added in pelletizer, add
Water is granulated, and is obtained attapulgite spherolite and attapulgite spherolite is placed in Muffle furnace, 100-600 DEG C of heat treatment 3- after dry
6h is then cooled to room temperature, i.e. attapulgite adsorbent.
Further, the diameter of the attapulgite spherolite is 2-4mm.
Further, the heat treatment temperature is 200-400 DEG C.
Above-mentioned attapulgite adsorbent is used to handle the application of fluoride waste, application method are as follows: add into fluoride waste
Attapulgite adsorbent is greater than 6 with sodium hydroxide tune pH after mixing, settles sand filtration after 15-20min.
Beneficial effects of the present invention:
1, fluoride removing rate is high under attapulgite adsorbent alkaline condition of the invention: because under alkaline condition, attapulgite
Fluorine removal is compared with the absorption for relying on tunnel site, and the structure that Low Temperature Heat Treatment makes attapulgite closely interweave becomes fluffy, thus more
Tunnel site is exposed, and original water is also because heat treatment abjection, this results in Low Temperature Heat Treatment under alkaline condition in tunnel
Attapulgite promotes fluorine adsorption rate.And under acid condition, the mechanism of attapulgite fluorine removal mainly forms Al-F on surface,
Si-F, Mg-F adsorption site, therefore adsorbance is mainly influenced by specific surface, Low Temperature Heat Treatment deviates from water binding site, while making to hand over
Knitting structure becomes loosely, meanwhile, the alkaline clay mineral under acid condition in attapulgite is easier to dissolution and forms clay colloid, shows
It writes and increases its specific surface area.
2, attapulgite adsorbent of the invention preparation is simple, and heat treatment temperature is not high, and heat treatment modification can be obviously improved
The performance of attapulgite, under the conditions of especially neutral with alkaline water.
Detailed description of the invention
Fig. 1 is fluoride removing rate of the 200 DEG C of heat treatment attapulgite adsorbents of embodiment 1 in the fluoride waste of pH6-11；
Fig. 2 is fluoride removing rate of the 400 DEG C of heat treatment attapulgite adsorbents of embodiment 2 in the fluoride waste of pH6-11；
Fig. 3 is fluoride removing rate of the 600 DEG C of heat treatment attapulgite adsorbents of embodiment 3 in the fluoride waste of pH6-11.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
A kind of attapulgite adsorbent, is prepared by the following method: concave and convex rod stone powder being taken to be added in pelletizer, add
Water is granulated, and is obtained the attapulgite spherolite that diameter is 3mm and attapulgite spherolite is placed in Muffle furnace, 200 DEG C of heat after dry
3h is handled, is then cooled to room temperature, i.e. attapulgite adsorbent.
Embodiment 2
A kind of attapulgite adsorbent, is prepared by the following method: concave and convex rod stone powder being taken to be added in pelletizer, add
Water is granulated, and is obtained the attapulgite spherolite that diameter is 3mm and attapulgite spherolite is placed in Muffle furnace, 400 DEG C of heat after dry
3h is handled, is then cooled to room temperature, i.e. attapulgite adsorbent.
Embodiment 3
A kind of attapulgite adsorbent, is prepared by the following method: concave and convex rod stone powder being taken to be added in pelletizer, add
Water is granulated, and is obtained the attapulgite spherolite that diameter is 3mm and attapulgite spherolite is placed in Muffle furnace, 600 DEG C of heat after dry
3h is handled, is then cooled to room temperature, i.e. attapulgite adsorbent.
Using test:
Test method: it adds the attapulgite adsorbent of embodiment 1-3 respectively into fluoride waste, uses hydrogen after mixing
Sodium oxide molybdena and nitric acid tune pH (adjust pH6,7,8,9,10,11) respectively, settle sand filtration after 20min, in surplus solution (when balancing)
Fluorinion concentration by Fluoride ion selective electrode method measure, its working principle is that Nernst equation, passes through initial ion concentration
Fluoride removing rate is calculated with ion concentration when balance, tests and calculates the attapulgite adsorbent of embodiment 1-3 under condition of different pH
Fluoride removing rate.
The result is shown in Figure 1,2 and 3, Fig. 1 are fluorine removal of the attapulgite adsorbent of embodiment 1 in the fluoride waste of pH6-11
Rate；Fig. 2 is fluoride removing rate of the attapulgite adsorbent of embodiment 2 in the fluoride waste of pH6-11；Fig. 3 is the recessed of embodiment 3
Fluoride removing rate of the convex stick stone adsorbent in the fluoride waste of pH6-11, it can be seen that attapulgite adsorbent of the invention with
When handling the fluoride waste of pH6-11, there is preferable defluorination effect.
Claims (4)
1. a kind of attapulgite adsorbent, which is characterized in that be prepared by the following method: taking concave and convex rod stone powder to be added to and make
In grain machine, water is added to be granulated, obtains attapulgite spherolite and attapulgite spherolite is placed in Muffle furnace, 100-600 DEG C after dry
It is heat-treated 3-6h, is then cooled to room temperature, i.e. attapulgite adsorbent.
2. attapulgite adsorbent as described in claim 1, which is characterized in that the diameter of the attapulgite spherolite is 2-4mm.
3. attapulgite adsorbent as claimed in claim 1 or 2, which is characterized in that the heat treatment temperature is 200-400 DEG C.
4. the application that claims 1 or 2 or the 3 attapulgite adsorbents are used to handle fluoride waste, which is characterized in that application
Method are as follows: add attapulgite adsorbent into fluoride waste, be greater than 6 with sodium hydroxide tune pH after mixing, settle 15-
Sand filtration after 20min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910344649.8A CN110038512A (en) | 2019-04-26 | 2019-04-26 | A kind of attapulgite adsorbent and its application |
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| CN201910344649.8A CN110038512A (en) | 2019-04-26 | 2019-04-26 | A kind of attapulgite adsorbent and its application |
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| CN110038512A true CN110038512A (en) | 2019-07-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112473617A (en) * | 2020-11-05 | 2021-03-12 | 安徽绿萝兰环保科技有限公司 | Method for preparing attapulgite drying agent for packaging |
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| CN1283517A (en) * | 2000-06-25 | 2001-02-14 | 宁波绿色医疗设备有限公司 | Process for preparing effecient granular adsorbent to adsorb anesthetic gas |
| CN101653722A (en) * | 2009-08-31 | 2010-02-24 | 合肥工业大学 | Preparation method and application of attapulgite clay dephosphorization adsorbent |
| CN103723785A (en) * | 2013-12-13 | 2014-04-16 | 陕西科技大学 | Method adopting lanthanum modified attapulgite to remove fluorinion in water |
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2019
- 2019-04-26 CN CN201910344649.8A patent/CN110038512A/en active Pending
Patent Citations (3)
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|---|---|---|---|---|
| CN1283517A (en) * | 2000-06-25 | 2001-02-14 | 宁波绿色医疗设备有限公司 | Process for preparing effecient granular adsorbent to adsorb anesthetic gas |
| CN101653722A (en) * | 2009-08-31 | 2010-02-24 | 合肥工业大学 | Preparation method and application of attapulgite clay dephosphorization adsorbent |
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Application publication date: 20190723 |