CN107200488B - Method for producing fluoroaluminate cement by using carbon waste of aluminum electrolytic cell in dry-process rotary kiln plant - Google Patents

Method for producing fluoroaluminate cement by using carbon waste of aluminum electrolytic cell in dry-process rotary kiln plant Download PDF

Info

Publication number
CN107200488B
CN107200488B CN201710601021.2A CN201710601021A CN107200488B CN 107200488 B CN107200488 B CN 107200488B CN 201710601021 A CN201710601021 A CN 201710601021A CN 107200488 B CN107200488 B CN 107200488B
Authority
CN
China
Prior art keywords
waste
calcium
fluoroaluminate
raw material
clinker
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710601021.2A
Other languages
Chinese (zh)
Other versions
CN107200488A (en
Inventor
尹小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changsha Zichen Technology Development Co Ltd
Original Assignee
Changsha Zichen Technology Development Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changsha Zichen Technology Development Co Ltd filed Critical Changsha Zichen Technology Development Co Ltd
Priority to CN201710601021.2A priority Critical patent/CN107200488B/en
Publication of CN107200488A publication Critical patent/CN107200488A/en
Application granted granted Critical
Publication of CN107200488B publication Critical patent/CN107200488B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/345—Hydraulic cements not provided for in one of the groups C04B7/02 - C04B7/34
    • C04B7/3453—Belite cements, e.g. self-disintegrating cements based on dicalciumsilicate
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The method for producing the fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant comprises the following steps: (1) and (3) crack granulation: crushing, and atomizing and spraying a cyanide detoxicant solution in the crushing process to obtain a granulated detoxicant material; (2) dealkalization and activation: adding strong oxidation activator and lime, adding water, stirring or rolling, filtering or filtering and washing to obtain fluorine-containing dealkalized activated carbon slag; (3) adding a catalytic combustion improver and fire coal, mixing and grinding to obtain modified fuel powder; (4) preparing a calcium fluoroaluminate or calcium fluoroaluminate-calcium sulfoaluminate clinker: mixing waste bauxite, calcium or waste gypsum raw materials, grinding, calcining with fuel powder, and quenching to obtain clinker; (5) preparing fluoroaluminate cement: controlling the aluminum/sulfur ratio in the cement, adding waste gypsum or adding slag and/or fly ash, retarder and grinding to obtain the cement. The method is safe and simple, has large treatment capacity, and has low energy consumption and cost.

Description

Method for producing fluoroaluminate cement by using carbon waste of aluminum electrolytic cell in dry-process rotary kiln plant
Technical Field
The invention relates to a method for producing fluoroaluminate cement, in particular to a method for producing fluoroaluminate cement by using carbon waste materials of aluminum electrolytic cells in a dry-process rotary kiln plant.
Background
At present, the electrolytic aluminum yield in our country and the world is rapidly developed. According to statistics, the capacity of the aluminum smelting enterprises for electrolyzing aluminum in China is 4369.8 ten thousand tons and 3673.9 ten thousand tons by 2016 (12 months) in 2016. Along with the increase of the yield of electrolytic aluminum, the yield of solid wastes generated in the electrolytic process, such as waste cathode carbon blocks, waste anode carbon granules, waste refractory bricks, waste heat-insulating bricks and waste heat-insulating furnace slag, is also rapidly increased, wherein the yield of waste cathodes generated in the electrolytic aluminum industry of China per year is up to 25 ten thousand tons, in recent years, the accumulated stocking amount of more than 400 ten thousand tons does not have a proper site for landfill, and the actual quantity of the waste cathode carbon blocks stockpiled all over the world is up to ten million tons.
The aluminum electrolysis cell carbon waste comprises waste cathode carbon blocks, waste anode carbon particles and the like generated in the aluminum electrolysis process, and mainly comprises the waste cathode carbon blocks. The main component of the waste cathode carbon block of the aluminum electrolytic cell is C and Na3AlF6、CaF2、NaF、AlF3、α-Al2O3And the like, wherein the carbon content is 50-70%, the electrolyte fluoride is 30-50%, and the cyanide is about 0.2%. The main component of anode carbon particles (also called anode carbon slag) which do not participate in electrolysis and absorb electrolyte in the aluminum electrolysis process is Na3AlF6Predominantly sodium aluminum fluorideCompound, alpha-Al2O3And C, the balance being electrolyte fluoride, wherein the carbon content is 40-60%.
The waste cathode carbon block of electrolytic aluminium is made up by using calcined anthracite, metallurgical coke and graphite as aggregate and coal pitch as binder through the processes of forming and roasting, and is used for carbon lining of aluminium-containing electrolytic cell. The electrolysis temperature of a modern large-scale aluminum electrolysis prebaking cell is 950-970 ℃, about 50kg of electrolytes such as cryolite, aluminum fluoride and magnesium fluoride are consumed for 1 ton of aluminum production, a cathode carbon block in the aluminum electrolysis cell is damaged after being used for a certain time due to molten salt reaction and chemical reaction caused by thermal action, chemical action, mechanical erosion action, electrical action, sodium and electrolyte permeation, general overhaul is needed after running for 4-7 years, the removed cathode carbon block mainly comprises a waste cathode carbon block, a waste refractory material, a waste heat insulation material and the like, and a certain amount of anode carbon particles are generated in the electrolysis process.
For the treatment technology of waste anode carbon particles with small quantity, the current research mainly focuses on recovering carbon and electrolyte by adopting a flotation process, grinding the waste anode carbon particles to a certain particle size, adding water for size mixing, and then adding a collecting agent to fully separate the carbon from the electrolyte, thereby obtaining two products mainly comprising the electrolyte and the carbon. The electrolyte can be returned to the aluminum cell again, and the carbon powder can be used as the raw material for preparing anode paste by using the aluminum electrolysis self-baking anode, but the treatment cost is high and the secondary pollution is large.
For the waste cathode carbon blocks of the aluminum electrolytic cell, the current technical methods for treating the waste cathode carbon blocks at home and abroad can be more than dozens of methods, and can be summarized into a wet method, a high-temperature hydrothermal method, an ultrahigh-temperature separation method, a combustion separation method, a fuel method, a safe landfill method and the like.
(1) And (2) wet method: the method is the main research direction of the current aluminum cell lining, and the basic procedures comprise grinding, water leaching/alkali leaching/acid washing, flotation, separation, drying and the like. Foreign representatives are the hydration of used cathode carbon blocks (electrolytes separated to give coarse carbon particles and fine particles) by m.m. williams, and the leaching of electrolytes in austria holfin aluminum plants and rustalum aluminum plants in the united states with alkaline liquors (leachate is used for the synthesis of cryolite, and carbon is used as a fuel for high temperature furnace matching). China aluminum industry, Inc., Beijing mining and metallurgy research institute, Zhongnan university, etc. also have carried out a great deal of research and practice, such as Luhuimin, etc. people use the flotation method to recover carbon and electrolyte, crush and classify the waste cathode carbon block to obtain powder with certain granularity, add water and mix pulp, then add collecting agent to realize the maximum separation of carbon and electrolyte, thus obtain two products mainly based on electrolyte and carbon. The electrolyte can be returned to the aluminum electrolytic cell again, and the graphitized carbon powder can be returned to the cathode production system. However, the carbon powder obtained by the existing wet separation method has low value, low resource utilization efficiency, high power consumption for grinding and other treatments, high treatment cost and serious secondary pollution.
(2) The high-temperature hydrothermal separation method comprises the following steps: most representative are j.e.dentschman and j.s.lobos, etc., which treat the waste cathode carbon blocks by a hot water hydrolysis method of 1200 ℃ or higher to react fluoride with water vapor to produce a hydrogen fluoride solution with a concentration of 25%, produce aluminum fluoride by a synthesis method, and collect fluoride ions in the solution by gypsum. However, the method has the disadvantages of large investment, high energy consumption, high treatment cost and difficult secondary pollution treatment.
(3) The ultra-high temperature separation method comprises the following steps: the 'AUMSET' process developed by Alcoa company is a representative foreign technology, lime and other fusing agents are added into crushed waste tank lining carbon blocks, the mixture is subjected to heat treatment in an AUS-MELT furnace at 1300 ℃, the lime and the like react with electrolyte in the waste cathode carbon blocks to obtain calcium fluoride, sodium fluoride and aluminum fluoride, HF gas in high-temperature flue gas is recovered to generate aluminum fluoride, the fluorine is solidified for reuse, the final product is molten slag, and the recovered carbon is reused for manufacturing cathode materials. The process is already applied industrially, the annual treatment of the waste tank lining can reach 12000t, but the investment is large, the treatment energy consumption is high, and the treatment cost is too high. For example, CN105642649A discloses a high-temperature treatment method for waste cathode of electrolytic aluminum, which comprises crushing carbon blocks of the waste cathode of electrolytic aluminum to 3-15 mm, then roasting in a high-temperature vacuum electric furnace at 2600-2800 ℃ to volatilize fluoride therein and decompose cyanide therein to nitride, absorbing high-temperature flue gas by water mist absorption, and then filtering and drying to obtain recyclable fluoride, wherein the cathode carbon material after the high-temperature roasting is cooled to obtain carbon material with fixed carbon content of 97%. However, the method has the following problems obviously: firstly, generating cyanide-containing toxic dust and toxic gas in the crushing and screening process of the waste cathode carbon of the electrolytic aluminum; secondly, the actual power consumption is very high when the electric heating is carried out to 2600-2800 ℃, the power consumption for maintaining vacuum suction is higher, and the requirement and the manufacturing cost of equipment are also very high; thirdly, the requirement of fluoride gas volatilized at 2600-2800 ℃ on equipment is too high by adopting water mist absorption, and the 1200 ℃ water vapor can directly convert fluorides such as calcium fluoride and the like into highly toxic and highly corrosive hydrogen fluoride; fourthly, serious secondary pollution is easy to generate, the recycled carbon material still contains 3 percent or more of fluoride, and the recycling can shorten the overhaul period and is not cost-effective. CN106269787A discloses a high-temperature continuous treatment method for disposing waste cathode of electrolytic aluminum, which teaches that a waste cathode carbon block of electrolytic aluminum is crushed to particles with a size not larger than 3mm, the particles are kneaded with asphalt and the like to prepare mixture particles with a size of 3-100 mm, then the mixture particles are placed in an ultrahigh-temperature vacuum electric furnace, the mixture particles are continuously roasted in the ultrahigh-temperature vacuum electric furnace at a temperature not lower than 2000 ℃ (2300-2600 ℃) to obtain high-temperature electric forging smoke and waste cathode carbon particles of electrolytic aluminum, the high-temperature electric forging smoke is subjected to secondary combustion to completely combust carbon powder, carbon dust and cryolite in volatile matter smoke, cyanide in the volatile matter smoke is decomposed into nitride, and after cooling, dust removal, desulfurization and denitration, recycled fluoride and carbon material with a fixed carbon content of 95% are obtained. However, the method has the following problems obviously: firstly, generating cyanide-containing toxic dust and toxic gas in the crushing and screening process of the waste cathode carbon of the electrolytic aluminum; secondly, the actual power consumption is very high when the electric heating is carried out to 2000-2600 ℃, the power consumption for maintaining vacuum suction is higher, and the requirement and the manufacturing cost of equipment are also very high; thirdly, the flue gas after secondary combustion has high purification investment and is easy to generate serious secondary pollution; fourthly, carbon calcined by an electric furnace at 2000-2600 ℃ still contains a large amount of fluoride, and the recycling of fluorine-containing carbon materials is not economical due to the fact that the boiling point of calcium fluoride is as high as 2497 ℃.
(3) The combustion separation method comprises the following steps: the method adopts a professional incinerator and fluidized bed furnace process and the like, and the electrolytic aluminum waste cathode carbon is different from fire coal, although the calorific value is generally as high as 4000-5500 kcal/kg, the activation energy required by oxidation reaction is high, and the oxidation combustion can be effectively carried out only by reaching 1500 ℃, so that the combustion method has the problems of complicated separation process method, long heating time required by burnout, large energy consumption, difficulty in effectively recovering fluoride in the separation process, and great difficulty in treating secondary pollution problem.
(4) The fuel method comprises the following steps: as the main component of the waste cathode carbon block of the electrolytic aluminum is carbon, the theoretical calorific value of complete combustion generally reaches more than 4000kcal/kg, and the theoretical calorific value as high as 5500kcal/kg is equivalent to the calorific value of common anthracite, a large number of technical workers at home and abroad make continuous efforts, and the effect is extremely unsatisfactory so far. The domestic fuel method is the identification result of 'recycling of waste cathode carbon blocks of aluminum electrolytic cells' of Shandong aluminum factories organized in 11, 16 th 1988 by the general company of nonferrous metal industry in China. The specific method comprises the following steps: in alumina production in Shandong aluminum factories, waste cathode carbon blocks are ground and used as a desulfurizer to replace part of anthracite to be added into an alumina clinker kiln to produce alumina sinter cakes. The fluoride salt contained in the red mud is converted into insoluble calcium fluoride in the clinker firing process, and the insoluble calcium fluoride enters the red mud, and the red mud is used for cement production ingredients to replace fluorite as a mineralizer in the cement preparation process. However, the method has high grinding energy consumption and increases the discharge amount of harmful gases in the flue gas. In order to further solve the problem of fuel utilization of the waste cathode carbon blocks, the research institute of Yangtze Jubin, a Shandong division company, Inc. of China aluminum industry, carries out deep research practice on a cement production line of an Shandong aluminum plant, and the like, uses the waste cathode carbon blocks with the heat value of 21MJ/kg (5024 kcal/kg) to be applied to an industrial test of the cement production line, and specifically, the waste cathode carbon blocks are firstly crushed, and are matched into a coal mill to be ground together when grinding coal powder according to the maximum proportion usage amount (which is less than about 3 percent of the coal usage amount) of 5kg of the waste cathode carbon blocks per ton of clinker, and the test conclusion is that the 5kg of the waste cathode carbon blocks per ton of clinker has no visible influence on the quality (the application research of the waste cathode carbon blocks in the cement production, such as Yangtze Bin, light metal, No. 2, No. 2008, P59-64.). The method is characterized in that under the conditions of high reaction temperature inside a cement kiln, long retention time of carbon blocks in a flow and the like, the Poplar and the like decompose and replace harmful substances in the waste cathode carbon blocks in a high-temperature environment, finally solidify the harmful substances in cement clinker, and try to reduce coal consumption by using carbon in the waste cathode carbon blocks as fuel. However, it still has problems of safety, addition amount and influence on production, and after all, the waste cathode carbon is not coal-fired, and the carbon in the waste cathode carbon block is extremely difficult to burn. However, the real defect is not the problems of corrosion of refractory materials and over-standard fluorine in smoke caused by fluoride, because the production of fluoroaluminate cement can also ensure the safety of the refractory materials and the over-standard fluorine in the smoke, after all, a normal cement kiln preheater system objectively has a preheater for realizing the exchange and collection of five-grade alkaline high-concentration powder; the method is not a problem of extremely high alkali content, because the coal consumption per ton of clinker is only 0.15-0.18 t generally, the electrolytes in a small amount of cathode carbon blocks are mainly aluminum fluoride, sodium fluoroaluminate and magnesium fluoroaluminate, the total alkali content in the sodium fluoroaluminate and the sodium fluoride is limited when the clinker is used for a long time, and the influence on the later strength of cement is limited generally. Therefore, the true reason why Shandong aluminum factories have not been able to use cathode carbon as a substitute coal for normal use is: the grinding efficiency of the coal mill is influenced, and the overall combustion performance of the coal powder is seriously reduced by the low-activity graphite carbon, the normal combustion efficiency of the coal powder is seriously influenced, carbon which cannot be effectively combusted in time to release heat falls into clinker or is wrapped into powder to generate strong reduction, the working condition of a kiln system is influenced, and the quality of the clinker is influenced. Obviously, the prior art has not been able to use the aluminum electrolysis spent cathode carbon block as an effective alternative fuel.
(5) A safe landfill method: because the existing treatment method has the problems of high energy consumption, high cost, secondary pollution and the like, the problem of environmental pollution of the waste cathode carbon blocks of the electrolytic aluminum is not effectively solved all the time, so that most of the waste cathode carbon blocks of the aluminum electrolytic cell are still abandoned, and the high-cost safe landfill method is mainly adopted at present. The method for treating the electrolytic aluminum solid waste by adopting the currently and generally adopted landfill method can cause great harm to the environment, continuous pollution can be generated even if the electrolytic aluminum solid waste is completely treated by harmless landfill according to dangerous waste, and a large amount of resources are wasted.
In addition, since the electrolytic aluminum solid waste contains a large amount of soluble fluorides and a small amount of cyanides (mainly sodium cyanide and sodium ferricyanide), it is a hazardous waste and needs to be properly treated. Under the condition of the prior art, the solid wastes are treated by the landfill method and the stockpiling method which are commonly adopted by electrolytic aluminum plants, and the contained soluble fluoride and cyanide can be transferred or volatilized into the atmosphere under the actions of wind blowing, solarization and rain, or can be mixed into rivers along with rainwater and permeate into underground polluted soil and underground water, so that great damage is generated to animals, plants and human bodies, the ecological environment is damaged, the agricultural ecological balance is influenced, the yield of crops is reduced, and the damage is long-term. For the treatment of cyanide in the waste cathode carbon block, the treatment technology mainly comprises the technologies of weak acid dissolution and conversion of polysulfide into thiocyanate and metal sulfide, the technologies of manganese ion and ultraviolet light catalytic oxidation, ozone and sodium hypochlorite combined oxidation, high-temperature chlorination treatment, high-temperature oxidation and biochemical treatment of cyanide. However, the existing cyanide treatment technical methods are complicated, high in cost and have secondary pollution. CN101811695A discloses a method for recovering graphite from waste cathode carbon blocks of electrolytic aluminum, which comprises the steps of grinding, water leaching, floatation, acid leaching and the like to remove fluoride, separating and recovering carbon materials in the carbon materials, and drying to obtain fine graphite powder. However, the method has the disadvantages of complicated process, large secondary pollution, high energy consumption and high impurity content of the recovered fine graphite powder.
In summary, as a common problem in the electrolytic aluminum industry, it is necessary to break through the technical problem of harmless industrialization of electrolytic aluminum solid waste as soon as possible. How to utilize the characteristics of the electrolytic aluminum solid waste material to implement resource utilization, especially safe, low-energy-consumption and low-cost resource utilization, is a technical method problem worthy of research and solution.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide the method for producing the fluoroaluminate cement by using the carbon waste materials of the aluminum electrolytic cell in the dry-process rotary kiln plant, which is safe, simple, large in treatment capacity, low in energy consumption, low in cost, free of secondary pollution and suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for producing fluoroaluminate cement by using carbon waste materials of aluminum electrolytic cells in a dry-process rotary kiln plant comprises the following steps:
(1) and (3) crack granulation: crushing the carbon waste of the aluminum electrolytic cell into a granular material with the particle size of less than 10mm by adopting an extrusion or impact crushing mode, and atomizing and spraying a cyanide detoxicant solution in the crushing process to obtain a granulated detoxicant material;
(2) dealkalization and activation: placing the granulated detoxified material obtained in the step (1) into a leaching tank/tank with a stirring or rolling device, adding a strong oxidation activator and lime, adding water, stirring or rolling for oxidizing dealkalization, filtering or filtering and washing with water to obtain fluorocarbon slag;
(3) preparing modified fuel powder: adding a catalytic combustion improver or coal into the fluorocarbon slag obtained in the step (2), mixing and grinding until the sieved residue of 80 mu m is less than 8 percent to obtain modified fuel powder;
(4) preparing a calcium fluoroaluminate or calcium fluoroaluminate-calcium sulfoaluminate clinker: taking the modified fuel powder obtained in the step (3) as fuel powder for producing calcium fluoroaluminate clinker or calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry-process rotary kiln; waste bauxite and calcium raw materials are mixed and ground until the screen residue of 80 mu m is less than 25 percent, and then the mixture is used as raw material powder for producing calcium fluoroaluminate clinker by a dry-process rotary kiln;
or taking the modified fuel powder obtained in the step (3) as fuel powder for producing calcium fluoroaluminate clinker or calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry-process rotary kiln; waste bauxite, calcium raw materials and waste gypsum are mixed and ground until the screen residue of 80 mu m is less than 25 percent, and then the mixture is used as raw material powder for producing calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry rotary kiln;
respectively sending the raw material powder and the fuel powder into a dry-process rotary kiln cement production line system simultaneously, wherein the using amount of the fuel powder is such that the firing temperature of the raw material is 1200-1400 ℃, and calcining and quenching the raw material by a grate cooler at the temperature to obtain belite-calcium fluoroaluminate clinker or belite-calcium fluoroaluminate-calcium sulfoaluminate clinker;
(5) preparing fluoroaluminate cement: and (3) controlling the aluminum/sulfur ratio in the cement, adding waste gypsum or furnace slag and/or fly ash and a retarder into the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker obtained in the step (4), and mixing and grinding the mixture to powder with 80 mu m and less than 12 percent of screen residue to obtain the double-fast hard fluoroaluminate cement or the double-fast hard fluoroaluminate-sulfoaluminate cement.
In the technical scheme, the modified fuel powder and the fire coal are used as fuel components, and the waste gypsum, the waste alumina and the calcium raw materials are used as raw material components. The raw material components and the fuel components are simultaneously used as raw materials and fuels for producing the belite-calcium fluoroaluminate clinker by a dry cement production line, raw material powder is fed into a kiln system for calcination, the fuel components substitute for heat required by the calcination of a coal combustion supply kiln system, and inorganic mineral components in the raw material components and the fuel components are automatically mixed and homogenized in the moving process from a decomposing furnace of the kiln system to a rotary kiln and enter the rotary kiln to be calcined into a burning zone. The belite-calcium fluoroaluminate-calcium sulfoaluminate clinker containing part of calcium sulfoaluminate minerals is prepared by adding waste gypsum and calcining in an oxidizing atmosphere.
Preferably, in the step (1), the aluminum electrolysis cell carbon waste is waste cathode carbon blocks and/or waste anode carbon particles, wherein the aluminum electrolysis cell carbon waste comprises 18-72% of C, 5-25% of F, 5-20% of Na, 2-10% of Al, 0.2-2.0% of Fe, 1-10% of Si, 0.2-2.0% of Ca and 0.2-2.0% of Mg, the total weight of the elements is less than or equal to 100% by mass, and the heat value is 3000-6000 kcal/kg. By adopting an extrusion/impact crushing mode, the carbon material and other inorganic components in the carbon waste material of the aluminum electrolytic cell can generate obvious interfaces to crack.
Preferably, in the step (1), the amount of the cyanide detoxifier is 1-8% (more preferably 2-6%) of the mass of the carbon waste of the aluminum electrolysis cell.
Preferably, in the step (1), the cyanide detoxifier is capable of decomposing cyanide into carbon dioxide and nitrogen gas or converting cyanide into thiocyanide with high efficiency to eliminate substances with high toxicity, and is one or more of commercially available products or raw materials, namely ferrate detoxifier, dichromate detoxifier, dichromic anhydride detoxifier, thiosulfate detoxifier, perchlorate detoxifier, hydroxide detoxifier, hypochlorite detoxifier or chlorine dioxide; the ferrate detoxifier is one or more of potassium ferrate, lithium ferrate or sodium ferrate, the dichromate detoxifier is one or more of potassium dichromate, sodium dichromate or cobalt dichromate, the thiosulfate detoxifier is sodium thiosulfate and/or potassium thiosulfate, the perchlorate is lithium perchlorate and/or cobalt perchlorate, the hydroxide is one or more of cobalt hydroxide, iron hydroxide or potassium hydroxide, and the hypochlorite is sodium hypochlorite and/or calcium hypochlorite. By atomizing and spraying the cyanide detoxicant solution, the cyanide on the decomposed particles can be oxidized into carbon dioxide and nitrogen to remove toxicity while dust suppression is carried out, and the safety of the waste recycling process is ensured.
Still more preferably, in the step (1), the cyanide detoxicant solution is a ZC-XJ1 type detoxicant solution (i.e., a saturated solution prepared by mixing a ferrate detoxicant and a hypochlorite detoxicant in a mass ratio of 1: 1), a ZC-XJ3 type detoxicant solution (i.e., a saturated solution prepared by mixing a dichromate detoxicant and a hypochlorite detoxicant in a mass ratio of 1: 1), all available from environmental energy science and technology development Co., Ltd, of vain, Hunan province; or a saturated solution prepared by dissolving lithium ferrate, cobalt perchlorate and sodium hypochlorite in water according to the mass ratio of 2:1: 2.
Preferably, in the step (2), the amounts of the strong oxidation activator and the lime are respectively 1-8% (more preferably 2-6%) and 5-40% (more preferably 15-39%) of the mass of the carbon waste of the aluminum electrolysis cell, and the amount of the added water is 1-10 times (more preferably 4-8 times) of the mass of the carbon waste of the aluminum electrolysis cell.
Preferably, in the step (2), the strong oxidation activator is a substance which can destroy/activate the reticular carbon structure of graphite, activate carbon and efficiently oxidize and decompose cyanide, and is one or more of a commercially available product or raw material chlorosulfonic acid strong oxidation activator, dichromate strong oxidation activator, dichromic anhydride strong oxidation activator, ferrate strong oxidation activator, perchlorate strong oxidation activator or chlorate strong oxidation activator; the dichromate strong oxidation activator is one or more of potassium dichromate, sodium dichromate or cobalt dichromate, the ferrate strong oxidation activator is one or more of potassium ferrate, sodium ferrate or lithium ferrate, the perchlorate strong oxidation activator is cobalt perchlorate, and the like, and the chlorate strong oxidation activator is cobalt chlorate, and the like. In the strong oxidizing solution, calcium hydroxide reacts with sodium fluoride and sodium fluoroaluminate containing alkali to be converted into calcium fluoride, sodium hydroxide and the like for dealkalization, and simultaneously, the graphite carbon material in the solution is activated by strong oxidation, and cyanide is decomposed by oxidation to detoxify. Recovering the alkali-containing filtrate obtained by filtering to prepare concentrated alkali, and recovering the water washing liquid obtained by filtering and washing for dealkalization and leaching. And (3) the fluorocarbon slag obtained in the step (2) is dealkalized activated carbon slag containing calcium fluoride.
Still more preferably, in the step (2), the strong oxidation activator is ZC-JO7 type strong oxidation activator (i.e. a mixture of dichromate strong oxidation activator and hypochlorite strong oxidation activator in a mass ratio of 2: 1) available from yinji environmental energy science and technology development ltd; or prepared by mixing potassium ferrate, potassium dichromate and cobalt chlorate in a mass ratio of 2:1: 2.
Preferably, in the step (3), the amounts of the catalytic combustion improver and the fire coal are respectively 0.5-5% (more preferably 2.0-4.5%) and 0-50% (more preferably 25-45%) of the mass of the fluorocarbon slag. When the mixture of the catalytic combustion improver and the fire coal is added, the blending amount of the fire coal is determined according to the content of fluorine in the fluorocarbon slag, the heat value of the carbon component and the heat quantity required by the calcination of a kiln system, if the total fluorine content in the fluorocarbon slag is high, the proportion of chemical components exceeding the generated calcium fluoroaluminate is more, and the heat value of the carbon component is lower, the proportion of the blended fire coal is higher.
Preferably, in the step (3), the catalytic combustion improver is a substance capable of effectively promoting the oxidation combustion reaction of the carbon material at a high temperature of more than 600 ℃, and is one or more of commercially available raw materials or products such as ammonium dichromate, metavanadate, lithium perchlorate or nitrate, or a compound thereof. The metavanadate is ammonium metavanadate and the like, and the nitrate is cerium nitrate and/or strontium nitrate and the like.
Still more preferably, in the step (3), the catalytic combustion improver is a ZC-27 type catalytic combustion improver (i.e. a compound of metavanadate and nitrate in a mass ratio of 1: 1), and a ZC-29 type catalytic combustion improver (i.e. a compound of ammonium dichromate and nitrate in a mass ratio of 1: 1), which are all purchased from Emilian who is not concerned with environmental energy science and technology development Limited in Hunan province; or the composite material is prepared by mixing ammonium dichromate, ammonium metavanadate, lithium perchlorate, cerium nitrate and strontium nitrate according to the mass ratio of 4:1:2:3: 1.
Preferably, in the step (4), when the waste alumina and the calcium raw material are used for proportioning, the mass ratio of the waste alumina to the calcium raw material is 30-65: 70-35 (more preferably 35-60: 65-40).
Preferably, in the step (4), when the waste alumina, the calcium raw material and the waste gypsum are used for mixing, the mass ratio of the waste alumina to the calcium raw material to the waste gypsum is 20-60: 60-32: 3-25 (more preferably 40-55: 50-40: 5-10).
Preferably, in the step (4), the waste bauxite is one or more of a waste bauxite raw material, a waste high-alumina brick, high-alumina fly ash or high-alumina coal cinder and the like in the production of alumina.
Preferably, in the step (4), the calcium raw material is one or more of carbide slag, waste lime or limestone.
Preferably, in the step (4), the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum.
Preferably, in the step (4), the calcination time is 15-60 min (more preferably 20-40 min).
Preferably, steps (3), (4) are replaced by:
(3) preparing aged fluorocarbon slag: adding a catalytic combustion improver which is 0.5-5% (more preferably 1-3%) of the fluorocarbon slag obtained in the step (2) in mass, uniformly mixing, and aging for 0.5-72 h (more preferably 5-15 h) to obtain aged fluorocarbon slag;
(4) preparing a calcium fluoroaluminate clinker or a calcium fluoroaluminate-calcium sulfoaluminate clinker: and (3) mixing the aged fluorocarbon slag obtained in the step (3), waste alumina, a calcium raw material and waste gypsum according to a mass ratio of 10-25: 20-55: 60-30: 0-25, grinding the mixture until the sieved residue of 80 mu m is less than 25% to obtain raw material powder for producing the calcium fluoroaluminate clinker or the calcium fluoroaluminate-calcium sulfoaluminate clinker by using a dry rotary kiln, feeding the raw material powder into a dry rotary kiln system, calcining for 15-60 min (more preferably 20-40 min) at the temperature of 1200-1400 ℃ in an oxidizing atmosphere, quenching a grate cooler to obtain the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker.
In the technical scheme, the catalytic combustion improver is one or more of ammonium dichromate, metavanadate, lithium perchlorate or nitrate and the like, or a compound thereof and the like; the metavanadate is ammonium metavanadate and the like, and the nitrate is cerium nitrate and/or strontium nitrate and the like. The waste bauxite is one or more of a waste bauxite raw material, a waste high-alumina brick, high-alumina fly ash or high-alumina coal cinder and the like in the production of alumina; the calcareous raw material is one or more of carbide slag, waste lime or limestone and the like; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum and the like; the oxidizing atmosphere is an air atmosphere or an oxygen atmosphere.
In the step (3), when the carbon waste of the aluminum electrolytic cell mainly contains anode carbon particles, the inorganic matter content of the carbon waste is high, and the carbon waste is low, namely the carbon waste is not suitable to be used as a modified fuel, a catalytic combustion improver is added and aged to prevent carbon from generating strong reduction in a raw material, and the carbon waste can be directly used as a calcium fluoride raw material and prepared into raw material powder together with waste alumina and calcium raw materials for producing calcium fluoroaluminate clinker.
Preferably, in the step (5), the aluminum/sulfur ratio is 1.1 to 2.2 (more preferably 1.3 to 2.0).
Preferably, in the step (5), the amounts of the waste gypsum, the slag and/or the fly ash and the retarder are respectively 8 to 60% (more preferably 30 to 50%), 0 to 50% (more preferably 10 to 30%), and 0 to 3% (more preferably 0.2 to 1.0%) of the mass of the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker.
Preferably, in the step (5), the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum.
Preferably, in the step (5), the retarder is one or more of citric acid, citrate or tartaric acid, or a compound of citric acid and a water reducing agent.
The lime in the method is hydrated lime and/or quicklime.
The technical principle of the invention is as follows: dealkalize the carbon waste of the aluminum electrolytic cell, take fluorine in the waste as a calcium fluoride raw material for producing the calcium fluoroaluminate clinker, and activate or catalytically activate carbon in the waste as a main fuel for producing the calcium fluoroaluminate clinker, wherein the method is used for producing the calcium fluoroaluminate clinker as follows.
(1) Aiming at the physical and mechanical characteristics of the waste cathode carbon block of the electrolytic aluminum, the waste cathode carbon block has the characteristics of high hardness, small friction coefficient, difficult crushing and extremely difficult grinding, and the carbon material and other components in the waste cathode material of the aluminum electrolytic cell have obvious interfaces, the waste cathode carbon block is crushed by adopting a high-efficiency and energy-saving extrusion/impact type crushing system, and according to the characteristic that the toxic substances contained in the waste cathode carbon block are sodium cyanide and sodium ferricyanide, by adopting the efficient cyanide detoxicant in the crushing process, the crushing energy consumption is saved, the dealkalization in the subsequent application process as fuel and the grinding energy consumption is reduced, and the waste cathode carbon block is crushed into irregular granular materials containing a large number of cracks, so that the adsorption and deep penetration of the cyanide detoxicant are facilitated, so as to be conveniently and efficiently oxidized and decomposed into carbon dioxide and nitrogen to remove toxicity, and the safety of the waste utilization process is ensured;
(2) aiming at the characteristics that main minerals of the aluminum electrolytic cell carbon waste are graphitized carbon and fluoride, main chemical components are carbon, fluorine, alkali, aluminum and the like, and the alkali content is high, the aluminum electrolytic cell carbon waste is placed in a strong oxidizing solution to be subjected to lime causticization dealkalization treatment, the fluoride is converted into calcium fluoride, and strong oxidation is carried out to activate graphite structure carbon to be used as a main raw combustion material for producing calcium fluoroaluminate;
(3) aiming at the process and equipment characteristics of the currently and generally adopted dry-process rotary kiln cement production line, the raw materials for producing the belite-calcium fluoroaluminate clinker are creatively divided into a fuel powder component and a raw material powder component, and are simultaneously applied to the dry-process cement production, so that the economic, efficient and energy-saving production effect is finally achieved;
(4) because the electrolytic aluminum waste cathode carbon block is a graphitized or graphite carbon material, the carbon structure is stable and extremely difficult to combust, and can be effectively oxidized only at 1500 ℃, the reticular carbon structure capable of destroying or activating graphite is adopted, and a strong oxidation activator capable of effectively promoting carbon oxidation reaction is adopted to modify the carbon structure, so that the activation energy of the carbon oxidation combustion reaction in the electrolytic aluminum waste cathode carbon block is greatly reduced, and dynamic heterogeneous catalytic oxidation combustion is realized, so that the energy for calcining can be provided instead of fire coal.
The method has the following beneficial effects:
(1) the double quick hardening cement obtained by the method has good economical efficiency and excellent performance, the 4h pressure resistance reaches 34.7MPa, the fracture resistance reaches 5.4MPa, the 1d pressure resistance reaches 44.8MPa, the fracture resistance reaches 5.7MPa, the 28d pressure resistance reaches 57.8MPa, the fracture resistance reaches 7.2MPa, the 180d pressure resistance reaches 71.8MPa, and the fracture resistance reaches 9.8 MPa;
(2) the method can utilize a great amount of aluminum-silicon-calcium-containing wastes, such as waste alumina and industrial waste gypsum, as resources while utilizing the carbon waste of the aluminum electrolytic cell as the raw combustion material, and is beneficial to implementing circular economy and no waste discharge;
(3) the method can utilize the mature dry-process rotary kiln cement production process and equipment, is safe and simple, has large treatment capacity, low energy consumption and cost, has no secondary pollution, and is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
The starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.
Example 1
The carbon waste of the aluminum electrolytic cell used in the embodiment of the invention is taken from bulk waste cathode carbon waste stored in a certain aluminum factory, and the main chemical components of the carbon waste are as follows: c64.57%, F9.13%, Na 10.45%, Al 2.42%, Fe 0.68%, Si2.33%, Ca1.06%, Mg 0.57%, and a calorific value of 5071 kcal/kg; the cyanide detoxifying agent solution used in this example is ZC-XJ1 type detoxifying agent solution (i.e. saturated solution prepared by ferrate detoxifying agent and hypochlorite detoxifying agent in a mass ratio of 1: 1), the strong oxidation activator used in this example is ZC-JO7 type strong oxidation activator (i.e. mixture of dichromate strong oxidation activator and hypochlorite strong oxidation activator in a mass ratio of 1: 1), and the catalytic combustion improver used in this example is ZC-27 type catalytic combustion improver (i.e. composite of metavanadate and nitrate in a mass ratio of 1: 1), which are all available from xiao environmental energy science and technology development ltd.
(1) And (3) crack granulation: crushing the carbon waste of the aluminum electrolytic cell into granular materials with the grain size less than 8mm by adopting an impact crushing mode, and atomizing and spraying a ZC-XJ1 type detoxicant solution which is equivalent to 4 percent of the carbon waste of the aluminum electrolytic cell in the crushing process to obtain the granulated detoxicant material;
(2) dealkalization and activation: placing the granulated detoxified material obtained in the step (1) into a leaching tank with a rolling mixing device, adding a ZC-JO7 type strong oxidation activator and slaked lime which are respectively equal to 3.2% of the mass of the carbon waste of the aluminum electrolytic tank and 18.6% of the mass of the carbon waste of the aluminum electrolytic tank, adding water which is equal to 4 times of the mass of the carbon waste of the aluminum electrolytic tank, rolling, oxidizing and dealkalizing, filtering and washing to obtain fluorocarbon slag; recovering alkali-containing filtrate to prepare concentrated alkali, and recovering water washing liquid for dealkalization and leaching;
(3) preparing modified fuel powder: adding a ZC-27 type catalytic combustion improver which accounts for 3% of the fluorocarbon slag obtained in the step (2) by mass, and mixing and grinding the mixture until the residual sieve mass of 80 mu m is 2% to obtain modified fuel powder;
(4) preparing calcium fluoroaluminate clinker: taking the modified fuel powder obtained in the step (3) as fuel powder for producing calcium fluoroaluminate clinker by a dry-process rotary kiln; mixing and batching bauxite raw materials and carbide slag according to the mass ratio of 55.2:44.8, grinding the mixture until the sieve residue of 80 mu m is less than 18 percent, taking the mixture as raw material powder for producing calcium fluoroaluminate clinker by a dry-process rotary kiln, simultaneously feeding the raw material powder and fuel powder into a cement production line system of the dry-process rotary kiln, wherein the use amount of the fuel powder is such that the firing temperature of the raw material is 1300-1400 ℃, calcining for 25min at the temperature, and quenching by a grate cooler to obtain the belite-calcium fluoroaluminate clinker;
(5) preparing fluoroaluminate cement: controlling the aluminum/sulfur ratio in the cement to be 1.8, adding 38% of fluorgypsum or sodium citrate with the mass of 0.3% of the fluorgypsum into the belite-calcium fluoroaluminate clinker obtained in the step (4), respectively, and respectively mixing and grinding the mixture to powder with the mass of 8% of 80 mu m screen residue to obtain 1.1 parts of the double-fast hard fluoroaluminate cement and 1.2 parts of the double-fast hard fluoroaluminate cement.
The doubly-hardened and doubly-hardened fluoroaluminate cement 1.1 and the doubly-hardened and doubly-hardened fluoroaluminate cement 1.2 obtained in the present example were respectively tested with reference to the national standard "sulphoaluminate cement" (GB 20472-2006).
The detection result of the double fast hardening fluoroaluminate cement 1.1 is as follows: initial setting time is 1 minute and 59 seconds, final setting time is 2 minutes and 40 seconds, 1 hour of compression resistance is 23.5MPa, and bending resistance is 4.3MPa, 2 hour of compression resistance is 27.9MPa, and bending resistance is 4.6MPa, 4 hour of compression resistance is 28.5MPa, and bending resistance is 4.9MPa, 1d of compression resistance is 37.3MPa, bending resistance is 5.1MPa, 28d of compression resistance is 55.4MPa, and bending resistance is 5.5MPa, 180d of compression resistance is 68.6MPa, and bending resistance is 9.2 MPa.
The detection result of the double fast hardening fluoroaluminate cement 1.2 is as follows: initial setting time is 12 minutes and 44 seconds, final setting time is 13 minutes and 13 seconds, 4h compression resistance is 32.1MPa, fracture resistance is 5.3MPa, 1d compression resistance is 41.6MPa, fracture resistance is 5.5MPa, 28d compression resistance is 55.7MPa, fracture resistance is 6.7MPa, 180d compression resistance is 67.9MPa, and fracture resistance is 9.1 MPa.
Example 2
The carbon waste of the aluminum cell used in the embodiment of the invention is taken from a carbon waste mixture stored in a certain aluminum factory, and the carbon waste mixture mainly comprises the following chemical components: c55.78%, F11.37%, Na 12.83%, Al 2.44%, Fe 0.76%, Si 4.12%, Ca 1.37%, Mg 0.52%, and heat value 4380 kcal/kg; the cyanide detoxifying agent used in the embodiment is a saturated solution prepared by dissolving lithium ferrate, cobalt perchlorate and sodium hypochlorite in water according to the mass ratio of 2:1: 2; the strong oxidation activator used in the present example is ZC-YO7 type strong oxidation activator (i.e. a mixture of dichromate strong oxidation activator and hypochlorite strong oxidation activator in a mass ratio of 1: 1), and the catalytic combustion improver used in the present example is ZC-29 type catalytic combustion improver (i.e. a compound of ammonium dichromate and nitrate in a mass ratio of 1: 1), which are all purchased from yoyin, province, and environmental energy science and technology development limited company; the retarder used in this example was a commercially available composite retarder (a composite of citric acid and a water reducing agent).
(1) And (3) crack granulation: crushing the carbon waste of the aluminum electrolytic cell into granular materials with the particle size of less than 8mm by adopting an impact crushing system, and atomizing and spraying cyanide detoxicant solution which is 5 percent of the carbon waste of the aluminum electrolytic cell in the crushing process to obtain the granular detoxicant material;
(2) dealkalization and activation: placing the granulated detoxified material obtained in the step (1) into a leaching tank with a rolling mixing device, adding a ZC-YO7 type strong oxidation activator and 20.8% of quicklime which respectively account for 3.8% of the mass of the carbon waste of the aluminum electrolytic tank, adding water rolling mixing oxidation dealkalization which accounts for 5 times of the mass of the carbon waste of the aluminum electrolytic tank, filtering and washing to obtain fluorocarbon slag; recovering alkali-containing filtrate to prepare concentrated alkali, and recovering water washing liquid for dealkalization and leaching;
(3) preparing modified fuel powder: adding ZC-29 type catalytic combustion improver and bituminous coal which are equivalent to 2.5% of the fluorocarbon slag obtained in the step (2) in mass and mixing and grinding the mixture until the residual sieve mass of 80 mu m is 3% to obtain modified fuel powder;
(4) preparing calcium fluoroaluminate clinker: taking the modified fuel powder obtained in the step (3) as fuel powder for producing calcium fluoroaluminate clinker by a dry-process rotary kiln; mixing and batching a bauxite raw material and waste lime of a calcium carbide plant according to the mass ratio of 40.7:59.3, grinding the mixture until the sieve residue of 80 mu m is less than 12 percent, taking the mixture as raw material powder for producing calcium fluoroaluminate clinker by a dry-process rotary kiln, simultaneously feeding the raw material powder and fuel powder into a cement production line system of the dry-process rotary kiln, wherein the fuel powder is used in an amount that the firing temperature of the raw material is 1250-1350 ℃, calcining the raw material for 30min at the temperature, and quenching a grate cooler to obtain the belite-calcium fluoroaluminate clinker;
(5) preparing fluoroaluminate cement: controlling the aluminum/sulfur ratio in the cement to be 1.9, adding 20% of waste slag, 40% of fluorgypsum and 0.8% of retarder by mass into the belite-calcium fluoroaluminate clinker obtained in the step (4), and respectively mixing and grinding the mixture to powder with the mass of 5% of 80 mu m screen residue to obtain the double-rapid hard fluoroaluminate cement.
With reference to the national standard "sulphoaluminate cement" (GB 20472-2006), the double rapid hardening sulphoaluminate cement obtained in this example has the following detection results: initial setting time is 13 minutes and 37 seconds, final setting time is 14 minutes and 09 seconds, 4h compression resistance is 27.9MPa, fracture resistance is 4.7MPa, 1d compression resistance is 33.6MPa, fracture resistance is 5.1MPa, 28d compression resistance is 54.8MPa, fracture resistance is 5.4MPa, 180d compression resistance is 62.7MPa, and fracture resistance is 8.8 MPa.
Example 3
The carbon waste of the aluminum electrolysis cell used in the embodiment is obtained from a mixture of waste cathode carbon blocks and anode carbon particles which are piled up in a certain aluminum factory warehouse and mixed according to the mass ratio of 2:1, and the aluminum electrolysis cell mainly comprises the following chemical components: 50.38% of C, 16.04% of F, 12.42% of Na, 6.04% of Al6, 0.61% of Fe, 2.01% of Si, 1.07% of Ca, 0.67% of Mg and 3956 kcal/kg of heat value; the cyanide detoxifying agent solution used in this example was ZC-XJ3 type detoxifying agent solution (i.e., a saturated solution prepared by mixing dichromate detoxifying agent and hypochlorite detoxifying agent at a mass ratio of 1: 1), purchased from yinal environmental energy science and technology development ltd, of south of Hunan province; the strong oxidation activator used in this example is prepared by mixing potassium ferrate, potassium dichromate and cobalt chlorate in a mass ratio of 2:1: 2; the catalytic combustion improver used in the present example is a ZC-27 type catalytic combustion improver (i.e., a compound of metavanadate and nitrate in a mass ratio of 1: 1), and is purchased from samyi environmental energy science and technology development ltd, of south of Hunan province.
(1) And (3) crack granulation: crushing the carbon waste of the aluminum electrolytic cell into a granular material with the grain size less than 8mm by adopting an impact crushing system, and atomizing and spraying a ZC-XJ3 type detoxicant solution which is 3.5 percent of the carbon waste of the aluminum electrolytic cell in the crushing process to obtain a granular detoxicant material;
(2) dealkalization and activation: placing the granulated detoxified material obtained in the step (1) into a leaching tank with a rolling mixing device, adding a strong oxidation activator and hydrated lime which respectively account for 5% and 38.5% of the mass of the carbon waste of the aluminum electrolytic tank, adding water which accounts for 6 times of the mass of the carbon waste of the aluminum electrolytic tank, rolling, oxidizing and dealkalizing, filtering and washing to obtain fluorocarbon slag; recovering alkali-containing filtrate to prepare concentrated alkali, and recovering water washing liquid for dealkalization and leaching;
(3) preparing modified fuel powder: adding ZC-27 type catalytic combustion improver and 42.5% semi-bituminous coal which are equivalent to 3% of the fluorocarbon slag obtained in the step (2) by mass, and mixing and grinding the mixture until the oversize mass of 80 mu m is 2.6% to obtain modified fuel powder;
(4) preparing calcium fluoroaluminate clinker: taking the modified fuel powder obtained in the step (3) as fuel powder for producing calcium fluoroaluminate clinker by a dry-process rotary kiln; mixing and batching waste high-alumina bricks and limestone according to the mass ratio of 38.3:61.7, grinding the mixture until the sieve residue of 80 mu m is less than 16 percent, taking the mixture as raw material powder for producing calcium fluoroaluminate clinker by a dry rotary kiln, simultaneously feeding the raw material powder and fuel powder into a cement production line system of the dry rotary kiln, wherein the use amount of the fuel powder is such that the firing temperature of the raw material is 1300-1400 ℃, calcining the raw material for 20min at the temperature, and quenching the raw material by a grate cooler to obtain the belite-calcium fluoroaluminate clinker;
(5) preparing fluoroaluminate cement: controlling the aluminum/sulfur ratio in the cement to be 1.35, adding 34.7 percent of fluorgypsum and 0.2 percent of tartaric acid which are respectively equivalent to the mass of the belite-calcium fluoroaluminate clinker obtained in the step (4), respectively mixing and grinding the mixture to powder with 80 mu m and the mass of the sieved powder being 6 percent, and obtaining the double-rapid-hardening fluoroaluminate cement.
With reference to the national standard "sulphoaluminate cement" (GB 20472-2006), the double rapid hardening sulphoaluminate cement obtained in this example has the following detection results: initial setting time of 11 minutes and 40 seconds, final setting time of 12 minutes and 13 seconds, 4h compression resistance of 30.2MPa, fracture resistance of 5.1MPa, 1d compression resistance of 39.7MPa, fracture resistance of 5.3MPa, 28d compression resistance of 57.8MPa, fracture resistance of 6.4MPa, 180d compression resistance of 70.8MPa and fracture resistance of 9.7 MPa.
Example 4
The carbon waste of the aluminum cell used in the embodiment of the invention is taken from a block carbon waste mixture stored in a certain aluminum factory, and the main chemical components of the carbon waste mixture are as follows: 67.32% of C, 9.06% of F, 11.23% of Na, 2.19% of Al, 0.59% of Fe, 2.17% of Si, 0.94% of Ca, 0.61% of Mg and 5286 kcal/kg of heat value; the cyanide detoxifying agent solution used in the embodiment of the invention is ZC-XJ1 type detoxifying agent solution (saturated solution prepared by ferrate detoxifying agent and hypochlorite detoxifying agent in a mass ratio of 1: 1), the strong oxidation activator used in the embodiment is ZC-JO7 type strong oxidation activator (namely mixture of dichromate strong oxidation activator and hypochlorite strong oxidation activator in a mass ratio of 2: 1), and the strong oxidation activator is purchased from environmental energy science development No. Co., Ltd, Yi in Hunan province; the catalytic combustion improver used in the embodiment is prepared by mixing ammonium dichromate, ammonium metavanadate, lithium perchlorate, cerium nitrate and strontium nitrate in a mass ratio of 4:1:2:3: 1.
(1) And (3) crack granulation: crushing the carbon waste of the aluminum electrolytic cell into a granular material with the grain size less than 5mm by adopting an impact crushing system, and atomizing and spraying a ZC-XJ1 type detoxicant solution which is equivalent to 4 percent of the carbon waste of the aluminum electrolytic cell in the crushing process to obtain a granulated detoxicant material;
(2) dealkalization and activation: placing the granulated detoxified material obtained in the step (1) into a leaching tank with a rolling mixing device, adding a ZC-JO7 type strong oxidation activator and hydrated lime, wherein the ZC-JO7 type strong oxidation activator and the hydrated lime are respectively equal to 3.8% of the mass of the carbon waste of the aluminum electrolytic tank, adding water which is equal to 5 times of the mass of the carbon waste of the aluminum electrolytic tank, rolling, oxidizing and dealkalizing, filtering and washing to obtain fluorocarbon slag; recovering alkali-containing filtrate to prepare concentrated alkali, and recovering water washing liquid for dealkalization and leaching;
(3) preparing modified fuel powder: adding a catalytic combustion improver which accounts for 4.5 percent of the mass of the fluorocarbon slag obtained in the step (2), mixing and grinding the mixture until the mass of the 80 mu m screen residue is 3.1 percent, and obtaining modified fuel powder;
(4) preparing a calcium fluoroaluminate-calcium sulfoaluminate clinker: taking the modified fuel powder obtained in the step (3) as fuel powder for producing calcium fluoroaluminate clinker by a dry-process rotary kiln; mixing and batching waste high-alumina bricks, carbide slag and desulfurized gypsum according to the mass ratio of 52.1:41.7:6.2, grinding the mixture until the sieve residue of 80 mu m is less than 17 percent, using the mixture as raw material powder for producing calcium fluoroaluminate clinker by a dry-process rotary kiln, simultaneously sending the raw material powder and fuel powder into a cement production line system of the dry-process rotary kiln, wherein the use amount of the fuel powder is such that the firing temperature of the raw material is 1300-1400 ℃, calcining the raw material for 30min at the temperature, and quenching a grate cooler to obtain the belite-calcium fluoroaluminate clinker;
(5) preparing fluoroaluminate cement: controlling the aluminum/sulfur ratio in the cement to be 1.6, adding fluorogypsum and potassium citrate which are respectively equivalent to 41 percent of the mass of the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker and 0.3 percent of the mass of the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker obtained in the step (4), and respectively mixing and grinding the materials to powder with 80 mu m and the mass of the sieved powder being 6 percent to obtain the double-fast hard fluoroaluminate cement.
With reference to the national standard "sulphoaluminate cement" (GB 20472-2006), the double rapid hardening sulphoaluminate cement obtained in this example has the following detection results: initial setting time is 14 minutes and 34 seconds, final setting time is 15 minutes and 06 seconds, 4h compression resistance is 28.4MPa, fracture resistance is 4.9MPa, 1d compression resistance is 43.6MPa, fracture resistance is 5.6MPa, 28d compression resistance is 58.7MPa, fracture resistance is 7.2MPa, 180d compression resistance is 71.8MPa, and fracture resistance is 9.8 MPa.
Example 5
The carbon waste of the aluminum electrolytic cell used in the embodiment of the invention is selected from waste anode carbon granules of electrolytic aluminum stored in certain aluminum plant storeroom, and the main chemical components of the carbon waste are as follows: c39.23%, F21.56%, Na 14.92%, Al 9.71%, Fe 0.52%, Si 1.6%, Ca 0.97%, Mg 0.79%, and the heat value 3080 kcal/kg; the cyanide detoxifying agent solution used in this example is ZC-XJ1 type detoxifying agent solution (saturated solution prepared by ferrate detoxifying agent and hypochlorite detoxifying agent in a mass ratio of 1: 1), the strong oxidation activator used in this example is ZC-JO7 type strong oxidation activator (i.e. mixture of dichromate strong oxidation activator and hypochlorite strong oxidation activator in a mass ratio of 2: 1), and the catalytic combustion improver used in this example is ZC-27 type catalytic combustion improver (i.e. composite of metavanadate and nitrate in a mass ratio of 1: 1), which are all available from samyian environmental energy science and technology development limited company in hunen province.
(1) And (3) crack granulation: crushing the carbon waste of the aluminum electrolytic cell into granular materials with the grain size less than 8mm by adopting an extrusion type crushing system, and atomizing and spraying a ZC-XJ1 type detoxicant solution which is equivalent to 4.8 percent of the carbon waste of the aluminum electrolytic cell in the crushing process to obtain the granular detoxicant material;
(2) dealkalization and activation: placing the granulated detoxified material obtained in the step (1) into a leaching tank with a rolling mixing device, adding a ZC-JO7 type strong oxidation activator and slaked lime which respectively account for 2.9% of the mass of the carbon waste of the aluminum electrolytic tank and 38.7% of the mass of the slaked lime, adding water which accounts for 7 times of the mass of the carbon waste of the aluminum electrolytic tank, rolling, oxidizing and dealkalizing, filtering and washing to obtain fluorocarbon slag; recovering alkali-containing filtrate to prepare concentrated alkali, and recovering water washing liquid for dealkalization and leaching;
(3) preparing aged fluorocarbon slag: adding a ZC-27 type catalytic combustion improver which accounts for 1.9 percent of the mass of the fluorocarbon slag obtained in the step (2) into the fluorocarbon slag, uniformly mixing, and aging for 8 hours to obtain aged fluorocarbon slag;
(4) preparing calcium fluoroaluminate clinker: mixing the aged fluorocarbon slag obtained in the step (3) with waste alumina and carbide slag according to the mass ratio of 18.4:38.7:42.9, grinding the mixture into raw powder with the mass of 80 mu m screen residue of 18 percent, using the raw powder as raw powder for producing calcium fluoroaluminate clinker or calcium fluoroaluminate-calcium sulfoaluminate clinker in a dry rotary kiln, sending the raw powder into a dry rotary kiln system, calcining the raw powder for 30min at 1250-1350 ℃ in air atmosphere, and quenching a grate cooler to obtain belite-calcium fluoroaluminate clinker;
(5) preparing fluoroaluminate cement: controlling the aluminum/sulfur ratio in the cement to be 1.8, adding 36% of fluorgypsum and 0.3% of sodium citrate which are respectively equivalent to the mass of the belite-calcium fluoroaluminate clinker obtained in the step (4), respectively mixing and grinding the materials to powder with the mass of 3% of 80 mu m screen residue, and obtaining the double-quick-hardening fluoroaluminate cement.
With reference to the national standard "sulphoaluminate cement" (GB 20472-2006), the double rapid hardening sulphoaluminate cement obtained in this example has the following detection results: initial setting time is 12 minutes and 27 seconds, final setting time is 12 minutes and 58 seconds, 4h compression resistance is 34.7MPa, fracture resistance is 5.4MPa, 1d compression resistance is 44.8MPa, fracture resistance is 5.7MPa, 28d compression resistance is 56.9MPa, fracture resistance is 6.9MPa, 180d compression resistance is 63.7MPa, and fracture resistance is 9.4 MPa.

Claims (28)

1. A method for producing fluoroaluminate cement by using carbon waste materials of aluminum electrolytic cells in a dry-process rotary kiln plant is characterized by comprising the following steps: (1) and (3) crack granulation: crushing the carbon waste of the aluminum electrolytic cell into a granular material with the particle size of less than 10mm by adopting an extrusion or impact crushing mode, and atomizing and spraying a cyanide detoxicant solution in the crushing process to obtain a granulated detoxicant material;
(2) dealkalization and activation: placing the granulated detoxified material obtained in the step (1) into a leaching tank/tank with a stirring or rolling device, adding a strong oxidation activator and lime, adding water, stirring or rolling for oxidizing dealkalization, filtering or filtering and washing with water to obtain fluorocarbon slag;
(3) preparing modified fuel powder: adding a catalytic combustion improver or coal into the fluorocarbon slag obtained in the step (2), mixing and grinding until the sieved residue of 80 mu m is less than 8 percent to obtain modified fuel powder;
(4) preparing a calcium fluoroaluminate or calcium fluoroaluminate-calcium sulfoaluminate clinker: taking the modified fuel powder obtained in the step (3) as fuel powder for producing calcium fluoroaluminate clinker or calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry-process rotary kiln; waste bauxite and calcium raw materials are mixed and ground until the screen residue of 80 mu m is less than 25 percent, and then the mixture is used as raw material powder for producing calcium fluoroaluminate clinker by a dry-process rotary kiln;
or taking the modified fuel powder obtained in the step (3) as fuel powder for producing calcium fluoroaluminate clinker or calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry-process rotary kiln; waste bauxite, calcium raw materials and waste gypsum are mixed and ground until the screen residue of 80 mu m is less than 25 percent, and then the mixture is used as raw material powder for producing calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry rotary kiln;
respectively sending the raw material powder and the fuel powder into a dry-process rotary kiln cement production line system simultaneously, wherein the using amount of the fuel powder is such that the firing temperature of the raw material is 1200-1400 ℃, and calcining and quenching the raw material by a grate cooler at the temperature to obtain belite-calcium fluoroaluminate clinker or belite-calcium fluoroaluminate-calcium sulfoaluminate clinker;
(5) preparing fluoroaluminate cement: and (3) controlling the aluminum/sulfur ratio in the cement, adding waste gypsum or furnace slag and/or fly ash and a retarder into the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker obtained in the step (4), and mixing and grinding the mixture to powder with 80 mu m and less than 12 percent of screen residue to obtain the double-fast hard fluoroaluminate cement or the double-fast hard fluoroaluminate-sulfoaluminate cement.
2. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 1, wherein the method comprises the following steps: in the step (1), the aluminum electrolysis cell carbon waste is waste cathode carbon blocks and/or waste anode carbon particles, wherein the aluminum electrolysis cell carbon waste comprises 18-72% of C, 5-25% of F, 5-20% of Na, 2-10% of Al, 0.2-2.0% of Fe, 1-10% of Si, 0.2-2.0% of Ca and 0.2-2.0% of Mg, the total weight of the elements is less than or equal to 100% by mass, and the heat value is 3000-6000 kcal/kg.
3. The method for producing the fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 1 or 2, wherein in the step (1), the dosage of the cyanide detoxifier is 1-8% of the mass of the carbon waste of the aluminum electrolytic cell; the cyanide detoxifier is one or more of ferrate detoxifier, dichromate detoxifier, dichromic anhydride detoxifier, thiosulfate detoxifier, perchlorate detoxifier, hydroxide detoxifier, hypochlorite detoxifier or chlorine dioxide; the ferrate detoxifier is one or more of potassium ferrate, lithium ferrate and sodium ferrate, the dichromate detoxifier is one or more of potassium dichromate, sodium dichromate or cobalt dichromate, the thiosulfate detoxifier is sodium thiosulfate and/or potassium thiosulfate, the perchlorate is lithium perchlorate and/or cobalt perchlorate, the hydroxide is one or more of cobalt hydroxide, iron hydroxide or potassium hydroxide, and the hypochlorite is sodium hypochlorite and/or calcium hypochlorite.
4. The method for producing fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 1 or 2, which is characterized by comprising the following steps of: in the step (2), the using amounts of the strong oxidation activator and the lime are respectively equal to 1-8% and 5-40% of the mass of the carbon waste of the aluminum electrolytic cell, and the adding amount of the water is equal to 1-10 times of the mass of the carbon waste of the aluminum electrolytic cell.
5. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 3, wherein the method comprises the following steps: in the step (2), the using amounts of the strong oxidation activator and the lime are respectively equal to 1-8% and 5-40% of the mass of the carbon waste of the aluminum electrolytic cell, and the adding amount of the water is equal to 1-10 times of the mass of the carbon waste of the aluminum electrolytic cell.
6. The method for producing fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 1 or 2, wherein in the step (2), the strong oxidation activator is one or more of chlorosulfonic acid strong oxidation activator, dichromate strong oxidation activator, dichromic anhydride strong oxidation activator, ferrate strong oxidation activator, perchlorate strong oxidation activator or chlorate strong oxidation activator; the dichromate strong oxidation activator is one or more of potassium dichromate, sodium dichromate or cobalt dichromate, the ferrate strong oxidation activator is one or more of potassium ferrate, sodium ferrate or lithium ferrate, the perchlorate strong oxidation activator is cobalt perchlorate, and the chlorate strong oxidation activator is cobalt chlorate.
7. The method for producing fluoroaluminate cement from carbon waste of aluminum electrolytic cells in dry-process rotary kiln plant according to claim 3, wherein in the step (2), the strong oxidation activator is one or more of chlorosulfonic acid strong oxidation activator, dichromate strong oxidation activator, dichromic anhydride strong oxidation activator, ferrate strong oxidation activator, perchlorate strong oxidation activator or chlorate strong oxidation activator; the dichromate strong oxidation activator is one or more of potassium dichromate, sodium dichromate or cobalt dichromate, the ferrate strong oxidation activator is one or more of potassium ferrate, sodium ferrate or lithium ferrate, the perchlorate strong oxidation activator is cobalt perchlorate, and the chlorate strong oxidation activator is cobalt chlorate.
8. The method for producing fluoroaluminate cement from carbon waste of aluminum electrolysis cell in dry-process rotary kiln plant according to claim 4, wherein in the step (2), the strong oxidation activator is one or more of chlorosulfonic acid strong oxidation activator, dichromate strong oxidation activator, dichromic anhydride strong oxidation activator, ferrate strong oxidation activator, perchlorate strong oxidation activator or chlorate strong oxidation activator; the dichromate strong oxidation activator is one or more of potassium dichromate, sodium dichromate or cobalt dichromate, the ferrate strong oxidation activator is one or more of potassium ferrate, sodium ferrate or lithium ferrate, the perchlorate strong oxidation activator is cobalt perchlorate, and the chlorate strong oxidation activator is cobalt chlorate.
9. The method for producing the fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 1 or 2, wherein in the step (3), the amounts of the catalytic combustion improver and the fire coal are respectively 0.5-5% and 0-50% of the mass of the fluorocarbon slag; the catalytic combustion improver is one or more of ammonium dichromate, metavanadate, lithium perchlorate or nitrate or a compound thereof.
10. The method for producing the fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell for the dry-process rotary kiln plant according to claim 3, wherein in the step (3), the use amounts of the catalytic combustion improver and the fire coal are respectively 0.5-5% and 0-50% of the mass of the fluorocarbon slag; the catalytic combustion improver is one or more of ammonium dichromate, metavanadate, lithium perchlorate or nitrate or a compound thereof.
11. The method for producing fluoroaluminate cement from carbon waste of aluminum electrolytic cells in a dry-process rotary kiln plant according to claim 4, wherein in the step (3), the amounts of the catalytic combustion improver and the fire coal are respectively 0.5-5% and 0-50% of the mass of the fluorocarbon slag; the catalytic combustion improver is one or more of ammonium dichromate, metavanadate, lithium perchlorate or nitrate or a compound thereof.
12. The method for producing fluoroaluminate cement from carbon waste of aluminum electrolytic cells in a dry-process rotary kiln plant according to claim 6, wherein in the step (3), the amounts of the catalytic combustion improver and the fire coal are respectively 0.5-5% and 0-50% of the mass of the fluorocarbon slag; the catalytic combustion improver is one or more of ammonium dichromate, metavanadate, lithium perchlorate or nitrate or a compound thereof.
13. The method for producing the fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 1 or 2, wherein in the step (4), when waste alumina and a calcium raw material are used for proportioning, the mass ratio of the waste alumina to the calcium raw material is 30-65: 70-35; when the waste bauxite, the calcium raw material and the waste gypsum are used for preparing the material, the mass ratio of the waste bauxite to the calcium raw material to the waste gypsum is 20-60: 60-32: 3-25; the waste bauxite is one or more of a waste bauxite raw material, a waste high-alumina brick, high-alumina fly ash or high-alumina coal slag in the production of alumina; the calcareous raw material is one or more of carbide slag, waste lime or limestone; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the calcining time is 15-60 min.
14. The method for producing the fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 3, wherein in the step (4), when waste alumina and a calcium raw material are used for proportioning, the mass ratio of the waste alumina to the calcium raw material is 30-65: 70-35; when the waste bauxite, the calcium raw material and the waste gypsum are used for preparing the material, the mass ratio of the waste bauxite to the calcium raw material to the waste gypsum is 20-60: 60-32: 3-25; the waste bauxite is one or more of a waste bauxite raw material, a waste high-alumina brick, high-alumina fly ash or high-alumina coal slag in the production of alumina; the calcareous raw material is one or more of carbide slag, waste lime or limestone; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the calcining time is 15-60 min.
15. The method for producing the fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 4, wherein in the step (4), when waste alumina and a calcium raw material are used for proportioning, the mass ratio of the waste alumina to the calcium raw material is 30-65: 70-35; when the waste bauxite, the calcium raw material and the waste gypsum are used for preparing the material, the mass ratio of the waste bauxite to the calcium raw material to the waste gypsum is 20-60: 60-32: 3-25; the waste bauxite is one or more of a waste bauxite raw material, a waste high-alumina brick, high-alumina fly ash or high-alumina coal slag in the production of alumina; the calcareous raw material is one or more of carbide slag, waste lime or limestone; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the calcining time is 15-60 min.
16. The method for producing the fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 6, wherein in the step (4), when waste alumina and a calcium raw material are used for proportioning, the mass ratio of the waste alumina to the calcium raw material is 30-65: 70-35; when the waste bauxite, the calcium raw material and the waste gypsum are used for preparing the material, the mass ratio of the waste bauxite to the calcium raw material to the waste gypsum is 20-60: 60-32: 3-25; the waste bauxite is one or more of a waste bauxite raw material, a waste high-alumina brick, high-alumina fly ash or high-alumina coal slag in the production of alumina; the calcareous raw material is one or more of carbide slag, waste lime or limestone; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the calcining time is 15-60 min.
17. The method for producing the fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 9, wherein in the step (4), when waste alumina and a calcium raw material are used for proportioning, the mass ratio of the waste alumina to the calcium raw material is 30-65: 70-35; when the waste bauxite, the calcium raw material and the waste gypsum are used for preparing the material, the mass ratio of the waste bauxite to the calcium raw material to the waste gypsum is 20-60: 60-32: 3-25; the waste bauxite is one or more of a waste bauxite raw material, a waste high-alumina brick, high-alumina fly ash or high-alumina coal slag in the production of alumina; the calcareous raw material is one or more of carbide slag, waste lime or limestone; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the calcining time is 15-60 min.
18. The method for producing fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 1 or 2, which is characterized by comprising the following steps of: replacing the steps (3) and (4) with:
(3) preparing aged fluorocarbon slag: adding a catalytic combustion improver which is 0.5-5% of the fluorocarbon slag obtained in the step (2), uniformly mixing, and aging for 0.5-72 h to obtain aged fluorocarbon slag;
(4) preparing a calcium fluoroaluminate clinker or a calcium fluoroaluminate-calcium sulfoaluminate clinker: and (3) mixing the aged fluorocarbon slag obtained in the step (3), waste alumina, a calcium raw material and waste gypsum according to a mass ratio of 10-25: 20-55: 60-30: 0-25, grinding the mixture until the sieved residue of 80 mu m is less than 25%, using the ground mixture as raw material powder for producing calcium fluoroaluminate clinker or calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry rotary kiln, feeding the raw material powder into a dry rotary kiln system, calcining the raw material powder for 15-60 min at the temperature of 1200-1400 ℃ in an oxidizing atmosphere, and quenching a grate cooler to obtain belite-calcium fluoroaluminate clinker or belite-calcium fluoroaluminate-calcium sulfoaluminate clinker.
19. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 3, wherein the method comprises the following steps: replacing the steps (3) and (4) with:
(3) preparing aged fluorocarbon slag: adding a catalytic combustion improver which is 0.5-5% of the fluorocarbon slag obtained in the step (2), uniformly mixing, and aging for 0.5-72 h to obtain aged fluorocarbon slag;
(4) preparing a calcium fluoroaluminate clinker or a calcium fluoroaluminate-calcium sulfoaluminate clinker: and (3) mixing the aged fluorocarbon slag obtained in the step (3), waste alumina, a calcium raw material and waste gypsum according to a mass ratio of 10-25: 20-55: 60-30: 0-25, grinding the mixture until the sieved residue of 80 mu m is less than 25%, using the ground mixture as raw material powder for producing calcium fluoroaluminate clinker or calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry rotary kiln, feeding the raw material powder into a dry rotary kiln system, calcining the raw material powder for 15-60 min at the temperature of 1200-1400 ℃ in an oxidizing atmosphere, and quenching a grate cooler to obtain belite-calcium fluoroaluminate clinker or belite-calcium fluoroaluminate-calcium sulfoaluminate clinker.
20. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 4, wherein the method comprises the following steps: replacing the steps (3) and (4) with:
(3) preparing aged fluorocarbon slag: adding a catalytic combustion improver which is 0.5-5% of the fluorocarbon slag obtained in the step (2), uniformly mixing, and aging for 0.5-72 h to obtain aged fluorocarbon slag;
(4) preparing a calcium fluoroaluminate clinker or a calcium fluoroaluminate-calcium sulfoaluminate clinker: and (3) mixing the aged fluorocarbon slag obtained in the step (3), waste alumina, a calcium raw material and waste gypsum according to a mass ratio of 10-25: 20-55: 60-30: 0-25, grinding the mixture until the sieved residue of 80 mu m is less than 25%, using the ground mixture as raw material powder for producing calcium fluoroaluminate clinker or calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry rotary kiln, feeding the raw material powder into a dry rotary kiln system, calcining the raw material powder for 15-60 min at the temperature of 1200-1400 ℃ in an oxidizing atmosphere, and quenching a grate cooler to obtain belite-calcium fluoroaluminate clinker or belite-calcium fluoroaluminate-calcium sulfoaluminate clinker.
21. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 6, wherein the method comprises the following steps: replacing the steps (3) and (4) with:
(3) preparing aged fluorocarbon slag: adding a catalytic combustion improver which is 0.5-5% of the fluorocarbon slag obtained in the step (2), uniformly mixing, and aging for 0.5-72 h to obtain aged fluorocarbon slag;
(4) preparing a calcium fluoroaluminate clinker or a calcium fluoroaluminate-calcium sulfoaluminate clinker: and (3) mixing the aged fluorocarbon slag obtained in the step (3), waste alumina, a calcium raw material and waste gypsum according to a mass ratio of 10-25: 20-55: 60-30: 0-25, grinding the mixture until the sieved residue of 80 mu m is less than 25%, using the ground mixture as raw material powder for producing calcium fluoroaluminate clinker or calcium fluoroaluminate-calcium sulfoaluminate clinker by a dry rotary kiln, feeding the raw material powder into a dry rotary kiln system, calcining the raw material powder for 15-60 min at the temperature of 1200-1400 ℃ in an oxidizing atmosphere, and quenching a grate cooler to obtain belite-calcium fluoroaluminate clinker or belite-calcium fluoroaluminate-calcium sulfoaluminate clinker.
22. The method for producing fluoroaluminate cement by using the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 1 or 2, which is characterized by comprising the following steps of: in the step (5), the aluminum/sulfur ratio is 1.1-2.2; the using amounts of the waste gypsum, the furnace slag and/or the fly ash and the retarder are respectively 8-60%, 0-50% and 0-3% of the mass of the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the retarder is one or more of citric acid, citrate or tartaric acid or a compound of citric acid and a water reducing agent.
23. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 3, wherein the method comprises the following steps: in the step (5), the aluminum/sulfur ratio is 1.1-2.2; the using amounts of the waste gypsum, the furnace slag and/or the fly ash and the retarder are respectively 8-60%, 0-50% and 0-3% of the mass of the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the retarder is one or more of citric acid, citrate or tartaric acid or a compound of citric acid and a water reducing agent.
24. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 4, wherein the method comprises the following steps: in the step (5), the aluminum/sulfur ratio is 1.1-2.2; the using amounts of the waste gypsum, the furnace slag and/or the fly ash and the retarder are respectively 8-60%, 0-50% and 0-3% of the mass of the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the retarder is one or more of citric acid, citrate or tartaric acid or a compound of citric acid and a water reducing agent.
25. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 6, wherein the method comprises the following steps: in the step (5), the aluminum/sulfur ratio is 1.1-2.2; the using amounts of the waste gypsum, the furnace slag and/or the fly ash and the retarder are respectively 8-60%, 0-50% and 0-3% of the mass of the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the retarder is one or more of citric acid, citrate or tartaric acid or a compound of citric acid and a water reducing agent.
26. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 9, wherein the method comprises the following steps: in the step (5), the aluminum/sulfur ratio is 1.1-2.2; the using amounts of the waste gypsum, the furnace slag and/or the fly ash and the retarder are respectively 8-60%, 0-50% and 0-3% of the mass of the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the retarder is one or more of citric acid, citrate or tartaric acid or a compound of citric acid and a water reducing agent.
27. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 13, wherein the method comprises the following steps: in the step (5), the aluminum/sulfur ratio is 1.1-2.2; the using amounts of the waste gypsum, the furnace slag and/or the fly ash and the retarder are respectively 8-60%, 0-50% and 0-3% of the mass of the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the retarder is one or more of citric acid, citrate or tartaric acid or a compound of citric acid and a water reducing agent.
28. The method for producing fluoroaluminate cement from the carbon waste of the aluminum electrolytic cell in the dry-process rotary kiln plant according to claim 18, wherein the method comprises the following steps: in the step (5), the aluminum/sulfur ratio is 1.1-2.2; the using amounts of the waste gypsum, the furnace slag and/or the fly ash and the retarder are respectively 8-60%, 0-50% and 0-3% of the mass of the belite-calcium fluoroaluminate clinker or the belite-calcium fluoroaluminate-calcium sulfoaluminate clinker; the waste gypsum is one or more of fluorgypsum, desulfurized gypsum or phosphogypsum, or anhydrite obtained by roasting the waste gypsum; the retarder is one or more of citric acid, citrate or tartaric acid or a compound of citric acid and a water reducing agent.
CN201710601021.2A 2017-07-21 2017-07-21 Method for producing fluoroaluminate cement by using carbon waste of aluminum electrolytic cell in dry-process rotary kiln plant Active CN107200488B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710601021.2A CN107200488B (en) 2017-07-21 2017-07-21 Method for producing fluoroaluminate cement by using carbon waste of aluminum electrolytic cell in dry-process rotary kiln plant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710601021.2A CN107200488B (en) 2017-07-21 2017-07-21 Method for producing fluoroaluminate cement by using carbon waste of aluminum electrolytic cell in dry-process rotary kiln plant

Publications (2)

Publication Number Publication Date
CN107200488A CN107200488A (en) 2017-09-26
CN107200488B true CN107200488B (en) 2019-12-24

Family

ID=59911956

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710601021.2A Active CN107200488B (en) 2017-07-21 2017-07-21 Method for producing fluoroaluminate cement by using carbon waste of aluminum electrolytic cell in dry-process rotary kiln plant

Country Status (1)

Country Link
CN (1) CN107200488B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108516710A (en) * 2018-07-07 2018-09-11 河源市极致知管信息科技有限公司 A kind of preparation method of fluoroaluminate cement
CN108585564B (en) * 2018-07-16 2023-05-16 长沙中硅环保科技有限公司 System and method for co-processing electrolytic aluminum waste residues and co-producing double quick cement by cement kiln

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6190449B1 (en) * 1997-04-08 2001-02-20 Carrieres Du Boulonnais Method for eliminating waste sulfurous acids coming from industrial treatments and for obtaining stable products

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102795795B (en) * 2012-08-31 2014-06-18 苏州展阳新能源科技有限公司 Method for preparing fluoaluminate cement from fluorine-containing sludge
CN103343363B (en) * 2013-06-28 2016-05-11 湖南中大冶金设计有限公司 The electrolytical production method of a kind of electrolgtic aluminium
CN106565120B (en) * 2016-11-07 2018-11-16 中国铝业股份有限公司 A kind of harmless treatment of aluminium electroloysis waste lining utilizes method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6190449B1 (en) * 1997-04-08 2001-02-20 Carrieres Du Boulonnais Method for eliminating waste sulfurous acids coming from industrial treatments and for obtaining stable products

Also Published As

Publication number Publication date
CN107200488A (en) 2017-09-26

Similar Documents

Publication Publication Date Title
CN107352819B (en) Method for producing calcium fluoroaluminate clinker by using aluminum cell carbon waste
AU647672B2 (en) Detoxification of aluminum spent potliner
CN111732353B (en) Method for treating sand-based waste incineration fly ash by using cement kiln in cooperation
CN102978659B (en) A kind of Deep method of comprehensive utilization of electrolytic cell overhaul slag
CN107401746B (en) Treatment system and treatment method for aluminum electrolysis overhaul slag
CN105964660B (en) A kind of method of harmless treatment aluminium electrolytic tank
CN1785537A (en) Treatment method of aluminium electrolytic bath waste cathode carbon blook innocuousnes
CN114105610A (en) Aluminum ash-based porous ceramic material and preparation method thereof
CN109136564A (en) A kind of processing method of the carbon containing waste residue of electrolytic aluminium
CN113909260B (en) Clean production and resource recycling treatment process for manganese products
CN111777344B (en) Method for treating waste incineration fly ash as admixture by cooperation of cement kiln
CN110106312A (en) A kind of technique using electrolytic aluminium carbon slag production LF slagging agent
CN107363074B (en) A kind of aluminium cell carbonaceous materials recycling is the method for alternative fire coal
CN111807731B (en) Method for cooperatively treating chlor-alkali salt mud in cement kiln
CN102989744A (en) Method for recycling mixed material dreg of overhauling groove slag of electrolytic cell
CN110093471A (en) A kind of efficient low-consume red mud method of comprehensive utilization
CN113683108A (en) Method for preparing calcium aluminate product by using secondary aluminum ash
CN107200488B (en) Method for producing fluoroaluminate cement by using carbon waste of aluminum electrolytic cell in dry-process rotary kiln plant
CN111943715A (en) Method for firing ceramsite based on modified sludge
CN110015672B (en) Method for producing magnesium fluoride by using electrolytic cell waste
CN107159688B (en) A kind of aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material
CN112456797B (en) Glass body preparation method and harmless disposal method of waste incineration fly ash and aluminum cell overhaul residues
CN107352542A (en) A kind of regeneration method and its application of aluminium cell carbonaceous waste material
CN103028592B (en) A kind of circulation utilization method of electrolytic cell overhaul slag recovery water
CN111777345B (en) Method for co-processing waste incineration fly ash by using cement kiln

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant