CN106345411A - Rare metal-based sludge activated carbon and application thereof in removal of sulfur, ammonia and phosphorus - Google Patents
Rare metal-based sludge activated carbon and application thereof in removal of sulfur, ammonia and phosphorus Download PDFInfo
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- CN106345411A CN106345411A CN201610871905.5A CN201610871905A CN106345411A CN 106345411 A CN106345411 A CN 106345411A CN 201610871905 A CN201610871905 A CN 201610871905A CN 106345411 A CN106345411 A CN 106345411A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The invention provides a rare metal-based sludge activated carbon and application thereof in the removal of sulfur, ammonia and phosphorus. The rare metal-based sludge activated carbon includes sludge activated carbon and metal elements such as manganese, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium and the like, and is specifically prepared by a method comprising the following steps: mixing pyrolusite powder with activated sludge, adding a zinc chloride compounded activating agent into the mixture, activating the mixture at a high temperature, carbonizing the mixture to obtain pyrolusite compounded activated sludge, mixing the activated sludge with rare earth oxide powder and a chelating agent after the activated sludge is modified by potassium hydroxide solution, heating the mixture in a microwave oven, carbonizing the mixture to obtain rare earth compounded activated sludge, and mixing the compounded activated sludge to obtain a product. The rare metal-based sludge activated carbon prepared by the method has the advantages of high activity, high porosity, uniform pore size distribution, high adsorption capacity, capability of chelating a plurality of metals and microorganisms, high capacity of adsorbing sulfur, ammonia and phosphorus and high rate of removing the sulfur, the ammonia and the phosphorus in sewage and waste.
Description
Technical field
The invention belongs to active sludge carbon field of material technology is and in particular to a kind of active sludge carbon based on rare metal
And the application in terms of sulphur removal ammonia phosphorus.
Background technology
The surging, along with substantial amounts of water pollution, and at sewage of fast development with national economy and water consumption
Reason and control water pollution also can produce substantial amounts of mud and odor pollution.The stench of mud mainly based on hydrogen sulfide and ammonia,
Stench not only produces harm, and also has unsafe impact to society to health, animal and plant growth.At present, both at home and abroad
The main method processing foul smell has absorption method, absorption process, combustion method and the biological clarification, wherein absorption method and biological clarification to be
Main methods, are because that biological clarification is with low cost, absorption method using method, and removal effect is stable.
The main material of absorption method is activated carbon, and activated carbon is easy to get due to raw material, and manufacturing process is simple and efficient, adsorption effect
Stablize and obtain the pro-gaze of people.Active sludge carbon be using activated sludge as raw material prepare, in activated sludge contain antibacterial,
The xenogeneic subject group such as funguses, protozoacide and Organic substance, because the physical absorption performance of active sludge carbon not only active charcoal,
Also contain a large amount of microorganisms, physics, biological and chemical process are carried out to the source of stench, comprehensive control is carried out to stench.China
The disclosed method preparing active sludge carbon using mud of patent cn 101423212b, will add flocculant and a huge sum of money in mud
Belong to chelating agen, after stirring thickening dry, be subsequently placed in half carbonization gasified boiler and carry out half dry distilling process, take out stone and
After irony, add Colophonium or tar as adhesive, black liquor, smokeless coal powder, potassium chloride, potassium hydroxide or hydrogen-oxygen
Change sodium as adjusting hole agent, mix homogeneously, pelletize, dry in the sun, be placed in activation processing in activation furnace, sieve powder processed and obtain sludge activity
Charcoal.In the active sludge carbon of the method preparation, macropore, mesopore and transitional pore enrich, and adsorption equilibrium ability projects, and adsorption rate is fast,
But it is not targeted to the process of waste water, waste gas.The system of active sludge carbon disclosed in Chinese patent cn 103495399b
Preparation Method and application, drying sludge is divided water to sieve, and is pyrolyzed, adds in hydrogen peroxide solution in ammonia atmosphere, vibration oxidation
Obtain sludge activity char combustion powdered carbon, then heat treated under ammonia atmosphere, obtain active sludge carbon ammonification powdered carbon, last submergence
In methylating reagent, washing is dried to obtain active sludge carbon.The active sludge carbon of the method preparation is to low concentration perchlorate
There is good removal effect, and do not result in secondary pollution.A kind of load manganese mud disclosed in Chinese patent cn 105833835a
Active carbon material and preparation method thereof, pulverizes after mud is dried and forms Granular sludge charcoal base, immerses acid solution and hydrochlorate
Activate in the composite activating agent of solution, take out and dry, then be placed in charing process in high temperature furnace, with acid solution rinsing, eluting, baking
Dry, finally it is placed in manganese metal loading solution, ultrasonic, dry, heating frozen obtains carrying the active sludge carbon of manganese.Prepared by the method
Load manganese active sludge carbon aperture flourishing, even particle distribution, activity function is good.
From above-mentioned prior art, by being modified to active sludge carbon arranging, the suction of mud not only can be improved
Attached performance, but also can be with the absorption property of object.But inhale for active sludge carbon currently for elements such as sulfur ammonia phosphorus
The research of attached dose of aspect is actually rare.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of active sludge carbon based on rare metal and in sulphur removal ammonia phosphorus
The application of aspect, should based in the active sludge carbon of rare metal contain active sludge carbon and manganese cerium praseodymium neodymium promethium sm-eu-gd terbium dysprosium holmium
The metallic elements such as erbium, method particularly includes: pyrolusite powder is mixed with activated sludge, adds zinc chloride composite activating agent, high temperature
Activation, carbonization obtains soft manganese complex enzyme/activated sludge, activated sludge is modified through potassium hydroxide solution, with RE oxide powder
With chelating agen mixing, microwave-oven-heating, carbonization obtains rare earth complex enzyme/activated sludge, and this complex enzyme/activated sludge is mixed to get product
Product.The sludge activity carbon activity based on rare metal of present invention preparation is big, and hole is high, even aperture distribution, high adsorption capacity,
Chelating various metals and microorganism, all have good absorbability to sulfur ammonia phosphorus, to sewage and discarded in sulfur ammonia phosphorus ligands
Rate is high.
For solving above-mentioned technical problem, the technical scheme is that
A kind of active sludge carbon based on rare metal, described based in the active sludge carbon of rare metal contain mud live
Property charcoal and rare metal, described rare metal provides by pyrolusite powder and RE oxide powder, and described rare metal includes
Manganese element, lanthanum element, Ce elements, praseodymium element, neodymium element, promethium element, samarium element, europium element, gadolinium element, terbium element, dysprosium element,
Holmium element, er element, thulium element, ytterbium element and lutecium element, described rare metal is 0.1 with the mass ratio of active sludge carbon:
99.9-5:95.
Preferred as technique scheme, in described pyrolusite powder, the content of manganese element is not less than 50%, described dilute
The particle diameter of native oxide powder is 150-300 mesh.
The main component of currently preferred pyrolusite powder is manganese dioxide, and manganese dioxide itself has good surface
Adsorption effect, redox and catalytic effect etc. act on, and aboundresources, cheap, environmental friendliness.
, in 150-300 mesh, air hole structure is good, high mechanical strength for the particle diameter of currently preferred RE oxide powder, raw
Produce simple, easy industrialized production.
Preferred as technique scheme, the preparation method of the described active sludge carbon based on rare metal includes following
Step:
(1) mud is dried after 24h, grind to form sewage sludge powder, pyrolusite powder is mixed homogeneously with sewage sludge powder, add
Zinc chloride and the composite activating agent of dilute sulfuric acid, the uniform 1-6h of ultrasonic mixing, stand 24h, dry activation 24- at 80-130 DEG C
72h, is placed in 550-650 DEG C of tube furnace, and high temperature carbonization reacts 1-5h, is washed to neutrality and obtains soft manganese composite sludge work after cooling
Property charcoal；
(2) sewage sludge powder prepared by step (1) is pyrolyzed under ammonia atmosphere, forms sludge activity powdered carbon, mud is lived
Property powdered carbon impregnated in potassium hydroxide solution, sealing stirring, wash drying, add RE oxide powder and citric acid, then
Microwave heating 2-3min under 400-500w, is placed in tube furnace, and by nitrogen and vapor, high-temperature activation reacts, water after cooling
It is washed till neutrality and obtain rare earth composite sludge activated carbon；
(3) the rare earth composite sludge activated carbon that soft manganese composite sludge activated carbon prepared by step (1) is prepared with step (2)
Mixing, grinds screening, obtains the active sludge carbon based on rare metal.
Preferred as technique scheme, the mud of preparation method step (1) is remaining dilute mud or dehydrated sludge cake,
Moisture content is 85-90%, and the ash content of coal is 35-50%.
Preferred as technique scheme, the particle diameter of the sewage sludge powder of preparation method step (1) or (2) is 200-
300 mesh.
Preferred as technique scheme, the pyrolusite powder of preparation method step (1) and the mass ratio of sewage sludge powder
For 0.1:45-5:45.
Preferred as technique scheme, in the zinc chloride of preparation method step (1) and the composite activating agent of dilute sulfuric acid
The volume of zinc chloride and dilute sulfuric acid is 3:1-6:1, and chlorination zinc concentration is 4-6mol/l, and the mass fraction of dilute sulfuric acid is 20-
45%.
Preferred as technique scheme, the RE oxide powder of preparation method step (2) and the matter of sewage sludge powder
Amount ratio is 0.1:45-5:45.
Preferred as technique scheme, the soft manganese composite sludge activated carbon of preparation method step (3) is combined with rare earth
The mass ratio of active sludge carbon is 1:0.7-1.3.
Additionally, the present invention also provides a kind of active sludge carbon based on rare metal in the application of sewage sulphur removal nitrogen phosphorus, wrap
Include following steps: after mud is diluted, add the active sludge carbon based on rare metal, quick stirring, absorption staticly settles；Will
It is placed in exhaust environment based on the active sludge carbon of rare metal, air-supply, standing adsorption.
Compared with prior art, the method have the advantages that
(1) manganese element, lanthanum element, Ce elements, praseodymium are contained in the active sludge carbon based on rare metal of present invention preparation
Element, neodymium element, promethium element, samarium element, europium element, gadolinium element, terbium element, dysprosium element, holmium element, er element, thulium element, ytterbium
Element and lutecium element, these yttriums have stronger catalysed oxidn, and yttrium adds lives to mud
Property charcoal in, be remarkably improved the adsorption effect to sulfur nitrogen phosphorus, be better achieved sewage separate, but the amount mistake of yttrium
Do not reach facilitation effect less, excessively can affect the absorption of sulfur nitrogen phosphorus on the contrary.
(2) active sludge carbon in the active sludge carbon based on rare metal of present invention preparation is molten through potassium hydroxide basic
After liquid is processed, the activity of active sludge carbon becomes apparent from, adsorption effect more preferably, to the clearance of sulfur nitrogen phosphorus up to more than 90%,
Can effectively purify water, prevent water pollution.
(3) porosity of the active sludge carbon based on rare metal of present invention preparation is high, and pore structure is flourishing and sews and mend
Uniformly, obvious projection is contained on the surface of active sludge carbon, and specific surface area is high, and adsorption activity point position is many, and active sludge carbon
Microorganism is contained on surface and rare metal can promote the absorption of sulfur nitrogen phosphorus, solves existing sludge activity poor to the absorption of sulfur nitrogen phosphorus
Problem.
(4) preparation method of the present invention is simple, and controllability is strong, preparing raw material wide material sources, cheap, the economy of product
Profitable, there is the very strong market competitiveness and promotional value, and good stability in water body for this absorption, do not result in water
The secondary pollution of body, has good application prospect.
Specific embodiment
To describe the present invention, the illustrative examples of the here present invention and explanation below in conjunction with specific embodiment in detail
It is used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1:
(1) by moisture content be 85%, the ash content of coal be 35% the dilute mud of residue dry 24h after, grind to form 200-300 mesh
Sewage sludge powder, mass ratio is 0.1:45, particle diameter is that the pyrolusite powder of 150 mesh is mixed homogeneously with sewage sludge powder, add chlorine
Change the composite activating agent of zinc and dilute sulfuric acid, the wherein volume of zinc chloride and dilute sulfuric acid is 3:1, and chlorination zinc concentration is 4mol/l,
The mass fraction of dilute sulfuric acid is 20%, the uniform 1h of ultrasonic mixing, stands 24h, dries activation 24h, be placed in 550 DEG C of pipes at 80 DEG C
In formula stove, high temperature carbonization reacts 1h, is washed to neutrality and obtains soft manganese composite sludge activated carbon after cooling.
(2) sewage sludge powder of 200 mesh is pyrolyzed under ammonia atmosphere, forms sludge activity powdered carbon, by weight, by matter
Amount impregnated in 20% potassium hydroxide solution than the sludge activity powdered carbon for 45 parts, sealing stirring 60min, washs drying, plus
Enter the citric acid of the RE oxide powder that 0.1 part of particle diameter is 150 mesh and 2 parts, microwave heating 2min, is placed in pipe under 400w
In formula stove, by the nitrogen for 1:1 for the volume ratio and vapor, high-temperature activation reaction 1h at 900 DEG C, it is washed to neutral after cooling
To rare earth composite sludge activated carbon.
(3) by mass ratio, the soft manganese composite sludge activated carbon for 1:0.7 is mixed with rare earth composite sludge activated carbon, grinds sieve
Point, obtain the active sludge carbon based on rare metal.
Embodiment 2:
(1) by moisture content be 90%, the ash content of coal be 50% dehydrated sludge cake dry 24h after, grind to form the mud of 300 mesh
Powder, mass ratio is 5:45, and particle diameter is that the pyrolusite powder of 300 mesh is mixed homogeneously with sewage sludge powder, adds zinc chloride and dilute
The volume of the composite activating agent of sulphuric acid, wherein zinc chloride and dilute sulfuric acid is 6:1, and chlorination zinc concentration is 6mol/l, dilute sulfuric acid
Mass fraction is 45%, the uniform 6h of ultrasonic mixing, stands 24h, dries activation 72h, be placed in 650 DEG C of tube furnaces at 130 DEG C,
High temperature carbonization reacts 5h, is washed to neutrality and obtains soft manganese composite sludge activated carbon after cooling.
(2) sewage sludge powder of 300 mesh is pyrolyzed under ammonia atmosphere, forms sludge activity powdered carbon, by weight, by matter
Amount impregnated in 20% potassium hydroxide solution than the sludge activity powdered carbon for 45 parts, sealing stirring 60min, washs drying, plus
Enter the citric acid of the RE oxide powder that 5 parts of particle diameter is 300 mesh and 10 parts, microwave heating 3min, is placed in pipe under 500w
In formula stove, by the nitrogen for 1:1 for the volume ratio and vapor, high-temperature activation reaction 5h at 900 DEG C, it is washed to neutral after cooling
To rare earth composite sludge activated carbon.
(3) by mass ratio, the soft manganese composite sludge activated carbon for 1:1.3 is mixed with rare earth composite sludge activated carbon, grinds sieve
Point, obtain the active sludge carbon based on rare metal.
Embodiment 3:
(1) by moisture content be 88%, the ash content of coal be 45% the dilute mud of residue dry 24h after, grind to form the dirt of 250 mesh
Mud powder, mass ratio is 1:45, and particle diameter is that the pyrolusite powder of 200 mesh is mixed homogeneously with sewage sludge powder, add zinc chloride and
The volume of the composite activating agent of dilute sulfuric acid, wherein zinc chloride and dilute sulfuric acid is 4:1, and chlorination zinc concentration is 5mol/l, dilute sulfuric acid
Mass fraction be 25%, the uniform 3h of ultrasonic mixing, stand 24h, at 100 DEG C dry activation 36h, be placed in 600 DEG C of tube furnaces
Interior, high temperature carbonization reacts 2h, is washed to neutrality and obtains soft manganese composite sludge activated carbon after cooling.
(2) sewage sludge powder of 250 mesh is pyrolyzed under ammonia atmosphere, forms sludge activity powdered carbon, by weight, by matter
Amount impregnated in 20% potassium hydroxide solution than the sludge activity powdered carbon for 45 parts, sealing stirring 60min, washs drying, plus
Enter the citric acid of the RE oxide powder that 2 parts of particle diameter is 250 mesh and 8 parts, microwave heating 2.5min, is placed in pipe under 450w
In formula stove, by the nitrogen for 1:1 for the volume ratio and vapor, high-temperature activation reaction 3h at 900 DEG C, it is washed to neutral after cooling
To rare earth composite sludge activated carbon.
(3) by mass ratio, the soft manganese composite sludge activated carbon for 1:1 is mixed with rare earth composite sludge activated carbon, grinds sieve
Point, obtain the active sludge carbon based on rare metal.
Embodiment 4:
(1) by moisture content be 89%, the ash content of coal be 42% dehydrated sludge cake dry 24h after, grind to form the mud of 300 mesh
Powder, mass ratio is 2.5:45, and particle diameter is that the pyrolusite powder of 150-300 mesh is mixed homogeneously with sewage sludge powder, adds chlorination
Zinc and the composite activating agent of dilute sulfuric acid, the wherein volume of zinc chloride and dilute sulfuric acid are 5:1, and chlorination zinc concentration is 5mol/l, dilute
The mass fraction of sulphuric acid is 35%, the uniform 3h of ultrasonic mixing, stands 24h, dries activation 50h, be placed in 650 DEG C of pipes at 110 DEG C
In formula stove, high temperature carbonization reacts 2h, is washed to neutrality and obtains soft manganese composite sludge activated carbon after cooling.
(2) sewage sludge powder of 200 mesh is pyrolyzed under ammonia atmosphere, forms sludge activity powdered carbon, by weight, by matter
Amount impregnated in 20% potassium hydroxide solution than the sludge activity powdered carbon for 45 parts, sealing stirring 60min, washs drying, plus
Enter the citric acid of the RE oxide powder that 3 parts of particle diameter is 300 mesh and 8 parts, microwave heating 2min, is placed in tubular type under 450w
In stove, by the nitrogen for 1:1 for the volume ratio and vapor, at 900 DEG C, high-temperature activation reaction 3h, is washed to neutrality and obtains after cooling
Rare earth composite sludge activated carbon.
(3) by mass ratio, the soft manganese composite sludge activated carbon for 1:1.1 is mixed with rare earth composite sludge activated carbon, grinds sieve
Point, obtain the active sludge carbon based on rare metal.
Embodiment 5:
(1) by moisture content be 90%, the ash content of coal be 45% the dilute mud of residue dry 24h after, grind to form the dirt of 200 mesh
Mud powder, mass ratio is 1.5:45, and particle diameter is that the pyrolusite powder of 250 mesh is mixed homogeneously with sewage sludge powder, adds zinc chloride
Volume with the composite activating agent of dilute sulfuric acid, wherein zinc chloride and dilute sulfuric acid is 5:1, and chlorination zinc concentration is 1.5mol/l, dilute
The mass fraction of sulphuric acid is 35%, the uniform 4h of ultrasonic mixing, stands 24h, dries activation 72h, be placed in 550 DEG C of tubular types at 90 DEG C
In stove, high temperature carbonization reacts 4h, is washed to neutrality and obtains soft manganese composite sludge activated carbon after cooling.
(2) sewage sludge powder of 200 mesh is pyrolyzed under ammonia atmosphere, forms sludge activity powdered carbon, by weight, by matter
Amount impregnated in 20% potassium hydroxide solution than the sludge activity powdered carbon for 45 parts, sealing stirring 60min, washs drying, plus
Enter the citric acid of the RE oxide powder that 3 parts of particle diameter is 200 mesh and 6 parts, microwave heating 2min, is placed in tubular type under 500w
In stove, by the nitrogen for 1:1 for the volume ratio and vapor, high-temperature activation reaction 3.5h at 900 DEG C, it is washed to neutral after cooling
To rare earth composite sludge activated carbon.
(3) by mass ratio, the soft manganese composite sludge activated carbon for 1:1.2 is mixed with rare earth composite sludge activated carbon, grinds sieve
Point, obtain the active sludge carbon based on rare metal.
Embodiment 6:
(1) by moisture content be 90%, the ash content of coal be 40% dehydrated sludge cake dry 24h after, grind to form the mud of 300 mesh
Powder, mass ratio is 0.1:45, and particle diameter is that the pyrolusite powder of 300 mesh is mixed homogeneously with sewage sludge powder, add zinc chloride and
The volume of the composite activating agent of dilute sulfuric acid, wherein zinc chloride and dilute sulfuric acid is 3:1, and chlorination zinc concentration is 6mol/l, dilute sulfuric acid
Mass fraction be 20%, the uniform 6h of ultrasonic mixing, stand 24h, at 80 DEG C dry activation 72h, be placed in 650 DEG C of tube furnaces
Interior, high temperature carbonization reacts 1h, is washed to neutrality and obtains soft manganese composite sludge activated carbon after cooling.
(2) sewage sludge powder of 300 mesh is pyrolyzed under ammonia atmosphere, forms sludge activity powdered carbon, by weight, by matter
Amount impregnated in 20% potassium hydroxide solution than the sludge activity powdered carbon for 45 parts, sealing stirring 60min, washs drying, plus
Enter the citric acid of the RE oxide powder that 5 parts of particle diameter is 150 mesh and 10 parts, microwave heating 3min, is placed in pipe under 400w
In formula stove, by the nitrogen for 1:1 for the volume ratio and vapor, high-temperature activation reaction 1h at 900 DEG C, it is washed to neutral after cooling
To rare earth composite sludge activated carbon.
(3) by mass ratio, the soft manganese composite sludge activated carbon for 1:1.3 is mixed with rare earth composite sludge activated carbon, grinds sieve
Point, obtain the active sludge carbon based on rare metal.
The preparation of embodiment 1-6 is used for sewage and the absorption of discarded sulfur nitrogen phosphorus based on the active sludge carbon of rare metal
In, method particularly includes:
After mud is diluted, add the active sludge carbon based on rare metal, quick stirring, absorption staticly settles.
To be placed in exhaust environment based on the active sludge carbon of rare metal, air-supply, standing adsorption.
After testing, embodiment 1-6 preparation the active sludge carbon based on rare metal and prior art unmodified
The clearance result to sewage and discarded sulfur nitrogen phosphorus of activated carbon is as follows:
In sewage:
In waste gas:
As seen from the above table, the active sludge carbon based on rare metal of present invention preparation and unmodified active sludge carbon phase
Ratio significantly improves to the adsorption effect of sulfur nitrogen phosphorus, clearance is up to 90%.
Above-described embodiment only principle of the illustrative present invention and its effect, not for the restriction present invention.Any ripe
The personage knowing this technology all can carry out modifications and changes without prejudice under the spirit and the scope of the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
All equivalent modifications becoming or change, must be covered by the claim of the present invention.
Claims (10)
1. a kind of active sludge carbon based on rare metal it is characterised in that: described based in the active sludge carbon of rare metal
Containing active sludge carbon and rare metal, described rare metal is provided by pyrolusite powder and RE oxide powder, described dilute
Metal is had to include manganese element, lanthanum element, Ce elements, praseodymium element, neodymium element, promethium element, samarium element, europium element, gadolinium element, terbium unit
The quality of element, dysprosium element, holmium element, er element, thulium element, ytterbium element and lutecium element, described rare metal and active sludge carbon
Than for 0.1:99.9-5:95.
2. a kind of active sludge carbon based on rare metal according to claim 1 is it is characterised in that described pyrolusite powder
In end, the content of manganese element is not less than 50%, and the particle diameter of described RE oxide powder is 150-300 mesh.
3. a kind of active sludge carbon based on rare metal according to claims 1 or 2 is it is characterised in that described base
Preparation method in the active sludge carbon of rare metal comprises the following steps:
(1) mud is dried after 24h, grind to form sewage sludge powder, pyrolusite powder is mixed homogeneously with sewage sludge powder, add chlorination
Zinc and the composite activating agent of dilute sulfuric acid, the uniform 1-6h of ultrasonic mixing, stand 24h, dry activation 24-72h at 80-130 DEG C, put
In 550-650 DEG C of tube furnace, high temperature carbonization reacts 1-5h, is washed to neutrality and obtains soft manganese composite sludge activated carbon after cooling；
(2) sewage sludge powder prepared by step (1) is pyrolyzed under ammonia atmosphere, forms sludge activity powdered carbon, by active sludge carbon
Powder impregnated in potassium hydroxide solution, sealing stirring, washs drying, adds RE oxide powder and citric acid, then 400-
Microwave heating 2-3min under 500w, is placed in tube furnace, and by nitrogen and vapor, high-temperature activation reacts, is washed to after cooling
Neutrality obtains rare earth composite sludge activated carbon；
(3) the rare earth composite sludge activated carbon being prepared soft manganese composite sludge activated carbon prepared by step (1) with step (2) is mixed
Close, grind screening, obtain the active sludge carbon based on rare metal.
4. a kind of active sludge carbon based on rare metal according to claim 3 is it is characterised in that preparation method step
(1) mud is remaining dilute mud or dehydrated sludge cake, and moisture content is 85-90%, and the ash content of coal is 35-50%.
5. a kind of active sludge carbon based on rare metal according to claim 3 is it is characterised in that preparation method step
(1) or (2) sewage sludge powder particle diameter be 200-300 mesh.
6. a kind of active sludge carbon based on rare metal according to claim 3 is it is characterised in that preparation method step
(1) pyrolusite powder is 0.1:45-5:45 with the mass ratio of sewage sludge powder.
7. a kind of active sludge carbon based on rare metal according to claim 3 is it is characterised in that preparation method step
(1) in zinc chloride and the composite activating agent of dilute sulfuric acid, the volume of zinc chloride and dilute sulfuric acid is 3:1-6:1, and chlorination zinc concentration is
4-6mol/l, the mass fraction of dilute sulfuric acid is 20-45%.
8. a kind of active sludge carbon based on rare metal according to claim 3 is it is characterised in that preparation method step
(2) RE oxide powder is 0.1:45-5:45 with the mass ratio of sewage sludge powder.
9. a kind of active sludge carbon based on rare metal according to claim 3 is it is characterised in that preparation method step
(3) soft manganese composite sludge activated carbon is 1:0.7-1.3 with the mass ratio of rare earth composite sludge activated carbon.
10. a kind of active sludge carbon based on rare metal sewage sulphur removal nitrogen phosphorus application it is characterised in that: include following step
Rapid: after mud is diluted, add the active sludge carbon based on rare metal, quick stirring, absorption staticly settles；Will be based on rare
The active sludge carbon of metal is placed in exhaust environment, air-supply, standing adsorption.
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