CN109929560A - A method of magnetic bio-carrier is prepared using gangue - Google Patents
A method of magnetic bio-carrier is prepared using gangue Download PDFInfo
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Abstract
The invention discloses a kind of methods for preparing magnetic bio-carrier using gangue, include the following steps, S1: raw material test;S2: raw material is broken;S3: ingredient;S4: mixing;S5: molding;S6: calcining;S7: air-cooled;S8: magnetization modification;S9: slag-liquid separation;S10: drying.Magnetic bio-carrier of the invention, turns waste into wealth, and reduces production cost, in calcination process, so that forming more mesoporous and micropores in gangue, can provide carrier for biology;Pollutants removal rate can be improved for water treatment procedure, improve stable water outlet reduction raising bioreactor utilization rate, reduction occupied area and construction cost;After being applied in soil, moreover it is possible to change soil texture, increase the water-retaining property and gas permeability of soil;By magnetization modification, frerrous chloride and iron chloride produce ferroso-ferric oxide, and are attached to the surface of powder, so that powder has magnetism, accelerate the decomposition of organic matter and the breeding of microorganism.
Description
Technical field
The present invention relates to water process, water remediation and technical field of soil remediation, especially a kind of to be prepared using gangue
The method of magnetic bio-carrier.
Background technique
Gangue is the solid industrial waste generated in coal mining and process, includes multi mineral ingredient.
Wherein, the content of kaolin and quartz accounts for about 50% or more, it is also possible to contain illite, chlorite, muscovite, feldspar, Huang Tie
Other crystal phase mineral such as mine, siderite, bloodstone, calcite.Wherein kaolinite, illite, chlorite, muscovite, feldspar etc.
Bauxite clay class mineral are belonged to, good absorption property is embodied.The main chemical compositions of gangue include AL2O3, SiO2,
CaO, MgO, Fe2O3, K2O and Na2O etc..Coal geology age and from different places, these chemical composition contents have very great fluctuation process.
However, the gangue of coal enterprise's stockpiling is up to 5,000,000,000 t, and discharge amount is to be no less than annual 300000000 t in China
Speed increase.Before expecting 2020, the annual discharge amount of China's gangue will no less than 700,000,000 t.It stores up throughout the year
Gangue not only wastes a large amount of valuable land resources, can also destroy the ecological environment in mining area, influences the groundwater quality in mining area,
Destroy landscape etc..The spoils such as Pan Mei group, lotus group without ground can heap stage.The traditional treatment method of gangue is all
For brickmaking, generates electricity or repair the roads, and the gangue calorific value of certain areas is relatively low, is unsuitable for generating electricity, such as: Sichuan, because
This, the problem of gangue, has seriously affected the normal operation of coal mine.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology, provides and a kind of prepares magnetic bio-carrier using gangue
Method.
The purpose of the present invention is achieved through the following technical solutions: a kind of side preparing magnetic bio-carrier using gangue
Method, it the following steps are included:
S1: raw material test carries out chemical component and material phase analysis to coal shale in brick making, obtains the chemical component of gangue and its contain
Amount;
S2: raw material is broken, by raw material by being crushed crusher machine, obtains powder;
S3: ingredient carries out ingredient according to the gangue in S1 step, wherein the parts by weight of gangue are 50 parts, pore creating material 1 ~ 3
Part;
S4: the material prepared in S3 step is put into agitating device, obtains mixture by mixing;
S5: mixture is suppressed the microspheroidal of 3 ~ 20mm by molding by molding machine;
S6: calcining heats mixture molding in S5, and make its activation;
S7: air-cooled, the calcining material that activation in S6 is completed is cooling by air-cooled mode;
S8: the clinker that parts by weight are 50 parts is put into the liquid in reaction vessel, and makes solid-to-liquid ratio by magnetization modification are as follows:
Then the sum of parts by weight are put into reaction vessel and are carried out for 2 ~ 25 parts of frerrous chloride and iron chloride mixture by 1:5 ~ 1:50
Reaction adjusts pH value, makes its solution alkaline;
S9: the mixture after magnetization is separated by solid-liquid separation by slag-liquid separation by separator;
S10: the slag after separation is dried, obtains finished product by drying.
Preferably, including the following steps in the S2 step,
S21: raw material is carried out by jaw crusher rough and torn, obtains feed particulate material by coarse crushing;
S22: the feed particulate material in S21 is carried out grinding by ball mill, obtains powder by fine grinding.
Preferably, the granularity of the powder in the S22 after ball mill fine grinding is 160 ~ 250 mesh.
Preferably, heating equipment employed in the S6 step is tunnel oven, rotary kiln, chamber kiln, shuttle kiln, trolley
One kind of kiln and microwave kiln.
Preferably, it in the S6 step, when heating, before 500 DEG C, is heated up with the heating rate of 5 ~ 8 DEG C/min, 500 ~
800 DEG C are then heated up with 4 ~ 6 DEG C/min, and 800 DEG C or more are then heated up with 2 ~ 4 DEG C/min, then in 1100 ~ 1300 DEG C of temperature
1 ~ 3h of lower heat preservation.
Preferably, the fluid temperature in the S8 in reaction vessel is 40 ~ 90 DEG C.
Preferably, the S10 drying temperature is 60 ~ 120 DEG C.
Preferably, the frerrous chloride in the S8: the molar ratio of iron chloride is 1 ~ 2
The invention has the following advantages that
1, porous biological carrier of the invention uses gangue for main production raw material, so that the cost of raw material reduces, to drop
It is excessive to can solve existing Piling of Gangue for the low production cost of porous biological carrier, and gangue is turned waste into wealth
Status;
2, in calcination process, interior carbon in gangue reacts with the oxygen in air and generates carbon dioxide, and carbon dioxide overflows
Out, so that forming mesoporous and micropore in gangue, in the present embodiment, pore creating material is flour or stalk particle, it is preferred that
Pore creating material is flour, and flour burns under high temperature action, can also generate carbon dioxide, carbon dioxide overflows, to be formed mesoporous
And micropore, and the mesoporous and micropore formed, then it can be used as the carrier of biology, pollutant removal can be improved for water treatment procedure
Rate improves stable water outlet reduction raising bioreactor utilization rate, reduces occupied area and construction cost;It is applied in soil
Afterwards, moreover it is possible to change soil texture, increase the water-retaining property and gas permeability of soil;
3, by magnetization modification, under conditions of hydro-thermal, alkalinity, the frerrous chloride and iron chloride of addition produce ferroso-ferric oxide,
And it is attached to the surface of powder, so that powder has magnetism, and the microorganism in mesoporous and micropore, in four magnetic oxidations
Under the action of three-iron, the metabolism of microorganism can speed up, to accelerate the decomposition of organic matter and the breeding of microorganism.
Specific embodiment
Embodiment one:
A method of preparing magnetic bio-carrier using gangue, it the following steps are included:
S1: raw material test carries out chemical component and material phase analysis to coal shale in brick making, obtains the chemical component of gangue and its contain
Amount;
S2: raw material is broken, by raw material by being crushed crusher machine, obtains powder;Further, raw material is broken is divided into two steps,
That is coarse crushing and fine grinding first carries out coarse crushing, raw material is rough and torn by the progress of rough and torn equipment, it is preferred that be carried out using jaw crusher
It is rough and torn, feed particulate material is obtained, the main purpose of coarse crushing is to be crushed big block-like coal shale in brick making, is broken into graininess
Raw material refined so that gangue is able to enter in Refining apparatus, secondly, sending granular raw material to fine grinding
It goes to be ground in equipment, preferred Refining apparatus is ball mill, obtains powder, it is generally the case that pass through ball mill milled
Powder be needed for powder, i.e., ball mill fine grinding after powder particles be 160 mesh, certainly, in the actual production process, can will
The powder of ball mill milled is screened by screening machine, filters out the powder of 160 mesh, is then greater than the powder of 160 mesh, then again
Secondary progress ball mill is ground.
S3: ingredient carries out ingredient according to the gangue in S1 step, wherein the parts by weight of gangue are 50 parts, pore creating material
1 ~ 3 part;
S4: the material prepared in S3 step is put into agitating device, obtains mixture by mixing;
S5: mixture is passed through molding machine 3 millimeters of microspheroidal of compacting by molding;
S6: calcining heats mixture molding in S5, and make its activation, and when calcining, used heating equipment was tunnel
One kind of road kiln, rotary kiln, chamber kiln, shuttle kiln, car-bottom kiln and microwave kiln, further, when heated, before 500 DEG C, with
The heating rate of 5 DEG C/min heats up, and 500 ~ 800 DEG C are then heated up with 4 DEG C/min, and 800 DEG C or more are then heated up with 2 DEG C/min,
Then 1100 at a temperature of keep the temperature 1h, in calcination process, in gangue in carbon, react with the oxygen in air generate two
Carbonoxide, carbon dioxide overflow, so that forming mesoporous and micropore in gangue, in the present embodiment, pore creating material is flour
Or stalk particle, it is preferred that pore creating material is flour, and flour burns under high temperature action, can also generate carbon dioxide, carbon dioxide
It overflows, so that the mesoporous and micropore for forming mesoporous and micropore, and being formed, then can be used as the carrier of biology;
S7: air-cooled, the calcining material that activation in S6 is completed is cooling by air-cooled mode;
S8: the clinker that parts by weight are 50 parts is put into the liquid in reaction vessel, and makes solid-to-liquid ratio by magnetization modification are as follows:
Then the sum of parts by weight are put into reaction vessel and are reacted for 2 parts of frerrous chloride and iron chloride mixture, adjusted by 1:5
Whole pH value makes its solution alkaline, and the fluid temperature in reaction vessel is 40 DEG C, it is preferred that frerrous chloride: iron chloride
Molar ratio is 1;
S9: the mixture after magnetization is separated by solid-liquid separation by slag-liquid separation by separator;
S10: the slag after separation is dried, obtains finished product by drying, and in the present embodiment, drying temperature is 60 DEG C.
Coal shale in brick making produces a large amount of carbon dioxide, dioxy under calcining effect and under the action of pore creating material calcining
Change carbon to overflow, so that forming mesoporous and micropore in powder, and there is very big reference area, and by magnetization modification, in water
Under conditions of heat, alkalinity, the frerrous chloride and iron chloride of addition produce ferroso-ferric oxide, and are attached to the surface of powder, thus
So that powder has magnetism, and the microorganism in mesoporous and micropore can speed up micro- under the action of magnetic ferroso-ferric oxide
The metabolism of biology, to accelerate the decomposition of organic matter and the breeding of microorganism.
Embodiment two:
A method of preparing magnetic bio-carrier using gangue, it the following steps are included:
S1: raw material test carries out chemical component and material phase analysis to coal shale in brick making, obtains the chemical component of gangue and its contain
Amount;
S2: raw material is broken, by raw material by being crushed crusher machine, obtains powder;Further, raw material is broken is divided into two steps,
That is coarse crushing and fine grinding first carries out coarse crushing, raw material is rough and torn by the progress of rough and torn equipment, it is preferred that be carried out using jaw crusher
It is rough and torn, feed particulate material is obtained, the main purpose of coarse crushing is to be crushed big block-like coal shale in brick making, is broken into graininess
Raw material refined so that gangue is able to enter in Refining apparatus, secondly, sending granular raw material to fine grinding
It goes to be ground in equipment, preferred Refining apparatus is ball mill, obtains powder, it is generally the case that pass through ball mill milled
Powder be needed for powder, i.e., ball mill fine grinding after powder particles be 250 mesh, certainly, in the actual production process, can will
The powder of ball mill milled is screened by screening machine, filters out the powder of 250 mesh, is then greater than the powder of 250 mesh, then again
Secondary progress ball mill is ground.
S3: ingredient carries out ingredient according to the gangue in S1 step, wherein the parts by weight of gangue are 50 parts, pore creating material
3 parts;
S4: the material prepared in S3 step is put into agitating device, obtains mixture by mixing, when stirring, needs the material that will be prepared
It is sufficiently mixed;
S5: mixture is passed through molding machine 20 millimeters of microspheroidal of compacting by molding;;
S6: calcining heats mixture molding in S5, and make its activation, and when calcining, used heating equipment was tunnel
One kind of road kiln, rotary kiln, chamber kiln, shuttle kiln, car-bottom kiln and microwave kiln, further, when heated, before 500 DEG C, with
The heating rate of 8 DEG C/min heats up, and 500 ~ 800 DEG C are then heated up with 6 DEG C/min, and 800 DEG C or more are then heated up with 4 DEG C/min,
Then 1300 DEG C at a temperature of keep the temperature 3h, in calcination process, in gangue in carbon, react generation with the oxygen in air
Carbon dioxide, carbon dioxide overflow, so that forming mesoporous and micropore in gangue, in the present embodiment, pore creating material is face
Powder or stalk particle, it is preferred that pore creating material is flour, and flour burns under high temperature action, can also generate carbon dioxide, titanium dioxide
Carbon overflows, so that the mesoporous and micropore for forming mesoporous and micropore, and being formed, then can be used as the carrier of biology.
S7: air-cooled, the calcining material that activation in S6 is completed is cooling by air-cooled mode;
S8: the clinker that parts by weight are 50 parts is put into the liquid in reaction vessel, and makes solid-to-liquid ratio by magnetization modification are as follows:
Then the sum of parts by weight are put into reaction vessel and are reacted for 25 parts of frerrous chloride and iron chloride mixture by 1:50,
PH value is adjusted, its solution alkaline is made, and the fluid temperature in reaction vessel is 90 DEG C, it is preferred that frerrous chloride: iron chloride
Molar ratio be 2;
S9: the mixture after magnetization is separated by solid-liquid separation by slag-liquid separation by separator;
S10: the slag after separation is dried, obtains finished product by drying, and in the present embodiment, drying temperature is 120 DEG C.
Coal shale in brick making produces a large amount of carbon dioxide, dioxy under calcining effect and under the action of pore creating material calcining
Change carbon to overflow, so that forming mesoporous and micropore in powder, and there is very big reference area, and by magnetization modification, in water
Under conditions of heat, alkalinity, the frerrous chloride and iron chloride of addition produce ferroso-ferric oxide, and are attached to the surface of powder, thus
So that powder has magnetism, and the microorganism in mesoporous and micropore can speed up micro- under the action of magnetic ferroso-ferric oxide
The metabolism of biology, to accelerate the decomposition of organic matter and the breeding of microorganism.
Embodiment three:
S1: raw material test carries out chemical component and material phase analysis to coal shale in brick making, obtains the chemical component of gangue and its contain
Amount;
S2: raw material is broken, by raw material by being crushed crusher machine, obtains powder;Further, raw material is broken is divided into two steps,
That is coarse crushing and fine grinding first carries out coarse crushing, raw material is rough and torn by the progress of rough and torn equipment, it is preferred that be carried out using jaw crusher
It is rough and torn, feed particulate material is obtained, the main purpose of coarse crushing is to be crushed big block-like coal shale in brick making, is broken into graininess
Raw material refined so that gangue is able to enter in Refining apparatus, secondly, sending granular raw material to fine grinding
It goes to be ground in equipment, preferred Refining apparatus is ball mill, obtains powder, it is generally the case that pass through ball mill milled
Powder be needed for powder, i.e., ball mill fine grinding after powder particles be 205 mesh, certainly, in the actual production process, can will
The powder of ball mill milled is screened by screening machine, filters out the powder of 205 mesh, is then greater than the powder of 205 mesh, then again
Secondary progress ball mill is ground.
S3: ingredient carries out ingredient according to the gangue in S1 step, wherein the parts by weight of gangue are 50 parts, pore creating material
2 parts;
S4: the material prepared in S3 step is put into agitating device, obtains mixture by mixing;
S5: mixture is passed through molding machine 12 millimeters of microspheroidal of compacting by molding;
S6: calcining heats mixture molding in S5, and make its activation, and when calcining, used heating equipment was tunnel
One kind of road kiln, rotary kiln, chamber kiln, shuttle kiln, car-bottom kiln and microwave kiln, further, when heated, before 500 DEG C, with
The heating rate of 7 DEG C/min heats up, and 500 ~ 800 DEG C are then heated up with 5 DEG C/min, and 800 DEG C or more are then heated up with 3 DEG C/min,
Then 1150 at a temperature of keep the temperature 2h, in calcination process, in gangue in carbon, react with the oxygen in air generate two
Carbonoxide, carbon dioxide overflow, so that forming mesoporous and micropore in gangue, in the present embodiment, pore creating material is flour
Or stalk particle, it is preferred that pore creating material is flour, and flour burns under high temperature action, can also generate carbon dioxide, carbon dioxide
It overflows, so that the mesoporous and micropore for forming mesoporous and micropore, and being formed, then can be used as the carrier of biology;
S7: air-cooled, the calcining material that activation in S6 is completed is cooling by air-cooled mode;
S8: the clinker that parts by weight are 50 parts is put into the liquid in reaction vessel, and makes solid-to-liquid ratio by magnetization modification are as follows:
Then the sum of parts by weight are put into reaction vessel and are reacted for 15 parts of frerrous chloride and iron chloride mixture by 1:25,
PH value is adjusted, its solution alkaline is made, and the fluid temperature in reaction vessel is 65 DEG C, it is preferred that frerrous chloride: iron chloride
Molar ratio be 1.5;
S9: the mixture after magnetization is separated by solid-liquid separation by slag-liquid separation by centrifuge;
S10: the slag after separation is dried, obtains finished product by drying, and in the present embodiment, drying temperature is 90 DEG C.
Coal shale in brick making produces a large amount of carbon dioxide, dioxy under calcining effect and under the action of pore creating material calcining
Change carbon to overflow, so that forming mesoporous and micropore in powder, and there is very big reference area, and by magnetization modification, in water
Under conditions of heat, alkalinity, the frerrous chloride and iron chloride of addition produce ferroso-ferric oxide, and are attached to the surface of powder, thus
So that powder has magnetism, and the microorganism in mesoporous and micropore can speed up micro- under the action of magnetic ferroso-ferric oxide
The metabolism of biology, to accelerate the decomposition of organic matter and the breeding of microorganism.
Although reference be made herein to invention has been described for multiple explanatory embodiments of the invention, however, it is to be understood that
Those skilled in the art can be designed that a lot of other modification and implementations, these modifications and implementations will fall in this Shen
It please be within disclosed scope and spirit.It more specifically, within the scope of the present disclosure and claims, can be to master
The building block and/or layout for inscribing composite configuration carry out a variety of variations and modifications.In addition to what is carried out to building block and/or layout
Outside modification and improvement, to those skilled in the art, other purposes also be will be apparent.
Claims (8)
1. a kind of method for preparing magnetic bio-carrier using gangue, it is characterised in that: it the following steps are included:
S1: raw material test carries out chemical component and material phase analysis to coal shale in brick making, obtains the chemical component of gangue and its contain
Amount;
S2: raw material is broken, by raw material by being crushed crusher machine, obtains powder;
S3: ingredient carries out ingredient according to the gangue in S1 step, wherein the parts by weight of gangue are 50 parts, pore creating material 1 ~ 3
Part;
S4: the material prepared in S3 step is put into agitating device, obtains mixture by mixing;
S5: mixture is suppressed the microspheroidal of 3 ~ 20mm by molding by molding machine;
S6: calcining heats mixture molding in S5, and make its activation;
S7: air-cooled, the calcining material that activation in S6 is completed is cooling by air-cooled mode;
S8: the clinker that parts by weight are 50 parts is put into the liquid in reaction vessel, and makes solid-to-liquid ratio by magnetization modification are as follows:
Then the sum of parts by weight are put into reaction vessel and are carried out for 2 ~ 25 parts of frerrous chloride and iron chloride mixture by 1:5 ~ 1:50
Reaction adjusts pH value, makes its solution alkaline;
S9: the mixture after magnetization is separated by solid-liquid separation by slag-liquid separation by separator;
S10: the slag after separation is dried, obtains finished product by drying.
2. a kind of method for preparing magnetic bio-carrier using gangue according to claim 1, it is characterised in that: described
It is in S2 step the following steps are included:
S21: raw material is carried out by jaw crusher rough and torn, obtains feed particulate material by coarse crushing;
S22: the feed particulate material in S21 is carried out grinding by ball mill, obtains powder by fine grinding.
3. a kind of method for preparing magnetic bio-carrier using gangue according to claim 2, it is characterised in that: described
The granularity of powder in S22 after ball mill fine grinding is 160 ~ 250 mesh.
4. a kind of method for preparing magnetic bio-carrier using gangue according to claim 1, it is characterised in that: described
Heating equipment employed in S6 step is one kind of tunnel oven, rotary kiln, chamber kiln, shuttle kiln, car-bottom kiln and microwave kiln.
5. a kind of method for preparing magnetic bio-carrier using gangue according to claim 1, it is characterised in that: described
In S6 step, when heating, before 500 DEG C, heated up with the heating rate of 5 ~ 8 DEG C/min, 500 ~ 800 DEG C then with 4 ~ 6 DEG C/min liter
Temperature, 800 DEG C or more are then heated up with 2 ~ 4 DEG C/min, then 1100 ~ 1300 DEG C at a temperature of keep the temperature 1 ~ 3h.
6. a kind of method for preparing magnetic bio-carrier using gangue according to claim 1, it is characterised in that: described
Fluid temperature in S8 in reaction vessel is 40 ~ 90 DEG C.
7. a kind of method for preparing magnetic bio-carrier using gangue according to claim 1, it is characterised in that: described
S10 drying temperature is 60 ~ 120 DEG C.
8. a kind of method for preparing magnetic bio-carrier using gangue according to claim 1, it is characterised in that: described
Frerrous chloride in S8: the molar ratio of iron chloride is 1 ~ 2.
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CN113104953B (en) * | 2021-04-13 | 2022-04-12 | 北京石油化工学院 | Preparation method of biological filler and sewage treatment method |
CN115340424A (en) * | 2022-08-15 | 2022-11-15 | 昌晖自动化科技(济南)有限公司 | Coal gangue magnetized soil conditioner and preparation method thereof |
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