CN102247800A - Composite ceramsite prepared from bentonite, perlite and zeolite serving as main raw materials and preparation method of composite ceramsite - Google Patents
Composite ceramsite prepared from bentonite, perlite and zeolite serving as main raw materials and preparation method of composite ceramsite Download PDFInfo
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Abstract
The invention discloses composite ceramsite prepared from bentonite, perlite and zeolite serving as main raw materials. The raw materials are molded, roasted at a high temperature, and scattered to form spherical or columnar porous ceramsite. The composite ceramsite has the obvious advantages that: 1, an environment-friendly product with high economic value and long service life is prepared from natural nonmetallic minerals and clay which have adsorption property and are used as raw materials, so that the aim of treating waste by using the natural minerals is fulfilled; 2, microporous ceramsite with a good structure is prepared by firing abundant natural minerals, namely the bentonite and the zeolite which have an interlayer structure and a natural pore channel structure and are used as raw materials, and micropores formed in the firing process are communicated with the natural pore channel structure and the interlayer structure, so that the prepared ceramsite has a good pore channel and high adsorption capacity; and 3, after the ceramsite is used for a certain period of time, the adsorption capacity is in a saturated state, adsorption capability is reduced, and the ceramsite can be dried and regenerated at a high temperature, so that a pollution treatment material is recycled, and secondary pollutants are not generated.
Description
Technical field
The invention belongs to technical field of waste water processing, being specifically related to a kind of is primary raw material through porous ceramic grain of high temperature sintering and preparation method thereof with perlite, bentonite and natural zeolite.
Background technology
Method to industrial wastewater and city domestic sewage improvement is a lot of at present, generally can be divided into physical-chemical process, chemical method and bioanalysis.As adopt the coagulation improvement city domestic sewage that combines with bio-aeration; Adopt coagulation to combine and administer industrial dyeing waste water with chemical oxidation; Adopt combine with absorption deep treatment coking chemical waste water and adopt the nitrification and denitrification biotechnology to administer high ammonia nitrogen organic wastewater etc. of coagulation, bio-aeration, above-mentioned technology of waste water control is in the existing application widely of industry-by-industry.Yet existing at present technology of waste water control all has different defectives.Low as bio-aeration technical finesse efficient, floor space is big; Waste water sorbing material cost height, enterprise is difficult to bear expensive pollution treatment; Membrane filtration or reverse osmosis technical operation cost height, condition harshness.These methods are generally adopted in the enterprise larger, that the intensification degree is high, but are difficult to be used widely in the natural water body that has polluted in, exhausting waste water control little in production scale and river course, lake etc.
In recent years, carry out fixed bed biofilter deep treatment Technology of Sewage both at home and abroad energetically, and represent good prospects for application.The core of fixed bed biofilter is the preparation of bio-carrier material and at the control in the special-purpose duct of certain pollutant, and the seed selection of special bacteria.At present aspect the bio-carrier material often because of practical resin, active carbon, molecular sieve etc. cause cost too high, be difficult to the realization technology and popularize.Chinese patent 200810006102.9,02112755.7,200810162790.8,03153641.7 having introduced several is the method for main material production porous ceramic grain with clay and flyash, boccaro pottery and quartz, because of having carbon dust or active carbon composition in its raw material, so mainly be in sewage disposal because the suction-operated of powdered active carbon.Because the regeneration difficulty produces new solid waste in sewage disposal.Sichuan architecture science research institute is raw material with flyash by adding adhesive and water, and through moulding and SINTERING PRODUCTION lightweight, porous ceramicite concrete technology, this product distribution of pores also is not suitable for water treatment, is specifically designed to the filler of making lightweight concrete.Function haydite described in the Chinese patent 03136145.5 and 02129972.2 and filtration haydite all are based on haydite are supported material as microorganism, but in order to obtain desirable pore passage structure and porosity, have all used pore former and expanding agent.Though described method has improved sewage treating efficiency, prolonged haydite service life, fundamentally do not solve the high problem of bio-carrier cost yet.And, used active carbon, carbon dust or chemical cross-linking agent etc. again, and adopted complicated preparation technology and activation method in order to improve the compatibility of ceramsite material.In a word, above-mentioned material and the equal operating cost height of its functional structure perhaps easily bring the secondary environmental pollution problem owing to be difficult to recycling.
Chinese patent 03116257.6,200710025589.0,200810162554.8,200410018109.4 has been reported and has been utilized bentonite or modified alta-mud directly or at microwave, ultrasonic synergistic to handle the method for organic wastewater or heavy metal ion, contaminant removal efficiency height, simple to operate.Utilize bentonite under suspended state, to carry out organic sewage or heavy metal ion adsorbed but be in the described patent,, cause secondary pollution easily because bentonite clay particle is thin and superpower water imbibition, this method greatest drawback are arranged is the loaded down with trivial details or high energy consumption of subsequent treatment.
Chinese patent 200410065686.9,200510046470.2 bulletin patents 200810233426.6,201010000268.7 have been introduced organic matter or the heavy metal ion of utilizing in natural zeolite or the modified zeolite processing industrial wastewater.Natural zeolite has the characteristics pore passage structure, and processing cost is low, treating capacity is big and simple to operate.
Be single natural zeolite sorbing material but said method is used, because the pore passage structure narrow range causes adsorption capacity little, handling waste water has limitation, therefore, provides a kind of high power capacity, renewable, and the simple porous ceramic grain of preparation method has been a problem of needing solution badly.
Summary of the invention
The objective of the invention is in order to overcome problems such as high energy consumption, low capacity and regeneration difficulty in the improvement pollution that exists in the above-mentioned prior art, provide a kind of natural nonmetallic mineral perlite, bentonite and zeolite of utilizing to be haydite of primary raw material and preparation method thereof, this method has simple to operate, porosity height and low cost and other advantages.
Technical solution of the present invention is achieved in that
A kind of is the composite haydite of primary raw material with bentonite, perlite and zeolite, it is characterized in that being prepared from according to mass percent by following raw materials according: bentonite 15 ~ 60%, perlite 20 ~ 60%, zeolite 10 ~ 30%, clay 2 ~ 20%, auxiliary material 1 ~ 10%.
Described auxiliary material is any one or more than one composition in gelatin, polyethylene glycol, polyacrylamide, the charcoal powder.
Its preparation method is as follows:
The first step: the natural montmorillonite sodium is treated as sodium bentonite, natural zeolite is treated to the acidifying zeolite with 4M hydrochloric acid;
Second step: sodium bentonite, acidifying zeolite and the expanded perlite that makes in the first step is crushed to granularity reaches 40 ~ 200 orders;
The 3rd step: the material that crushes in second step is fully mixed with auxiliary material, send in the comminutor granulation after mixing or make ball, particle diameter is controlled at 10 ~ 150mm;
The 4th step: place the high temperature kiln to carry out drying and roasting the ball material or the pellet that obtain in the 3rd step;
The 5th step:, send into and be ground into granular pattern or column type in the powder machine with the material cooling after the roasting in the 4th step.
The abundant incorporation time of raw material is 40 ~ 60 minutes in the 3rd step, 8 ~ 20 minutes time of staying in the comminutor.
The 4th the step in the high temperature kiln baking temperature be 150 ℃ ~ 400 ℃, be 20 ~ 60 minutes drying time; Sintering temperature is 300 ~ 1000 ℃, and roasting time is 90 ~ 240 minutes.
Material air atmosphere in the 5th step after the roasting naturally cools to 25 ℃; In pulverizer, be ground into granular pattern or column type that granularity is 5 ~ 120mm.
Positive beneficial effect: be the environment-friendly products that raw material production has higher economic worth, longer life 1,, realized controlling useless purpose with natural minerals with natural nonmetallic mineral and clay with absorption property.2, be raw material with richness product natural minerals bentonite and zeolite with interlayer structure and natural pore passage structure, fire the micropore haydite that forms the well-formed under the condition at this, the micropore that forms in the sintering procedure communicates with interlayer structure with natural duct, has guaranteed duct that made haydite is good and big adsorption capacity.3, after using a period of time, the adsorption capacity state that reaches capacity, adsorption capacity descends, can be with high temperature regeneration again after the haydite drying, thus realize recycling of pollution treatment material, and do not produce secondary pollution.
Description of drawings
Fig. 1 is preparation method's process chart of the present invention.
The specific embodiment
Below in conjunction with each embodiment, the present invention will be further described in detail:
Before providing embodiment, earlier natural nonmetallic ore raw material perlite, bentonite and zeolite among the present invention are described.Expanded perlite be by material from acidic volcanic glass matter lava through moment a kind of light porous material of making of high temperature puffing, have cellular internal structure.Natural zeolite is the frame shape aluminium silicate mineral of the moisture sodium of gang (potassium), calcium or magnesium, barium etc.Its main chemical constituent is SiO
2, Al
2O
3, H
2O and alkali or alkaline-earth metal, zeolite crystal inside have a lot of uniform holes and passage, and the hole is connected with each other by the passage of opening, and the researcher adopts acidification usually, make it have bigger pore passage structure and hole, thereby have the good adsorption performance.Natural montmorillonite is a kind of 2:1 type silicate mineral with unique texture, and each layer is made of two Si-O tetrahedral layers and an Al-O octahedral layer, because of its special crystal structure has the good adsorption ability.In order to increase its interlamellar spacing, usually the natural calcium base bentonite is organised or sodium to strengthen its adsorption capacity.
A kind of is the composite haydite of primary raw material with bentonite, perlite and zeolite, it is characterized in that being prepared from according to mass percent by following raw materials according: bentonite 15 ~ 60%, perlite 20 ~ 60%, zeolite 10 ~ 30%, clay 2 ~ 20%, auxiliary material 1 ~ 10%.
Described auxiliary material is any one or more than one composition in gelatin, polyethylene glycol, polyacrylamide, the charcoal powder.
Its preparation method is as follows:
The first step: the natural montmorillonite sodium is treated as sodium bentonite, natural zeolite is treated to the acidifying zeolite with 4M hydrochloric acid;
Second step: sodium bentonite, acidifying zeolite and the expanded perlite that makes in the first step is crushed to granularity reaches 40 ~ 200 orders;
The 3rd step: the material that crushes in second step is fully mixed with auxiliary material, send in the comminutor granulation after mixing or make ball, particle diameter is controlled at 10 ~ 150mm;
The 4th step: place the high temperature kiln to carry out drying and roasting the ball material or the pellet that obtain in the 3rd step;
The 5th step:, send into and be ground into granular pattern or column type in the powder machine with the material cooling after the roasting in the 4th step.
The abundant incorporation time of raw material is 40 ~ 60 minutes in the 3rd step, 8 ~ 20 minutes time of staying in the comminutor.
The 4th the step in the high temperature kiln baking temperature be 150 ℃ ~ 400 ℃, be 20 ~ 60 minutes drying time; Sintering temperature is 300 ~ 1000 ℃, and roasting time is 90 ~ 240 minutes.
Material air atmosphere in the 5th step after the roasting naturally cools to 25 ℃; In pulverizer, be ground into granular pattern or column type that granularity is 5 ~ 120mm.
Embodiment 1
With expanded perlite, sodium bentonite and natural zeolite is primary raw material, is auxiliary material with clay and polyethylene glycol.Take by weighing respectively: expanded perlite (60 ~ 80 order) 500g, sodium bentonite 200g, acidifying zeolite 150g, clay 50g, polyethylene glycol 50g.
Bentonite, zeolite and clay are crushed to 200 orders respectively.
Above-mentioned main materials and auxiliary materials was fully mixed 60 minutes in mixing agitator.
The material that mixes is put into the tumbling disk granulator granulation, and particle diameter is controlled at 10 ~ 150mm.
The ball material is placed on sintering in the high temperature furnace air atmosphere.Be warming up to 200 ℃ earlier, dehydrated with this understanding 60 minutes; Continuation rising temperature to 600 ~ 800 ℃ is incubated 120 minutes.
The material that sinters naturally cools to 25 ℃, is ground into the spherical of granularity 5 ~ 120mm or post grain in pulverizer.
Embodiment 2
With expanded perlite, sodium bentonite and natural zeolite is primary raw material, is auxiliary material with clay and gelatin.Take by weighing respectively: expanded perlite (60 ~ 80 order) 300g, sodium bentonite 200g, acidifying zeolite 250g, clay 50g, gelatin 50g.
Bentonite, zeolite and clay are crushed to 200 orders respectively.
Above-mentioned main materials and auxiliary materials was fully mixed 50 minutes in mixing agitator.
The material that mixes is put into the tumbling disk granulator granulation, and particle diameter is controlled at 10 ~ 150mm.
The ball material is placed on sintering in the high temperature furnace air atmosphere.Be warming up to 250 ℃ earlier, dehydrated with this understanding 50 minutes; Continuation rising temperature to 650 ~ 900 ℃ is incubated 120 minutes.
The material that sinters naturally cools to 25 ℃, is ground into the spherical of granularity 5 ~ 120mm or post grain in pulverizer.
Embodiment 3
With sodium bentonite, expanded perlite and natural zeolite is primary raw material, is auxiliary material with clay and polyacrylamide.Take by weighing respectively: sodium bentonite 250g, expanded perlite (40 ~ 60 order) 350g, acidifying zeolite 200g, clay 60g, polyacrylamide 50g.
Bentonite, zeolite and clay are crushed to 200 orders respectively.
Above-mentioned main materials and auxiliary materials was fully mixed 60 minutes in mixing agitator.
The material that mixes is put into the tumbling disk granulator granulation, and particle diameter is controlled at 10 ~ 150mm.
The ball material is placed on sintering in the high temperature furnace air atmosphere.Be warming up to 300 ℃ earlier, dehydrated with this understanding 40 minutes; Continuation rising temperature to 600 ~ 700 ℃ is incubated 120 minutes.
The material that sinters naturally cools to 25 ℃, is ground into the spherical of granularity 5 ~ 120mm or post grain in pulverizer.
Embodiment 4
With sodium bentonite, expanded perlite and natural zeolite is primary raw material, is auxiliary material with clay and charcoal powder.Take by weighing respectively: sodium bentonite 150g, expanded perlite (60 ~ 80 order) 400g, acidifying zeolite 200g, clay 100g, charcoal powder 30g.
Bentonite, zeolite and clay are crushed to 200 orders respectively.
Above-mentioned main materials and auxiliary materials was fully mixed 60 minutes in mixing agitator.
The material that mixes is put into the tumbling disk granulator granulation, and particle diameter is controlled at 10 ~ 150mm.
The ball material is placed on sintering in the high temperature furnace air atmosphere.Be warming up to 320 ℃ earlier, dehydrated with this understanding 20 minutes; Continuation rising temperature to 600 ~ 800 ℃ is incubated 120 minutes.
The material that sinters naturally cools to 25 ℃, is ground into the spherical of granularity 5 ~ 120mm or post grain in pulverizer.
Embodiment 5
With sodium bentonite, expanded perlite and natural zeolite is primary raw material, is auxiliary material with clay and polyethylene glycol.Take by weighing respectively: sodium bentonite 430g, expanded perlite (60 ~ 80 order) 210g, acidifying zeolite 130g, clay 50g, each 20g of polyethylene glycol, polyacrylamide, charcoal powder and gelatin.
Bentonite, zeolite and clay are crushed to 200 orders respectively.
Above-mentioned main materials and auxiliary materials was fully mixed 60 minutes in mixing agitator.
The material that mixes is put into the tumbling disk granulator granulation, and particle diameter is controlled at 10 ~ 150mm.
The ball material is placed on sintering in the high temperature furnace air atmosphere.Be warming up to 180 ℃ earlier, dehydrated with this understanding 50 minutes; Continuation rising temperature to 500 ~ 750 ℃ is incubated 200 minutes.
The material that sinters naturally cools to 25 ℃, is ground into the spherical of granularity 5 ~ 120mm or post grain in pulverizer.
The application of haydite
With the haydite among the embodiment, carry out organic dyestuff adsorption test in the dyeing waste water respectively, with the 2g haydite (unit weight: 1.13g/ml) act on the dyeing waste water that 20ml contains Basic Violet 5BN (
COD1321.65), stirring at low speed can make the COD of this waste water reduce to 50 ~ 63.2 after 30 minutes.
The haydite reclaiming utilizes
Reclaim the saturated haydite of absorption, be dried to moisture content≤15%.Pellet is placed on the high temperature kiln roasting.
Regenerative process is as follows: be warming up to 300 ℃ earlier, dehydrated with this understanding 35 minutes; Continue to be warming up to 600 ~ 800 ℃, regenerative process is promptly finished in roasting 60 minutes.This haydite is reusable more than 15 times, and the effect of handling waste water does not descend substantially.
The haydite that is repeatedly used is reclaimed, after the drying, is crushed to 140 orders, can be used as the raw material of the inorganic foamed insulation material of preparation building, therefore in its production and use, do not produce secondary pollution.
In summary it can be seen that outstanding feature of the present invention and obvious improvement are effectively to utilize the rich intrinsic absorption property of natural nonmetallic mineral that produces, and effectively overcome single mineral material be difficult to separate the shortcoming single with the duct.Made haydite can recycle, and can not produce new solid secondary pollution.
Above embodiment only is used to illustrate preferred implementation of the present invention; but the present invention is not limited to above-mentioned embodiment; in the ken that described field those of ordinary skill is possessed; any modification of being done within the spirit and principles in the present invention, be equal to and substitute and improvement etc., it all should be encompassed within the technical scheme scope that the present invention asks for protection.
Claims (6)
1. one kind is the composite haydite of primary raw material with bentonite, expanded perlite and natural zeolite, it is characterized in that being prepared from according to mass percent by following raw materials according: bentonite 15 ~ 60%, perlite 20 ~ 60%, zeolite 10 ~ 30%, clay 2 ~ 20%, auxiliary material 1 ~ 10%.
According to claim 1 described a kind of be the composite haydite of primary raw material with bentonite, perlite and zeolite, it is characterized in that: described auxiliary material is any one or more than one composition in gelatin, polyethylene glycol, polyacrylamide, the charcoal powder.
According to claim 1 described a kind of be the composite haydite of primary raw material with bentonite, perlite and zeolite, its preparation method is as follows:
The first step: the natural montmorillonite sodium is treated as sodium bentonite, natural zeolite is treated to the acidifying zeolite with hydrochloric acid;
Second step: sodium bentonite, acidifying zeolite and the expanded perlite that makes in the first step is crushed to granularity reaches 40 ~ 200 orders;
The 3rd step: the material that crushes in second step is fully mixed with auxiliary material, send in the comminutor granulation after mixing or make ball, particle diameter is controlled at 10 ~ 150mm;
The 4th step: place the high temperature kiln to carry out drying and roasting the ball material or the pellet that obtain in the 3rd step;
The 5th step:, send into and be ground into granular pattern or column type in the powder machine with the material cooling after the roasting in the 4th step.
4. according to claim 3 a kind of be the preparation method of the composite haydite of primary raw material with bentonite, perlite and zeolite, it is characterized in that: the 3rd the step in the abundant incorporation time of raw material be 40 ~ 60 minutes, the time of staying 8 is ~ 20 minutes in the comminutor.
5. according to claim 3 a kind of be the preparation method of the composite haydite of primary raw material with bentonite, perlite and zeolite, it is characterized in that: the 4th the step in the high temperature kiln baking temperature be 150 ℃ ~ 400 ℃, be 20 ~ 80 minutes drying time; Sintering temperature is 300 ~ 1000 ℃, and roasting time is 90 ~ 240 minutes.
6. according to claim 3 a kind of be the preparation method of the composite haydite of primary raw material with bentonite, perlite and zeolite, it is characterized in that: the material air atmosphere in the 5th step after the roasting naturally cools to 25 ℃; In pulverizer, be ground into granular pattern or column type that granularity is 5 ~ 120mm.
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| CN104907039A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Composite volcanic rock absorbent |
| CN104923178A (en) * | 2015-05-21 | 2015-09-23 | 安徽凤凰滤清器股份有限公司 | Modified volcanic-rock acid-resistant adsorbent |
| CN105233808A (en) * | 2015-10-26 | 2016-01-13 | 苏州书瑞环保科技有限公司 | Heavy metal adsorption material and preparation method thereof |
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| CN104907043A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock adsorbent capable of recovering carbon monoxide |
| CN104907039A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Composite volcanic rock absorbent |
| CN104923178A (en) * | 2015-05-21 | 2015-09-23 | 安徽凤凰滤清器股份有限公司 | Modified volcanic-rock acid-resistant adsorbent |
| CN105233808A (en) * | 2015-10-26 | 2016-01-13 | 苏州书瑞环保科技有限公司 | Heavy metal adsorption material and preparation method thereof |
| CN105731562A (en) * | 2016-03-03 | 2016-07-06 | 刘佩佩 | Sewage treatment agent for printing and dyeing industry and preparation method of sewage treatment agent |
| CN105731562B (en) * | 2016-03-03 | 2018-08-07 | 江门市金松印染纺织有限公司 | A kind of sewage-treating agent and preparation method thereof for printing and dyeing industry |
| CN106242638A (en) * | 2016-08-11 | 2016-12-21 | 洛阳名力科技开发有限公司 | A kind of preparation method for water treatment ceramsite |
| CN106631144A (en) * | 2016-09-24 | 2017-05-10 | 甘肃华晨生态治理有限公司 | Cylindrical light ceramsite with air purification function, zeolite and through holes |
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| CN111848130A (en) * | 2020-08-19 | 2020-10-30 | 南通大学 | Modified ceramsite capable of efficiently removing phosphorus and preparation method thereof |
| CN114192124A (en) * | 2021-12-09 | 2022-03-18 | 中国地质大学（武汉） | Natural zeolite adsorption microsphere and preparation method and application thereof |
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Application publication date: 20111123 |