CN113929109A - Modification method of attapulgite clay and application of modification method to anaerobic and aerobic biochemical treatment method of organic wastewater - Google Patents

Modification method of attapulgite clay and application of modification method to anaerobic and aerobic biochemical treatment method of organic wastewater Download PDF

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Publication number
CN113929109A
CN113929109A CN202111372715.6A CN202111372715A CN113929109A CN 113929109 A CN113929109 A CN 113929109A CN 202111372715 A CN202111372715 A CN 202111372715A CN 113929109 A CN113929109 A CN 113929109A
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attapulgite clay
anaerobic
organic wastewater
aerobic
biochemical treatment
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Inventor
陈新德
黎海龙
熊莲
王璨
张海荣
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Xuyi Aotu Energy And Environmental Protection Materials R & D Center
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1205—Particular type of activated sludge processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • 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
    • 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
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Water Treatment By Sorption (AREA)
  • Treatment Of Sludge (AREA)
  • Biological Treatment Of Waste Water (AREA)

Abstract

The invention discloses a modification method of attapulgite clay and an application of the modification method to anaerobic and aerobic biochemical treatment methods of organic wastewater. Firstly, carrying out semidry sodium treatment on attapulgite clay to improve the viscosity of the attapulgite clay, then uniformly mixing the modified attapulgite clay and activated sludge, adding the mixture into an anaerobic and aerobic reactor, and carrying out biochemical treatment on organic wastewater. The semi-dry modification process has the advantages of low water consumption, no by-product, high viscosity and the like. In addition, the addition of the modified attapulgite clay enhances the COD removal effect of the activated sludge, shortens the starting time and improves the stability of the organic wastewater biochemical treatment system. The invention solves the defects and bad phenomena existing in the culture and use of granular sludge in the existing organic wastewater biochemical treatment process, and has wide application prospect.

Description

Modification method of attapulgite clay and application of modification method to anaerobic and aerobic biochemical treatment method of organic wastewater
Technical Field
The invention relates to the field of wastewater treatment, and in particular relates to a modification method of attapulgite clay and an application of the modification method to anaerobic and aerobic biochemical treatment methods of organic wastewater.
Background
Aerobic and anaerobic biochemical treatment technologies are the main means for treating urban and industrial organic wastewater, and the culture of granular sludge is the key for the successful implementation of the technology. The aerobic biochemical treatment is mainly applied to organic matter degradation and nitrogen and phosphorus removal in urban sewage treatment, and the existing aerobic granular sludge has the defects of poor stability, long culture time, poor settleability and the like, so that the aerobic biochemical treatment effect is poor, and the effluent quality of a sewage treatment plant is influenced. The anaerobic digestion technology is widely applied to the aspects of producing biogas by treating industrial organic wastewater and livestock and poultry excrement sewage, and the like, but in large-scale biogas engineering, the anaerobic granular sludge has the defects of large using amount, long starting time, low initial COD removal rate and the like, and the adverse phenomena of poor system stability, easy acidification, sludge leakage and the like in the use process exist. Therefore, reducing the amount of anaerobic granular sludge and enhancing the activity and stability of anaerobic granular sludge are problems that need to be solved in the engineering application of anaerobic digestion technology.
The attapulgite clay has larger specific surface area and abundant pore canal structures, so that the attapulgite clay has better adsorbability and expansibility. In addition, the attapulgite clay can improve the purity and the performance thereof after being modified, and is favorable for promoting the growth of granular sludge. Chinese invention patent CN 201410074518.X discloses that acid modified attapulgite is used for culturing aerobic nitrification activated sludge. Chinese patent CN 201610935478.2 discloses an organic modified attapulgite for accelerating anaerobic sludge granulation. However, the two modification methods cannot effectively increase the viscosity of the attapulgite clay.
Disclosure of Invention
The purpose of the invention is: the attapulgite clay modification method and the application thereof in organic wastewater anaerobic and aerobic biochemical treatment methods are provided, on one hand, after the attapulgite clay is subjected to sodium modification, the viscosity is greatly increased, the adsorption performance and the suspension performance are remarkably improved, the COD removal effect of the granular sludge is enhanced, and the start-up time is shortened; on the other hand, the sodium modified attapulgite clay is alkalescent in solution and can neutralize organic acid in the biochemical treatment process, so that the buffer effect is achieved, the phenomena of acidification and sludge leakage easily occurring in the biochemical treatment starting process are avoided, and the system stability is improved.
The invention is realized by the following technical scheme: a method for modifying attapulgite clay comprises adding pulverized attapulgite clay and sheared and dispersed attapulgite clay slurry into a stirrer, stirring and mixing; preparing a sodium carbonate solution, spraying the sodium carbonate solution on the surface of the mixed attapulgite clay by using an atomization device, and reacting; and (3) drying the reacted attapulgite clay in the sun, and crushing the attapulgite clay by using a Raymond mill to obtain the modified attapulgite clay.
Wherein the solid content of the attapulgite clay slurry after shearing and dispersing is 5-15%.
Wherein the mixing mass ratio of the crushed attapulgite clay to the sheared and dispersed attapulgite clay slurry is 1:2-2: 1.
Wherein the mass fraction of the sodium carbonate solution is 5-15%.
Wherein the mass ratio of the sodium carbonate solution to the mixed attapulgite clay is 1: 10-1: 5.
Wherein the modification reaction time is 0.5-2 h.
The modified attapulgite clay is applied to an anaerobic and aerobic biochemical treatment method of organic wastewater, organic wastewater is used as a substrate, the modified attapulgite clay and anaerobic or aerobic sludge are uniformly mixed and then added into an anaerobic or aerobic reactor to be used as an inoculum for anaerobic or aerobic fermentation.
Wherein the mixing mass ratio of the modified attapulgite clay to the anaerobic or aerobic sludge is 1:5-1: 15.
Wherein, the total addition of the inoculum is 20-80% of the total volume of the anaerobic or aerobic reactor.
Wherein the organic wastewater is one of pig manure wastewater, straw hydrolysate wastewater, molasses wastewater or other organic wastewater with good biodegradability.
The invention has the technical effects that:
1. the cohesiveness of the attapulgite clay after sodium modification is obviously improved, the sedimentation performance of the granular sludge is better, the granular sludge is not easy to flow out along with circulating water under the condition of large circulating amount, the using amount of anaerobic granular sludge is reduced, and the stability of the granular sludge is enhanced.
2. The sodium modified attapulgite clay can effectively adsorb organic matters, is beneficial to the propagation of microorganisms thereon, improves the removal rate of COD, promotes the proliferation of granular sludge and reduces the using amount of the granular sludge.
3. The sodium modified attapulgite clay is alkalescent in solution, can be neutralized with organic acid in biochemical treatment process, plays a role in buffering, avoids acidification phenomenon easily occurring in starting process, and improves system stability.
4. The semi-dry modification process has the advantages of low water consumption, no by-product, high viscosity and the like.
Detailed Description
The following examples are given to further illustrate the technical solutions of the present invention, but not to limit the present invention.
Example 1: pouring 150kg of crushed attapulgite clay and 75kg of sheared and dispersed attapulgite clay slurry (the solid content is 5%) into a stirrer, and uniformly stirring; preparing 45kg of sodium carbonate solution with the mass of 5%, spraying the solution on the surface of the mixed attapulgite clay by using an atomization device, and carrying out sodium modification reaction for 2 hours; after the reaction is finished, the sodium modified attapulgite clay is dried in the sun and crushed by a Raymond mill to obtain the sodium modified attapulgite clay with the viscosity of 1180 mPa.s.
Uniformly mixing sodium modified attapulgite clay and anaerobic sludge according to the mass ratio of 1:5, adding into an anaerobic reactor for anaerobic fermentation, wherein the total addition amount is 50% of the total volume of the anaerobic or aerobic reactor, and performing anaerobic digestion by adopting pig manure wastewater. After 21 days of fermentation, the COD removal rate is 87 percent, and the biogas yield is 0.48 m3/kg COD。
Example 2: pouring 150kg of crushed attapulgite clay and 75kg of sheared and dispersed attapulgite clay slurry (the solid content is 10%) into a stirrer to be uniformly stirred; preparing 30kg of sodium carbonate solution with the mass of 10%, spraying the solution on the surface of the mixed attapulgite clay by using an atomization device, and carrying out sodium modification reaction for 1 h; after the reaction is finished, the sodium modified attapulgite clay is dried in the sun and crushed by a Raymond mill to obtain the sodium modified attapulgite clay with the viscosity of 1350 mPa.s.
Uniformly mixing sodium modified attapulgite clay and anaerobic sludge according to the mass ratio of 1:15, adding into an anaerobic reactor for anaerobic fermentation, wherein the total addition amount is 80% of the total volume of the reactor, and performing anaerobic digestion by adopting straw hydrolysate wastewater. After 21 days of fermentation, the COD removal rate is 90 percent, and the biogas yield is 0.54 m3/kg COD。
Example 3: pouring 150kg of crushed attapulgite clay and 75kg of sheared and dispersed attapulgite clay slurry (the solid content is 15%) into a stirrer to be uniformly stirred; preparing 22.5kg of sodium carbonate solution with the mass of 15%, spraying the solution on the surface of the mixed attapulgite clay by using an atomization device, and carrying out sodium modification reaction for 0.5 h; after the reaction is finished, the sodiumized attapulgite clay is subjected to sun-drying treatment and is crushed by a Raymond mill to obtain the sodiumized modified attapulgite clay, and the viscosity of the sodiumized modified attapulgite clay reaches 1480 mPa.s.
Uniformly mixing sodium modified attapulgite clay and anaerobic sludge according to the mass ratio of 1:10, adding into an anaerobic reactor for anaerobic fermentation, wherein the total addition amount is 60% of the total volume of the reactor, and performing anaerobic digestion by adopting molasses wastewater. After 21 days of fermentation, the COD removal rate is 91 percent, and the biogas yield is 0.53 m3/kg COD。
Example 4: pouring 150kg of crushed attapulgite clay and 75kg of sheared and dispersed attapulgite clay slurry (the solid content is 10%) into a stirrer to be uniformly stirred; preparing 30kg of sodium carbonate solution with the mass of 10%, spraying the solution on the surface of the mixed attapulgite clay by using an atomization device, and carrying out sodium modification reaction for 1 h; after the reaction is finished, the sodium modified attapulgite clay is dried in the sun and crushed by a Raymond mill to obtain the sodium modified attapulgite clay with the viscosity of 1254 mPa.s.
Uniformly mixing sodium modified attapulgite clay and aerobic sludge according to the mass ratio of 1:6, adding into an aerobic reactor for aerobic treatment, wherein the total addition amount is 20% of the total volume of the aerobic reactor, and performing aerobic fermentation by adopting molasses wastewater. After 21 days of fermentation, the COD removal rate was 82%.
Example 5: pouring 150kg of crushed attapulgite clay and 75kg of sheared and dispersed attapulgite clay slurry (the solid content is 8%) into a stirrer to be uniformly stirred; preparing 40kg of sodium carbonate solution with the mass of 8%, spraying the solution on the surface of the mixed attapulgite clay by using an atomization device, and carrying out sodium treatment for 1.5 h; after the reaction is finished, the sodium modified attapulgite clay is dried in the sun and crushed by a Raymond mill to obtain the sodium modified attapulgite clay with the viscosity of 1321 mPa.s.
Uniformly mixing sodium modified attapulgite clay and aerobic sludge according to the mass ratio of 1:5, adding into an aerobic reactor for aerobic treatment, wherein the total addition amount is 30% of the total volume of the aerobic reactor, and performing aerobic fermentation by adopting straw hydrolysate wastewater. After 21 days of fermentation, the COD removal rate was 86%.
Example 6: pouring 60kg of crushed attapulgite clay and 120kg of sheared and dispersed attapulgite clay slurry (the solid content is 15%) into a stirrer to be uniformly stirred; preparing 30kg of sodium carbonate solution with the mass of 10%, spraying the solution on the surface of the mixed attapulgite clay by using an atomization device, and carrying out sodium modification reaction for 1 h; after the reaction is finished, the sodium modified attapulgite clay is dried in the sun and crushed by a Raymond mill to obtain the sodium modified attapulgite clay with the viscosity of 1160 mPa.s.
Uniformly mixing sodium modified attapulgite clay and aerobic sludge according to the mass ratio of 1:8, adding into an aerobic reactor for aerobic treatment, wherein the total addition amount is 25% of the total volume of the aerobic reactor, and performing aerobic fermentation by adopting molasses wastewater. After 21 days of fermentation, the COD removal rate was 82%.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (10)

1. A modification method of attapulgite clay is characterized in that: pouring the crushed attapulgite clay and the sheared and dispersed attapulgite clay slurry into a stirrer to be uniformly stirred; preparing a sodium carbonate solution, spraying the sodium carbonate solution on the surface of the mixed attapulgite clay by using an atomization device, and reacting; and (3) drying the reacted attapulgite clay in the sun, and crushing the attapulgite clay by using a Raymond mill to obtain the modified attapulgite clay.
2. The method for modifying attapulgite clay according to claim 1, wherein the method comprises the following steps: the solid content of the attapulgite clay slurry after shearing and dispersing is 5-15%.
3. The method for modifying attapulgite clay according to claim 1, wherein the method comprises the following steps: the mixing mass ratio of the crushed attapulgite clay to the sheared and dispersed attapulgite clay slurry is 1:2-2: 1.
4. The method for modifying attapulgite clay according to claim 1, wherein the method comprises the following steps: the mass fraction of the sodium carbonate solution is 5-15%.
5. The method for modifying attapulgite clay according to claim 1, wherein the method comprises the following steps: the mass ratio of the sodium carbonate solution to the mixed attapulgite clay is 1: 10-1: 5.
6. The method for modifying attapulgite clay according to claim 1, wherein the method comprises the following steps: the modification reaction time is 0.5-2 h.
7. The modified attapulgite clay is applied to the anaerobic and aerobic biochemical treatment method of organic wastewater, and is characterized in that: the organic wastewater is used as a substrate, the modified attapulgite clay and the anaerobic or aerobic sludge are uniformly mixed and then added into an anaerobic or aerobic reactor to be used as an inoculum for anaerobic or aerobic fermentation.
8. The modified attapulgite clay applied to the anaerobic and aerobic biochemical treatment method of organic wastewater according to claim 7, characterized in that: the mixing mass ratio of the modified attapulgite clay to the anaerobic or aerobic sludge is 1:5-1: 15.
9. The modified attapulgite clay applied to the anaerobic and aerobic biochemical treatment method of organic wastewater according to claim 7, characterized in that: the total addition of the inoculum is 20-80% of the total volume of the anaerobic or aerobic reactor.
10. The modified attapulgite clay applied to the anaerobic and aerobic biochemical treatment method of organic wastewater according to claim 7, characterized in that: the organic wastewater is one of pig manure wastewater, straw hydrolysate wastewater, molasses wastewater or other organic wastewater with good biodegradability.
CN202111372715.6A 2021-11-19 2021-11-19 Modification method of attapulgite clay and application of modification method to anaerobic and aerobic biochemical treatment method of organic wastewater Pending CN113929109A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1749798A1 (en) * 2005-07-28 2007-02-07 Sociedad Anonima Minera Catalano-Aragonesa Mineral product for the technological improvement of aerobic biological treatments and corresponding use thereof
CN1912015A (en) * 2006-08-25 2007-02-14 蒋文兰 Concave convex rod suspension agent
CN101348257A (en) * 2008-08-25 2009-01-21 许盛英 Production process of paste attapulgite clay
CN104016367A (en) * 2014-06-01 2014-09-03 许盛英 Sodium modified attapulgite clay
CN105502607A (en) * 2016-01-26 2016-04-20 山东科技大学 Composite flocculant for piggery wastewater and biological fermentation treatment method and equipment
CN106630131A (en) * 2016-10-25 2017-05-10 南京大学宜兴环保研究院 Preparation method of modified attapulgite particles and method for accelerating granulation of anaerobic sludge by modified attapulgite particles
CN108262017A (en) * 2016-12-30 2018-07-10 海门市源美美术图案设计有限公司 A kind of Attapulgite and the application in feeding wastewater treatment

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1749798A1 (en) * 2005-07-28 2007-02-07 Sociedad Anonima Minera Catalano-Aragonesa Mineral product for the technological improvement of aerobic biological treatments and corresponding use thereof
CN1912015A (en) * 2006-08-25 2007-02-14 蒋文兰 Concave convex rod suspension agent
CN101348257A (en) * 2008-08-25 2009-01-21 许盛英 Production process of paste attapulgite clay
CN104016367A (en) * 2014-06-01 2014-09-03 许盛英 Sodium modified attapulgite clay
CN105502607A (en) * 2016-01-26 2016-04-20 山东科技大学 Composite flocculant for piggery wastewater and biological fermentation treatment method and equipment
CN106630131A (en) * 2016-10-25 2017-05-10 南京大学宜兴环保研究院 Preparation method of modified attapulgite particles and method for accelerating granulation of anaerobic sludge by modified attapulgite particles
CN108262017A (en) * 2016-12-30 2018-07-10 海门市源美美术图案设计有限公司 A kind of Attapulgite and the application in feeding wastewater treatment

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