CN106560236B - Sewage treatment active sludge carbon and preparation method thereof with filled aperature distribution characteristics - Google Patents
Sewage treatment active sludge carbon and preparation method thereof with filled aperature distribution characteristics Download PDFInfo
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- CN106560236B CN106560236B CN201610493575.0A CN201610493575A CN106560236B CN 106560236 B CN106560236 B CN 106560236B CN 201610493575 A CN201610493575 A CN 201610493575A CN 106560236 B CN106560236 B CN 106560236B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000010802 sludge Substances 0.000 title claims abstract description 103
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 78
- 239000010865 sewage Substances 0.000 title claims abstract description 32
- 238000011282 treatment Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000009826 distribution Methods 0.000 title claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 56
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 50
- 239000012190 activator Substances 0.000 claims abstract description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 28
- 238000013329 compounding Methods 0.000 claims abstract description 25
- 239000011780 sodium chloride Substances 0.000 claims abstract description 25
- 239000011592 zinc chloride Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- YJCZGTAEFYFJRJ-UHFFFAOYSA-N n,n,3,5-tetramethyl-1h-pyrazole-4-sulfonamide Chemical compound CN(C)S(=O)(=O)C=1C(C)=NNC=1C YJCZGTAEFYFJRJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 98
- 229910052757 nitrogen Inorganic materials 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 29
- 238000007493 shaping process Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011280 coal tar Substances 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000010801 sewage sludge Substances 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000003463 adsorbent Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 230000002950 deficient Effects 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000001994 activation Methods 0.000 description 40
- 230000004913 activation Effects 0.000 description 39
- 239000000243 solution Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000003610 charcoal Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002956 ash Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 timber Substances 0.000 description 1
- 238000005406 washing 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
-
- 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
- B01J2220/42—Materials comprising a mixture of inorganic 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
- 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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention discloses the sewage treatment active sludge carbon and preparation method thereof with filled aperature distribution characteristics, under oxygen deficient atmospheres, with ZnCl2, phosphoric acid, K2S and NaCl composition compounding activator, activates sludge, mainly develops central hole structure, active sludge carbon K with phosphoric acid+And Na+Content increases, and is conducive to the displacement performance of enhancing with heavy metal ions in sewage.It is activated again with vapor, generates micropore abundant in mesopore surface, finally obtained active sludge carbon BET specific surface area is not less than 400m2/ g, aperture are continuously distributed in 0.5-50nm.Adsorbent of the active sludge carbon of preparation as sewage treatment, with Pb in absorption effluent2+For the heavy metal ion and macromolecule contaminant of representative, there is good effect.
Description
Technical field
The invention belongs to environmental resource technical fields, more specifically, relate to the use of the side that sludge prepares active carbon
Method, and active carbon is used for sewage treatment.
Background technique
It prepares active carbon and generallys use the carbon raw materials such as coal, timber, shell, influenced by resource, environmental protection etc., active carbon is raw
Cost is produced to increase year by year.For sludge because containing a large amount of organic matter, carbon content is higher, has the objective condition for preparing active carbon.With
Sludge is that raw material prepares active carbon, can be effectively reduced cost of material, while making sludge itself and rationally disposed, realizes resource
Change and utilizes.Sludge through charing process has solidification to the heavy metal of itself, can be used as the adsorbent of sewage treatment, realizes
The treatment of wastes with processes of wastes against one another.
Existing active sludge carbon technology of preparing mainly includes pyrolysismethod, chemical activation method and gas activation.Research knot
Fruit show single active carbon with pyrolytic process preparation have in, the pore structure based on macropore.Pyrolysis temperature at 400-650 DEG C,
Macropore proportion is 40%-55%, and specific surface area is smaller, is usually no more than 150m2/ g, absorption property are limited.Chemical activation
Method generallys use ZnCl2, KOH, phosphoric acid, sulfuric acid etc. be used as activator.When list is with phosphoric acid activation, active carbon is with central hole structure
It is main；Sulfuric acid activated pore volume and specific surface area is generally below phosphoric acid activation；Using ZnCl2It is activated with KOH, produces micropore knot
Structure, but ZnCl2Big with KOH consumption and strong to the corrosivity of equipment, economy is lower.Gas activation agent mainly includes flue
Gas and vapor, activation are conducive to the development of micropore, especially steam activation, hole can be made to deepen under high temperature, be conducive to enrich
Microcellular structure.Compared with chemical activation method, gas activation production cost is low, and avoids equipment corrosion and environment dirt
Dye.However, individually using gas activation, pore-forming efficiency is lower.It is bullied the control spread in vivo, the development of active carbon internal capillary
While, surface also can seriously burn mistake, reduce to obtain charcoal rate.
Active sludge carbon is used for sewage treatment, adsorbs different pollutants, and required aperture is different.Adsorb heavy metal ion etc.
When small molecule type pollutant, microcellular structure abundant is needed；When adsorbing larger molecular organics, mesoporous and macroporous structure more have
Effect.The active sludge carbon of existing activation method preparation is mostly based on central hole structure, microcellular structure shortcoming, it is difficult to realize heavy metal from
Efficient absorption while son and macromolecule contaminant.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide the sewage treatments with filled aperature distribution characteristics
With active sludge carbon and preparation method thereof, it is related to a kind of active sludge carbon preparation method for combining activation stage by stage, to be had
There is filled aperature distribution characteristics and obtains the high sewage treatment active sludge carbon of charcoal rate.The present invention proposes a kind of with continuous aperture
The active sludge carbon preparation method of diameter distribution characteristics creates mesoporous abundant using compounding activator and gas activator stage by stage
Structure and microcellular structure, and K+And Na+Content is higher, and carbon loss is lower.
Technical purpose of the invention is achieved by following technical proposals:
Sewage treatment active sludge carbon and preparation method thereof with filled aperature distribution characteristics, as steps described below into
Row preparation:
Step 1, by sludge with compound activator aqueous solution and be uniformly mixed and impregnate, wherein the drying base carbon content of sludge is not
Lower than 30%, ash content is not higher than 40%, and moisture content is in 10wt%-20wt%；Activator aqueous solution is compounded by ZnCl2, phosphoric acid,
K2S, NaCl and water composition, ZnCl2Concentration is 1-2.5mol/L, phosphoric acid concentration 2-5mol/L, K2S additional amount is dewatered sludge matter
The 8%-15% of amount, NaCl additional amount are the 0.5%-2% of dewatered sludge quality；Sludge quality with compound activator aqueous solution volume
Than impregnating 8-12h at 20-25 DEG C for 1:(1-2.5)；
In step 1, the sludge of sewage treatment plant is selected, dry base carbon content is not less than 30%, and ash content is not higher than 40%；
It is dried, dehydration, makes moisture content that sludge are prepared into 200 μm of dirts below of partial size through broken, sieving in 10%-20%
Mud powder, preferably 100-200 μm.
Step 2, sludge prepared by step 1 is lower than 10wt% with mixture drying to the moisture content for compounding activator, added
Enter binder molding, shaping raw material is prepared, in order to which finished activated charcoal is applied in sewage treatment；
In step 2, binder is coal tar, and from coal high-temperature retorting, wherein asphalt quality percentage is not less than
55%, carbolineum mass percent is not higher than 10%.
In step 2, sludge is 1:(0.2-0.35 with the mass ratio of the mixture and binder that compound activator).
In step 2, select granulating and forming for cylindrical body, diameter 6-9mm, length 12-18mm.
Step 3, the shaping raw material prepared by step 2 is carbonized in nitrogen, from 20-25 DEG C of room temperature, with 8-15
DEG C/heating rate of min is warming up to 450-650 DEG C and keeps the temperature 1-2.5h.
In step 3, first with the air (i.e. oxygen gas component) in nitrogen removal reaction system, so that in entire reaction system
Full of nitrogen, then from 20-25 DEG C of room temperature, 450-650 DEG C is warming up to the heating rate of 8-15 DEG C/min and keeps the temperature 1-
2.5h。
In step 3, from 20-25 DEG C of room temperature, 500-600 DEG C is warming up to the heating rate of 10-12 DEG C/min and is protected
1.5-2h of temperature.
In step 3, nitrogen flow, which is subject to, maintains nitrogen in reaction system, and with shaping raw material close contact, molding
The ratio between mass parts and the parts by volume of nitrogen flow of raw material are 1:(10-15), each mass parts are 1g, and each parts by volume is
1ml/min。
Step 4, after the heat preservation by step 3, second step processing is carried out to shaping raw material, with the liter of 12-20 DEG C/min
Warm rate raises the temperature to 700-850 DEG C, and is passed through into reaction system the mixed gas of vapor and nitrogen while keeping the temperature
React 0.5-2h, in mixed gas vapor percentage by volume be 30-80%, after completion of the reaction stop be passed through vapor and
The mixed gas of nitrogen, and continue to be passed through nitrogen into reaction system, so that cooled to room temperature 20-in a nitrogen atmosphere
25℃。
In step 4, it raises the temperature to 750-800 DEG C and is passed through the gaseous mixture of vapor and nitrogen into reaction system
Body while insulation reaction 1-2h.
In step 4, vapor percentage by volume is 40-60% in mixed gas.
In step 4, the mixed gas flow of vapor and nitrogen, which is subject to, maintains have sufficient vapor in reaction system,
And make vapor and shaping raw material close contact, the body of the mixed gas flow of the mass parts and vapor and nitrogen of shaping raw material
The ratio between product part is 1:(10-15), each mass parts are 1g, and each parts by volume is 1ml/min.
Step 5, after carrying out pickling to the product of cooled to room temperature, it is washed to neutrality.
In steps of 5, when carrying out pickling, the hydrochloride aqueous solution of mass percent 12-15% is used；It is direct when washing
Use distilled water.
Compared with prior art, the present invention creates mesoporous knot abundant using compounding activator and gas activator stage by stage
Structure and microcellular structure, and carbon loss is effectively reduced.First stage using compounding activator, to create based on central hole structure.?
Under oxygen deficient atmospheres, with ZnCl2, phosphoric acid, K2S and NaCl composition compounding activator, activates sludge.Mainly developed with phosphoric acid
Central hole structure makes mesopore volume not less than 0.15cm3/g；The ZnCl of low concentration2Develop a certain amount of microcellular structure；A small amount of K2S promotees
Into Pore development and increase the K of active sludge carbon+Content, micro NaCl increase the Na of active carbon+Content.Active sludge carbon K+With
Na+Content increases, and is conducive to the displacement performance of enhancing with heavy metal ions in sewage.Second stage uses gas activation, into
One step develops microcellular structure.Using vapor, micropore abundant is generated in mesopore surface, is not less than its Micropore volume
0.1cm3/ g, and iodine sorption value is not less than 420mg/g.It is activated through two stages, finally obtained active sludge carbon BET specific surface
Product is not less than 400m2/ g, aperture is continuously distributed in 0.5-50nm, can be used for multiple pollutant in absorption effluent.First stage is living
Change the central hole structure formed, the gas diffusion resistance of second stage can be reduced, carbon caused by avoiding because of diffusion control in gas
Loss, it is low to solve the problems, such as that gas activation obtains charcoal rate.Second stage uses gas activation sustainable development micropore, can reduce
ZnCl2The additive amount of equal chemicals, the problems such as reducing preparation cost, equipment is avoided to corrode.The active sludge carbon of preparation is as dirty
The adsorbent of water process, with Pb in absorption effluent2+For the heavy metal ion and macromolecule contaminant of representative, there is good effect
Fruit.
The present invention obtains the active sludge carbon with filled aperature distribution characteristics, can be used for major pollutants heavy metal in water
It is adsorbed while ion and organic matter, activated carbon surface K+、Na+Content is higher, further enhances the adsorptivity to heavy metal ion
Energy；Activation is combined using compounding activator, gas activation agent stage by stage, can reduce that chemical activation method is at high cost, corrosivity is strong, dirt
The problems such as metachromia is high can also solve the problems, such as the surface carbon loss of gas activation.
Detailed description of the invention
Fig. 1 is active sludge carbon prepared by the present invention to Pb2+Adsorbance schematic diagram.
Fig. 2 is the pore-size distribution schematic diagram of active sludge carbon prepared by the present invention.
Fig. 3 is influence schematic diagram of the steam activation time to iodine sorption value in present invention preparation.
Fig. 4 is influence schematic diagram of the phosphoric acid concentration to active sludge carbon mesopore volume in present invention preparation.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.Choose certain municipal sewage plant residue
Sludge, dry base carbon content 32.5%, ash content 29.8%；It is dried, after dehydration, moisture content is reduced to 12%, through broken, mistake
Sieve, partial size is at 100-200 μm；Binder coal tar is commercially available coal tar, from coal high-temperature retorting, wherein asphalt quality
Percentage is not less than 55%, and carbolineum mass percent is not higher than 10%；12% (the i.e. salt of mass percent of hydrochloride aqueous solution
Acid).
The drying base element composition that sludge is chosen in experiment is shown in Table 1.The Vario produced using German Elementar company
MACRO cube type elemental analyser, analyzes the constituent contents such as sludge C, H, N, S；The measurement of content of ashes is according to China
Standard GB/T/T212-2008 " proximate analysis of coal "；Oxygen content is calculated by minusing.
Table 1 tests the element composition of sludge
Embodiment 1
Sewage sludge powder is immersed into compounding activator solution, solid masses and liquor capacity ratio are 1:2, are impregnated under 20 degrees Celsius
12h；Compounding activator includes ZnCl2, phosphoric acid, K2S and NaCl, wherein ZnCl2Concentration is 2mol/L, phosphoric acid concentration 3mol/L,
K2S additional amount is that 10%, the NaCl additional amount of dewatered sludge quality is the 1% of dewatered sludge quality.Mixture is dry to moisture content
8%, coal tar is added, the mass ratio of mixture and coal tar is 1:0.3；Be granulated is diameter 8mm, the cylinder of length 15mm.?
Under the conditions of nitrogen flow 350ml/min, by shaping raw material 35g from 20 degrees Celsius of the room temperature heating rates with 10 DEG C/min, heat up
To 550 DEG C, and stop 1.5h.Then with the heating rate of 15 DEG C/min, 800 DEG C are raised the temperature to, while being passed through vapor
With the mixed gas of nitrogen, flow 350ml/min, vapor percentage by volume is 50%, activation time 1.5h, in isolation air
20 degrees Celsius are cooled to room temperature under the conditions of (i.e. nitrogen atmosphere).It is washed using hydrochloric acid solution, distilled water rinses to neutrality to arrive
The activated carbon product.
Embodiment 2
Sewage sludge powder is immersed into compounding activator solution, solid masses and liquor capacity ratio are 1:2.5, are soaked under 20 degrees Celsius
Stain 8h；Compounding activator includes ZnCl2, phosphoric acid, K2S and NaCl, wherein ZnCl2Concentration is 2.5mol/L, and phosphoric acid concentration is
2mol/L, K2S additional amount is that 15%, the NaCl additional amount of dewatered sludge quality is the 2% of dewatered sludge quality.Mixture is dry extremely
The mass ratio of moisture content 8%, addition coal tar, mixture and coal tar is 1:0.35；Being granulated is diameter 8mm, length 15mm's
Cylinder.Under the conditions of nitrogen flow 350ml/min, by shaping raw material 52.5g from 25 degrees Celsius of the room temperature heatings with 15 DEG C/min
Rate is warming up to 650 DEG C, and stops 1h.Then with the heating rate of 12 DEG C/min, 700 DEG C is raised the temperature to, is passed through simultaneously
The mixed gas of vapor and nitrogen, flow 350ml/min, vapor percentage by volume are 80%, and activation time 2h is completely cutting off
20 degrees Celsius are cooled to room temperature under the conditions of air (i.e. nitrogen atmosphere).It is washed using hydrochloric acid solution, distilled water is rinsed to neutrality, i.e.,
Obtain the activated carbon product.
Embodiment 3
Sewage sludge powder is immersed into compounding activator solution, solid masses and liquor capacity ratio are 1:2, are impregnated under 20 degrees Celsius
12h；Compounding activator includes ZnCl2, phosphoric acid, K2S and NaCl, wherein ZnCl2Concentration is 1mol/L, phosphoric acid concentration 5mol/L,
K2S additional amount is that 8%, the NaCl additional amount of dewatered sludge quality is the 0.5% of dewatered sludge quality.Mixture is dry to moisture content
6%, coal tar is added, the mass ratio of mixture and coal tar is 1:0.2；Be granulated is diameter 8mm, the cylinder of length 15mm.?
Under the conditions of nitrogen flow 350ml/min, by shaping raw material 40g from 20 degrees Celsius of the room temperature heating rates with 8 DEG C/min, it is warming up to
450 DEG C, and stop 2.5h.Then with the heating rate of 20 DEG C/min, 850 DEG C are raised the temperature to, at the same be passed through vapor and
The mixed gas of nitrogen, flow 350ml/min, vapor percentage by volume are 30%, activation time 1h, are completely cutting off air (i.e.
Nitrogen atmosphere) under the conditions of be cooled to room temperature 20 degrees Celsius.It is washed using hydrochloric acid solution, distilled water is rinsed to neutrality to get to institute
State activated carbon product.
Embodiment 4
Sewage sludge powder is immersed into compounding activator solution, solid masses and liquor capacity ratio are 1:1, are impregnated under 25 degrees Celsius
8h；Compounding activator includes ZnCl2, phosphoric acid, K2S and NaCl, wherein ZnCl2Concentration is 1.5mol/L, phosphoric acid concentration 4mol/
L, K2S additional amount is that 12%, the NaCl additional amount of dewatered sludge quality is the 1.5% of dewatered sludge quality.Mixture is dry to containing
The mass ratio of water rate 10%, addition coal tar, mixture and coal tar is 1:0.25；Be granulated is diameter 8mm, the circle of length 15mm
Column.Under the conditions of nitrogen flow 350ml/min, by shaping raw material 45g from 20 degrees Celsius of the room temperature heating rates with 12 DEG C/min,
600 DEG C are warming up to, and stops 2h.Then with the heating rate of 15 DEG C/min, 750 DEG C are raised the temperature to, while being passed through water steaming
The mixed gas of gas and nitrogen, flow 350ml/min, vapor percentage by volume is 60%, activation time 0.5h, in isolation sky
25 degrees Celsius are cooled to room temperature under the conditions of gas (i.e. nitrogen atmosphere).Washed using hydrochloric acid solution, distilled water rinse to neutrality to get
To the activated carbon product.
Embodiment 5
Sewage sludge powder is immersed into compounding activator solution, solid masses and liquor capacity ratio are 1:1, are impregnated under 25 degrees Celsius
10h；Compounding activator includes ZnCl2, phosphoric acid, K2S and NaCl, wherein ZnCl2Concentration is 2.5mol/L, and phosphoric acid concentration is
3.5mol/L, K2S additional amount is that 8%, the NaCl additional amount of dewatered sludge quality is the 0.8% of dewatered sludge quality.Mixture is done
Dry to be added coal tar to moisture content 6%, the mass ratio of mixture and coal tar is 1:0.3；Be granulated is diameter 8mm, length 15mm
Cylinder.Under the conditions of nitrogen flow 350ml/min, by shaping raw material 50g from 25 degrees Celsius of the room temperature heatings with 10 DEG C/min
Rate is warming up to 500 DEG C, and stops 2.5h.Then with the heating rate of 18 DEG C/min, 850 DEG C are raised the temperature to, is led to simultaneously
Enter the mixed gas of vapor and nitrogen, flow 350ml/min, vapor percentage by volume is 40%, activation time 2h, every
25 degrees Celsius are cooled to room temperature under the conditions of exhausted air (i.e. nitrogen atmosphere).It being washed using hydrochloric acid solution, distilled water is rinsed to neutrality,
Obtain the activated carbon product.
Embodiment 6
Sewage sludge powder is immersed into compounding activator solution, solid masses and liquor capacity ratio are 1:2.5, are soaked under 25 degrees Celsius
Stain 12h；Compounding activator includes ZnCl2, phosphoric acid, K2S and NaCl, wherein ZnCl2Concentration is 2mol/L, and phosphoric acid concentration is
4.5mol/L, K2S additional amount is that 12%, the NaCl additional amount of dewatered sludge quality is the 1.5% of dewatered sludge quality.Mixture is done
Dry to be added coal tar to moisture content 8%, the mass ratio of mixture and coal tar is 1:0.35；Be granulated is diameter 8mm, length
The cylinder of 15mm.Under the conditions of nitrogen flow 350ml/min, by shaping raw material 35g from 25 degrees Celsius of room temperature with 10 DEG C/min's
Heating rate is warming up to 550 DEG C, and stops 1.5h.Then with the heating rate of 15 DEG C/min, 700 DEG C are raised the temperature to, together
When be passed through the mixed gas of vapor and nitrogen, flow 350ml/min, vapor percentage by volume is 50%, activation time 2h,
25 degrees Celsius are cooled to room temperature under the conditions of completely cutting off air (i.e. nitrogen atmosphere).Washed using hydrochloric acid solution, distilled water rinse to
Neutrality to get arrive the activated carbon product.
Using Micromeritics company ASAP2020 surface area and pore structure study instrument, to the ratio table of active sludge carbon
Area, Kong Rong and pore-size distribution are analyzed.With high-purity N2Relative pressure is measured at liquid nitrogen temperature (77.3K) for adsorbate
(P/P0)10-7Absorption, desorption isotherm in~1 range.Total specific surface area is calculated using BET model, is measured by t-plot method micro-
Kong Kongrong measures mesopore volume by BJH adsorption curve, obtains micropore and mesopore pore size point using density functional theory (NLDFT)
Cloth.
According to specific embodiment, as shown in Fig. 4, when phosphoric acid concentration increases to 5mol/L, first stage from 2mol/L
The mesopore volume that activation is formed persistently increases, but increase tendency gradually slows down.Comprehensively consider preparation cost and the corrosion to equipment,
Phosphoric acid concentration more preferably takes 3-4mol/L.
Iodine sorption value is one of the index for analyzing active carbon pore structure performance, and size represents the flourishing journey of microcellular structure
Degree, iodine sorption value is bigger, microcellular structure more (nobleness stupid, Zhou Jianbin, Zuo Songlin, Hu Chengwen, Liu Qiming, the strongly fragrant husband iodine in peace portion
Relationship [J] the Nanjing Forestry University journal of value, methylene blue and Caramel adsorption and activated carbon pore structure, 1998,22 (4):
23-27).The measurement of iodine sorption value according to China's standard GB/T/T7702.7-2008 " coal quality granular activated carbon test method --
The measurement of iodine sorption value ".
Increase to 2h, sludge activity from 0.5h when the steam activation time as shown in Fig. 3 according to specific embodiment
The iodine sorption value of charcoal first increases to be reduced afterwards, reaches maximum value in 1.5h.When shorter between illustrating when activated, micropore development is not filled
Point, and activation time is too long, can widen micropore or hole wall is caused to burn, and reduces microcellular structure.
After tested, active sludge carbon BET specific surface area prepared by the present invention is average up to 400-450m2/ g, and aperture
0.5-50nm is continuously distributed.Combination activation method prepares active sludge carbon with single vapor activation and (uses stage by stage for comparison
Treatment of Sludge basic technology of the invention, directly activates sludge using single water vapour, does not carry out sublevel stage activation)
Charcoal rate and pore volume.0.12-0.15cm of active sludge carbon Micropore volume average out to prepared by the present invention3/ g, iodine sorption value
480-520mg/g of average out to, 0.17-0.20cm of mesopore volume average out to3/ g, obtaining charcoal rate is 55% -56%；Single water steams
Gas activation prepares active sludge carbon, and when obtaining charcoal rate is 55%, Micropore volume is 0.04-0.06cm3/ g, mesopore volume are
0.09-0.10cm3/g.Thus, when charcoal rate it is of substantially equal when, the pore structure of active carbon obtained by preparation method of the present invention is bright
It is aobvious to be higher than vapor activation.Also provable activation process of the present invention, which is mainly burnt, has lost internal carbon structure, so that hole is created,
Reduce surface carbon loss.
It is as follows to obtain charcoal rate calculation formula:
In formula: Y --- it obtains charcoal rate (%)
m0--- material quality (g) before activating
M --- active sludge carbon quality (g)
Prepared by the method active carbon is adsorbent, for be classified as by China the heavy metal lead of the first pollutant into
Row absorption.With Pb2+For adsorbed target, by the pure grade Pb (NO of the analysis of purchase3)2Pb is configured with deionized water2+Concentration is 40mg/L
Solution, investigate the active sludge carbon of preparation to Pb2+Absorption property, and be not added with K under identical preparation condition2S and NaCl
Active sludge carbon compare and (i.e. using preparation process of the invention, do not add K in compounding activator2S and NaCl).
Take 2 parts of 100mL Pb2+Concentration is that the solution of 40mg/L is respectively placed in 250mL conical flask, and 1.0000g sludge is added
Active carbon, one of which addition K2S and NaCl, another kind do not add both chemical reagent.In water bath with thermostatic control under the conditions of 25 DEG C
1h is vibrated in oscillator, takes supernatant after standing, through 0.45 μm of membrane filtration.1mL filtrate is pipetted in colorimetric cylinder, is diluted to
1~2 drop nitric acid is added, using Japanese Shimadzu Corporation ICPE-9800 type ICP-AES analysis-e/or determining Pb in 10mL2+Residual concentration,
As a result as shown in Fig. 1.
In formula: q --- Pb2+Adsorbance (mg/g)
C0——Pb2+Initial concentration (mg/L)
C——Pb2+Residual concentration (mg/L)
The volume (L) of V --- lead waste water
M --- active sludge carbon dosage (g)
In adsorption time 1h, preparation process adds a small amount of K2The active sludge carbon of S and NaCl reagent is to Pb2+Adsorbance
More, 1.3 times about un-added.
Active sludge carbon prepared by the present invention can be used for the processing of sanitary sewage or industrial wastewater, specific surface area, micropore
The Pore Characteristics such as volume, middle pore volume and pore-size distribution are the basic indexs for determining activated carbon adsorptive capacity, especially living
The pore-size distribution feature of property charcoal, can determine whether its absorption property to small molecule type or macromolecular pollutant.Sanitary sewage or work
Containing poisonous and harmful substances such as heavy metal ion, organic pollutants in industry waste water, wherein heavy metal ion category small molecule type pollutes
Object, microcellular structure (< 2nm) and its surface characteristic directly affect the absorption property to heavy metal ion；Organic matter generally belongs to big point
Subtype pollutant, central hole structure (2~50nm) adsorb the more effective (preparation of Li Wenhong active sludge carbon and its to dye to it
The Jinan research [D] of material absorption property: Shandong University, 2012).
The present invention obtains the active sludge carbon with filled aperature distribution characteristics, can be used for major pollutants heavy metal in water
It is adsorbed while ion and organic matter, activated carbon surface K+、Na+Content is higher, further enhances the adsorptivity to heavy metal ion
Energy；Activation is combined using compounding activator, gas activation agent stage by stage, can reduce that chemical activation method is at high cost, corrosivity is strong, dirt
The problems such as metachromia is high can also solve the problems, such as the surface carbon loss of gas activation.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (11)
1. the sewage treatment active sludge carbon with filled aperature distribution characteristics, which is characterized in that active sludge carbon specific surface
Product is average up to 400-450m2/ g, and aperture 0.5-50nm is continuously distributed, 0.12-0.15cm of Micropore volume average out to3/ g, in
0.17-0.20cm of Kong Kongrong average out to3/ g, is prepared as steps described below:
Step 1, by sludge with compound activator aqueous solution and be uniformly mixed and impregnate, wherein the drying base carbon content of sludge is not less than
30%, ash content is not higher than 40%, and moisture content is in 10wt%-20wt%；Activator aqueous solution is compounded by ZnCl2, phosphoric acid, K2S、
NaCl and water composition, ZnCl2Concentration is 1-2.5mol/L, phosphoric acid concentration 2-5mol/L, K2S additional amount is dewatered sludge quality
8%-15%, NaCl additional amount are the 0.5%-2% of dewatered sludge quality；Sludge quality is with activator aqueous solution volume ratio is compounded
1:(1-2.5), 8-12h is impregnated at 20-25 DEG C；
Step 2, sludge prepared by step 1 is lower than 10wt% with mixture drying to the moisture content for compounding activator, be added viscous
Agent molding is tied, shaping raw material is prepared, in order to which finished activated charcoal is applied in sewage treatment；Sludge and the mixing for compounding activator
The mass ratio of object and binder is 1:(0.2-0.35)；
Step 3, the shaping raw material prepared by step 2 is carbonized in nitrogen, from 20-25 DEG C of room temperature, with 8-15 DEG C/min
Heating rate be warming up to 450-650 DEG C and keep the temperature 1-2.5h；
Step 4, after the heat preservation by step 3, second step processing is carried out to shaping raw material, with the heating speed of 12-20 DEG C/min
Rate raises the temperature to 700-850 DEG C, and the mixed gas while insulation reaction of vapor and nitrogen are passed through into reaction system
0.5-2h, vapor percentage by volume is 30-80% in mixed gas, stops being passed through vapor and nitrogen after completion of the reaction
Mixed gas, and continue nitrogen is passed through into reaction system so that 20-25 DEG C of cooled to room temperature in a nitrogen atmosphere；
Step 5, after carrying out pickling to the product of cooled to room temperature, it is washed to neutrality.
2. the sewage treatment active sludge carbon according to claim 1 with filled aperature distribution characteristics, feature exist
In in step 1, selecting the sludge of sewage treatment plant, dry base carbon content is not less than 30%, and ash content is not higher than 40%；Through shining
Dry, dehydration makes moisture content that sludge are prepared into 200 μm of partial size sludge powder below through broken, sieving in 10%-20%
End.
3. the sewage treatment active sludge carbon according to claim 2 with filled aperature distribution characteristics, feature exist
In in step 1, sludge being prepared into 100-200 μm of partial size of sewage sludge powder.
4. the sewage treatment active sludge carbon according to claim 1 with filled aperature distribution characteristics, feature exist
In, in step 2, binder is coal tar, and from coal high-temperature retorting, wherein asphalt quality percentage is not less than 55%,
Carbolineum mass percent is not higher than 10%；Select granulating and forming for cylindrical body, diameter 6-9mm, length 12-18mm.
5. the sewage treatment active sludge carbon according to claim 1 with filled aperature distribution characteristics, feature exist
In in step 3, first with the air in nitrogen removal reaction system, so as to be full of nitrogen in entire reaction system, then from room temperature
20-25 DEG C are risen, and are warming up to 450-650 DEG C with the heating rate of 8-15 DEG C/min and are kept the temperature 1-2.5h；From 20-25 DEG C of room temperature
It rises, be warming up to 500-600 DEG C with the heating rate of 10-12 DEG C/min and keep the temperature 1.5-2h；Nitrogen flow is to maintain reaction system
Subject to interior nitrogen, and with shaping raw material close contact, the ratio between mass parts of shaping raw material and the parts by volume of nitrogen flow are 1:
(10-15), each mass parts are 1g, and each parts by volume is 1ml/min.
6. the sewage treatment active sludge carbon according to claim 1 with filled aperature distribution characteristics, feature exist
In in step 4, raising the temperature to 750-800 DEG C and the mixed gas for being passed through vapor and nitrogen into reaction system be same
When insulation reaction 1-2h；Vapor percentage by volume is 40-60% in mixed gas；The mixed gas stream of vapor and nitrogen
Amount, which is subject to, maintains have sufficient vapor in reaction system, and makes vapor and shaping raw material close contact, the matter of shaping raw material
Measuring the ratio between parts by volume of mixed gas flow of part and vapor and nitrogen is 1:(10-15), each mass parts are 1g, each
Parts by volume is 1ml/min.
7. the preparation method of the sewage treatment active sludge carbon with filled aperature distribution characteristics, which is characterized in that under
Step is stated to be prepared:
Step 1, by sludge with compound activator aqueous solution and be uniformly mixed and impregnate, wherein the drying base carbon content of sludge is not less than
30%, ash content is not higher than 40%, and moisture content is in 10wt%-20wt%；Activator aqueous solution is compounded by ZnCl2, phosphoric acid, K2S、
NaCl and water composition, ZnCl2Concentration is 1-2.5mol/L, phosphoric acid concentration 2-5mol/L, K2S additional amount is dewatered sludge quality
8%-15%, NaCl additional amount are the 0.5%-2% of dewatered sludge quality；Sludge quality is with activator aqueous solution volume ratio is compounded
1:(1-2.5), 8-12h is impregnated at 20-25 DEG C；
Step 2, sludge prepared by step 1 is lower than 10wt% with mixture drying to the moisture content for compounding activator, be added viscous
Agent molding is tied, shaping raw material is prepared, in order to which finished activated charcoal is applied in sewage treatment；Sludge and the mixing for compounding activator
The mass ratio of object and binder is 1:(0.2-0.35)；
Step 3, the shaping raw material prepared by step 2 is carbonized in nitrogen, from 20-25 DEG C of room temperature, with 8-15 DEG C/min
Heating rate be warming up to 450-650 DEG C and keep the temperature 1-2.5h；
Step 4, after the heat preservation by step 3, second step processing is carried out to shaping raw material, with the heating speed of 12-20 DEG C/min
Rate raises the temperature to 700-850 DEG C, and the mixed gas while insulation reaction of vapor and nitrogen are passed through into reaction system
0.5-2h, vapor percentage by volume is 30-80% in mixed gas, stops being passed through vapor and nitrogen after completion of the reaction
Mixed gas, and continue nitrogen is passed through into reaction system so that 20-25 DEG C of cooled to room temperature in a nitrogen atmosphere；
Step 5, after carrying out pickling to the product of cooled to room temperature, it is washed to neutrality.
8. the preparation side of the sewage treatment active sludge carbon according to claim 7 with filled aperature distribution characteristics
Method, which is characterized in that in step 1, select the sludge of sewage treatment plant, dry base carbon content is not less than 30%, and ash content is not high
In 40%；It is dried, dehydration, makes moisture content that sludge are prepared into 200 μm of partial size through broken, sieving in 10%-20%
Sewage sludge powder below.
9. the preparation side of the sewage treatment active sludge carbon according to claim 7 with filled aperature distribution characteristics
Method, which is characterized in that in step 2, binder is coal tar, from coal high-temperature retorting, wherein asphalt quality percentage
Not less than 55%, carbolineum mass percent is not higher than 10%；Select granulating and forming for cylindrical body, diameter 6-9mm, length 12-
18mm。
10. the preparation side of the sewage treatment active sludge carbon according to claim 7 with filled aperature distribution characteristics
Method, which is characterized in that in step 3, first with the air in nitrogen removal reaction system, so as to be full of nitrogen in entire reaction system
Gas, then from 20-25 DEG C of room temperature, be warming up to 450-650 DEG C with the heating rate of 8-15 DEG C/min and keep the temperature 1-2.5h；From room
20-25 DEG C of temperature are risen, and are warming up to 500-600 DEG C with the heating rate of 10-12 DEG C/min and are kept the temperature 1.5-2h；Nitrogen flow is to tie up
Hold in reaction system subject to nitrogen, and with shaping raw material close contact, the mass parts of shaping raw material and the parts by volume of nitrogen flow
The ratio between be 1:(10-15), each mass parts be 1g, each parts by volume be 1ml/min.
11. the preparation side of the sewage treatment active sludge carbon according to claim 7 with filled aperature distribution characteristics
Method, which is characterized in that in step 4, raise the temperature to 750-800 DEG C and be passed through vapor and nitrogen into reaction system
Mixed gas while insulation reaction 1-2h；Vapor percentage by volume is 40-60% in mixed gas；Vapor and nitrogen
Mixed gas flow, which is subject to, maintains have sufficient vapor in reaction system, and makes vapor and shaping raw material close contact, at
The ratio between mass parts and vapor and the parts by volume of mixed gas flow of nitrogen of type raw material are 1:(10-15), each mass parts
For 1g, each parts by volume is 1ml/min.
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| CN106560236A (en) | 2017-04-12 |
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