CN116639993A - Novel method for preparing ceramsite by synergistic co-treatment of gangue and sludge - Google Patents
Novel method for preparing ceramsite by synergistic co-treatment of gangue and sludge Download PDFInfo
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- 239000010802 sludge Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000011278 co-treatment Methods 0.000 title claims description 12
- 230000002195 synergetic effect Effects 0.000 title claims description 7
- 238000000197 pyrolysis Methods 0.000 claims abstract description 64
- 239000003245 coal Substances 0.000 claims abstract description 55
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims 2
- 239000000446 fuel Substances 0.000 claims 1
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 24
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003546 flue gas Substances 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
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- 230000009286 beneficial effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000002817 coal dust Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/1321—Waste slurries, e.g. harbour sludge, industrial muds
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract
Aiming at the current situations of huge quantity of gangue and sludge, low recycling utilization rate and the like, the invention discloses a novel method for preparing ceramsite by co-processing the gangue and the sludge, which belongs to the fields of solid waste disposal and recycling utilization. The whole process mainly comprises the steps of mixing and forming gangue and dewatered sludge, drying, co-pyrolysis, co-sintering and the like. The co-pyrolysis effectively releases volatile matters in the raw materials to obtain co-product pyrolysis oil and combustible gas, and simultaneously, the disordered distribution of ceramsite pore channels caused by the large escape of high-temperature gas in the next sintering step is reduced. In addition, N, S and other elements in the raw materials are removed in the co-pyrolysis process, so that pollutants such as NOx and the like in the flue gas during aerobic sintering are avoided. Finally, in the aerobic sintering step, the remaining organics and fixed carbon in the feedstock can burn to provide heat for the previous co-pyrolysis and drying process. The invention is beneficial to protecting the ecological environment of the coal-producing area and simultaneously provides a new economic and reliable way for producing the light ceramsite.
Description
Technical Field
The invention belongs to the field of solid waste disposal and resource utilization, and particularly relates to a novel method for preparing ceramsite by co-processing coal gangue and sludge.
Background
The gangue refers to carbon-containing rock discharged from coal mines in the production processes of development tunneling, coal mining, coal washing and selecting and the like, the yield is about 15-20% of the total yield of raw coal, the accumulation amount of the gangue exceeds 70 hundred million tons, and the gangue is increased at the speed of 1.5 hundred million tons per year, so that the gangue becomes one of the largest industrial solid wastes in the discharge amount of China. At present, coal gangue is used for mining backfilling, which easily causes serious water pollution and resource waste ， The recycling way is mainly to utilize carbon combustion heat release in the coal gangue to produce building materials with low added value, and the profit margin is very small due to high freight cost. The large amount of the accumulated coal gangue and the large treatment difficulty restrict the healthy development of the coal industry in China, so the method has urgency and necessity in comprehensive utilization of the coal gangue, especially production of high added value products.
On the other hand, a large amount of wastewater is generated in both coal mining and downstream processing, and sludge obtained by treating the wastewater may be simply referred to as coal-based sludge. The sludge is a complex heterogeneous colloid composed of a large amount of coal dust, colloid, organic residue, bacterial thallus, inorganic particles and the like. Traditional sludge disposal methods include landfill, composting and incineration. The transportation cost of the sludge landfill is high, and the occupied land resources are large. For disposal means such as pyrolysis and incineration, the sludge has high water content, so that the drying energy consumption is high and the economical efficiency is poor. The coal-based sludge is different from domestic sludge, and has more toxic components and higher disposal difficulty.
The ceramsite is rich in SiO 2 、Al 2 O 3 Is added with proper additives and sintered under high temperature. The porous ceramic material has the advantages of high porosity, strong adsorption capacity, small volume density, high strength, stable chemical performance and the like, and is widely applied to the fields of building materials, sewage treatment, landscaping, refractory materials, heat storage materials, petrochemical industry and the like. The traditional haydite is prepared by using clay, shale, zeolite and other natural resources as main raw materialsThe local ecological environment causes potential harm.
Both solid waste, coal gangue and coal-based sludge, have the dual properties of pollution and resources, and if the solid waste cannot be properly disposed of and recycled, serious environmental pollution and resource waste can be caused. Aiming at the current situations of huge quantity of gangue and coal-based sludge, high treatment difficulty, low recycling utilization rate and the like, the invention discloses a novel recycling utilization method of the gangue and the coal-based sludge, which is used for producing ceramsite products with wide application and high added value by using the gangue and the coal-based sludge as raw materials and adopting the gangue and the coal-based sludge as the raw materials to cooperatively co-pyrolyze and co-sinter. The two kinds of solid waste cooperative treatment can exert the advantages of rich relevant raw materials, short transportation radius or no need of transportation in western regions of China, is a very effective way for recycling and high-value utilization of the two main coal-based solid wastes and changing waste into valuables, has important significance in promoting sustainable healthy development of coal industry.
Disclosure of Invention
The gangue and the sludge have obvious component difference but complementarity, the two co-sintered ceramsite has a synergistic effect, the organic components of the sludge are more, the H/C ratio is high, the heat generated by the combustion of the sludge in the sintering process can supply heat for the sintering step, and the generated gas can be used as a pore-forming agent in the ceramsite sintering process. In addition, the sludge can also accelerate the sintering speed of the gangue, and the gangue can play a role of a catalyst to promote the sintering of the sludge, so that the two have obvious synergistic effect in a co-location. If coal gangue and coal-based sludge can be used as raw materials to prepare a ceramsite product with high added value in a synergistic way, the method is certainly an effective way for changing waste into valuable and recycling utilization of the two coal-based solid wastes, and has important significance.
However, the direct co-sintering of both gangue and sludge to produce ceramsite has the following disadvantages: (1) Organic matters in the sludge are released in a large amount in the sintering process, so that pore channels in the ceramsite are distributed in disorder and uncontrollable; (2) N, S and other hetero elements contained in sludge or gangue generate NO in high-temperature aerobic environment x 、SO x And toxic gases and the like, and causes secondary pollution to the atmospheric environment. (3) The energy utilization rate of the direct mixed sintering process is low, and the process economy is poor.
Aiming at the defect of direct co-sintering of mixed raw materials, the invention adds a co-pyrolysis step before co-sintering, and the two steps are mutually promoted. The co-pyrolysis can effectively release partial volatile matters in the raw materials to obtain co-product pyrolysis oil and combustible gas, and simultaneously, the unordered distribution of ceramsite pore channels caused by the large escape of high-temperature gas in the next sintering step is reduced. In addition, N, S and other miscellaneous elements in the raw materials are removed in the co-pyrolysis process, so that pollutants such as NOx and the like in the flue gas during aerobic sintering are avoided. And finally, introducing air in the high-temperature sintering step of the ceramsite, wherein residual organic matters and fixed carbon in the raw materials can burn and supply heat, and the generated high-temperature flue gas provides heat for the co-pyrolysis in the previous step. The mixed raw materials are subjected to flocculation dehydration, anaerobic co-pyrolysis at 500-600 ℃, pyrolysis carbon residue co-sintering at 1000-1150 ℃ and the like successively, heat is utilized in a gradient manner, and the heat utilization efficiency of the whole process is also obviously improved. Therefore, compared with the direct sintering ceramsite of the gangue and the coal-based sludge, the novel method for combining and co-treating the gangue and the coal-based sludge by the combination of 'co-pyrolysis and co-sintering' has remarkable advantages in the aspects of improving the product quality, eliminating pollutants, improving the energy utilization rate and increasing the economic competitiveness. The novel method is not reported in related patents and literature, and the innovative idea is shown in the following figure.
In summary, aiming at the current situation and the demand of treatment and utilization of the coal gangue and the coal-based sludge with extremely large quantity, the invention aims to produce the light ceramsite with wide application by using the coal gangue and the coal-based sludge as raw materials and cooperatively co-processing the two raw materials, and establishes a new method for recycling the coal gangue and the coal-based sludge. The invention is based on improving the product quality of the gangue and sludge mixed sintered ceramsite, reducing the process cost, and developing a novel process of combining the co-pyrolysis and co-sintering of the gangue and the sludge and coupling and utilizing the process energy step by step so as to achieve the aims of minimum external energy demand, energy optimal utilization and product quality optimal design. The invention promotes the healthy development of coal industry in western regions of China, and simultaneously provides a new economic and reliable way for producing light ceramsite with wide application.
The invention provides a novel method for the synergistic co-treatment and utilization of coal gangue and coal-based sludge, and the whole process mainly comprises the following three steps: (1) Mixing gangue with dehydrated sludge, drying and forming to obtain a ceramic ball cold blank; (2) performing co-pyrolysis poly-generation on the coal gangue and the sludge; (3) And (3) co-sintering the solid phase product after co-pyrolysis to prepare the light ceramsite.
According to different requirements of sludge sources, different water contents, different heat values and ceramsite characteristics, the ratio of coal gangue to sludge can be adjusted in a larger range, the sludge ratio is improved, the porosity of the ceramsite product is increased, but the strength is reduced. The formed Tao Qiuleng blank enters a dryer, the dryer uses 600-800 ℃ flue gas from a heating system of a co-pyrolysis reactor, the dryer can be a partition wall type dryer or a dryer with gas-solid direct contact, the water content after optimal drying is lower than 15%, and the cracking in the pyrolysis process can be caused by the excessive water content, mainly because of the excessive internal pressure caused by vaporization of a large amount of water vapor.
The dried cold blank enters a pyrolysis reactor, the temperature of the co-pyrolysis is 300-750 ℃, the average heating rate of the cold blank is 3-100 ℃/min, and the pyrolysis time is 0.5-2.5 hours. The condensation system behind the co-pyrolysis reactor separates gas, liquid and solid three-phase products, and the solid is the raw material fed into the sintering furnace and can be also called as semi-finished products. The main component of the liquid is mixed tar mainly comprising low-temperature coal tar, the gas is combustible gas, and the gas can be used as heating fuel gas of a ceramic sintering furnace. Based on experimental groping experience, co-pyrolysis can take two modes: the method is characterized by mild pyrolysis conditions, low damage rate and high strength; the method can also be used for fast pyrolysis, and is characterized in that the byproduct oil quantity is large, but the ceramsite strength is slightly low.
The whole heat utilization process is that fuel gas generated by co-pyrolysis condensation supplies heat for combustion of a sintering furnace, 800-1300 ℃ flue gas exhausted by the sintering furnace supplies heat for a co-pyrolysis reactor, and the flue gas enters a cold blank dryer to continue to dry water after supplying heat.
Drawings
FIG. 1 is a process flow of the present invention
Detailed Description
Example 1 dehydration of coal-based sludge by pressure filtrationAnd primarily drying, mixing with coal gangue according to the ratio of 1:3, forming and granulating to obtain Tao Qiuleng billets with the particle size of 30 mm. And (3) drying to obtain cold blanks with the water content of 12%, and feeding the cold blanks into a rotary kiln pyrolysis reactor, wherein the operation temperature of the pyrolysis reactor is 600 ℃, and the retention time is 30 minutes. The co-pyrolysis process yields were as follows: tar 12% (based on dry raw material yield, weight percent), pyrolysis gas 15% (based on dry raw material yield, weight percent). And (3) burning pyrolysis gas to supply heat for the ceramsite sintering step, and enabling the solid-phase semi-finished blank after pyrolysis to enter a sintering reactor to complete ceramsite sintering at 1200 ℃. The characteristic parameters of the obtained ceramsite product are as follows: cylinder pressure 3.5MPa, water absorption 12% and bulk density 700kg/m 3 The boiling loss is 0.09%, the mud content is 0.07% and the loss on ignition is 0.06%.
Example 2 the pharmaceutical sludge was subjected to press filtration, dehydration and preliminary drying, mixed with coal gangue in a ratio of 1:4, and formed and granulated to obtain Tao Qiuleng billets with a particle size of 30 mm. And drying to obtain cold blanks with the water content of 12%, and feeding the cold blanks into a moving bed pyrolysis reactor, wherein the operation temperature of the pyrolysis reactor is 450 ℃, and the retention time is 100 minutes. The co-pyrolysis process yields were as follows: tar 8% (based on dry raw material yield, weight percent), pyrolysis gas 12% (based on dry raw material yield, weight percent). And (3) burning pyrolysis gas to supply heat for the ceramsite sintering step, and enabling the solid-phase semi-finished blank after pyrolysis to enter a sintering reactor to complete ceramsite sintering at 1000 ℃. The characteristic parameters of the obtained ceramsite product are as follows: cylinder pressure 3MPa, water absorption 10% and bulk density 800kg/m 3 The boiling loss is 0.07%, the mud content is 0.09%, and the loss on ignition is 0.08%.
Example 3 municipal sludge is subjected to filter pressing dehydration and preliminary drying, is mixed with coal gangue according to a ratio of 1:6, and is formed and granulated to obtain Tao Qiuleng billets with a particle size of 30 mm. And (3) drying to obtain cold blanks with the water content of 12%, and feeding the cold blanks into a rotary kiln pyrolysis reactor, wherein the operation temperature of the pyrolysis reactor is 550 ℃, and the retention time is 60 minutes. The co-pyrolysis process yields were as follows: tar 16% (based on dry raw material yield, weight percent), pyrolysis gas 18% (based on dry raw material yield, weight percent). The pyrolysis gas burns to supply heat for the ceramsite sintering step, and the solid-phase semi-cooked blank after pyrolysis enters into the sinteringAnd (3) a reactor is combined, and the ceramsite sintering is completed at 1100 ℃. The characteristic parameters of the obtained ceramsite product are as follows: cylinder pressure 3.8MPa, water absorption 14% and bulk density 750kg/m 3 The boiling loss is 0.08%, the mud content is 0.09%, and the loss on ignition is 0.09%.
Example 4 the papermaking sludge was subjected to press filtration, dehydration and preliminary drying, mixed with coal gangue in a ratio of 1:5, and formed and granulated to obtain Tao Qiuleng billets with a particle size of 30 mm. And (3) drying to obtain cold blanks with the water content of 12%, and feeding the cold blanks into a rotary kiln pyrolysis reactor, wherein the operation temperature of the pyrolysis reactor is 650 ℃, and the residence time is 50 minutes. The co-pyrolysis process yields were as follows: tar 10% (based on dry raw material yield, weight percent), pyrolysis gas 16% (based on dry raw material yield, weight percent). And (3) burning pyrolysis gas to supply heat for the ceramsite sintering step, and enabling the solid-phase semi-finished blank after pyrolysis to enter a sintering reactor to complete ceramsite sintering at 900 ℃. The characteristic parameters of the obtained ceramsite product are as follows: cylinder pressure 4MPa, water absorption 9% and bulk density 750kg/m 3 The boiling loss is 0.05%, the mud content is 0.04%, and the loss on ignition is 0.07%.
Example 5 a Tao Qiuleng blank with a particle size of 30mm was obtained by press filtration, dehydration and preliminary drying of tannery sludge, mixing with coal gangue in a ratio of 1:3, and shaping and granulating. And (3) drying to obtain cold blanks with the water content of 12%, and feeding the cold blanks into a rotary kiln pyrolysis reactor, wherein the operation temperature of the pyrolysis reactor is 500 ℃, and the retention time is 40 minutes. The co-pyrolysis process yields were as follows: tar 10% (based on dry raw material yield, weight percent), pyrolysis gas 9% (based on dry raw material yield, weight percent). The pyrolysis gas burns to supply heat for the ceramsite sintering step, and the solid-phase semi-finished blank after pyrolysis enters a sintering reactor to complete ceramsite sintering at 1050 ℃. The characteristic parameters of the obtained ceramsite product are as follows: cylinder pressure 4.2MPa, water absorption 8% and bulk density 800kg/m 3 The boiling loss is 0.08%, the mud content is 0.06% and the loss on ignition is 0.07%.
Claims (9)
1. The method for preparing the ceramsite by the synergistic co-treatment of the gangue and the sludge is characterized by comprising the following steps of: the mixture of the dehydrated coal gangue and the sludge is subjected to molding granulation, drying and co-pyrolysis, and then enters a sintering reactor for sintering to obtain the ceramsite.
2. The method for preparing ceramsite by co-treatment of coal gangue and sludge according to claim 1, which is characterized by comprising the following steps: the sludge can be municipal sludge, coal-based sludge, papermaking sludge, pharmaceutical sludge, tanning sludge and other industrial sludge.
3. The method for preparing ceramsite by co-treatment of coal gangue and sludge according to claim 1, which is characterized by comprising the following steps: the temperature of the co-pyrolysis is 300-750 ℃, the average heating rate of the formed cold blank is 3-100 ℃/min, and the time is 0.5-2.5 hours.
4. The method for preparing ceramsite by co-treatment of coal gangue and sludge according to claim 1, which is characterized by comprising the following steps: the sintering temperature of the ceramsite is 800-1300 ℃.
5. The method for preparing ceramsite by co-treatment of coal gangue and sludge according to claim 1, which is characterized by comprising the following steps: the mixture ratio of the dehydrated coal gangue to the sludge is 2:1-8:1.
6. The method for preparing ceramsite by co-treatment of coal gangue and sludge according to claim 1, which is characterized by comprising the following steps: the reactor used for co-pyrolysis may be either a moving bed or a rotating kiln.
7. The method for preparing ceramsite by co-treatment of coal gangue and sludge according to claim 6, which is characterized by comprising the following steps: the heating medium of the co-pyrolysis reactor is the tail gas of the sintering reactor.
8. The method for preparing ceramsite by co-treatment of coal gangue and sludge according to claim 1, which is characterized by comprising the following steps: the dry heating medium is the gas after the heat supply of the co-pyrolysis hot gas.
9. The method for preparing ceramsite by co-treatment of coal gangue and sludge according to claim 1, which is characterized by comprising the following steps: and the combustible gas generated by co-pyrolysis is used as the heating fuel of the ceramsite sintering reactor.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875003A (en) * | 2012-11-05 | 2013-01-16 | 天津城市建设学院 | Integrated technology of thermal decomposing, dry distilling and gasifying sludge and preparing of ceramsite |
| CN103880472A (en) * | 2014-02-21 | 2014-06-25 | 周弼 | Sludge porous material and preparation method thereof |
| CN112880394A (en) * | 2021-01-27 | 2021-06-01 | 山东义科节能科技股份有限公司 | Kiln system and method for firing ceramsite containing heat value raw material and by-producing waste heat |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875003A (en) * | 2012-11-05 | 2013-01-16 | 天津城市建设学院 | Integrated technology of thermal decomposing, dry distilling and gasifying sludge and preparing of ceramsite |
| CN103880472A (en) * | 2014-02-21 | 2014-06-25 | 周弼 | Sludge porous material and preparation method thereof |
| CN112880394A (en) * | 2021-01-27 | 2021-06-01 | 山东义科节能科技股份有限公司 | Kiln system and method for firing ceramsite containing heat value raw material and by-producing waste heat |
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