CN106904849B - A kind of system and method using Industrial Solid Waste production sulphate aluminium cement co-producing sulfuric acid - Google Patents
A kind of system and method using Industrial Solid Waste production sulphate aluminium cement co-producing sulfuric acid Download PDFInfo
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- CN106904849B CN106904849B CN201710160162.5A CN201710160162A CN106904849B CN 106904849 B CN106904849 B CN 106904849B CN 201710160162 A CN201710160162 A CN 201710160162A CN 106904849 B CN106904849 B CN 106904849B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Treatment Of Sludge (AREA)
Abstract
The invention discloses a kind of system and method using Industrial Solid Waste production sulphate aluminium cement co-producing sulfuric acid, it is raw materials used to derive from large Industrial Solid Waste, by techniques such as material homogenizer, mechanical stirring, filters pressing, drying, grinding, raw material preheating, calcined by rotary kiln decomposition, sinter leaching, cement grinding, kiln gas acid-scrubbing cleaning, sulfur dioxide drying, double-absorptions.Its clinker mineral being burnt into mainly forms are as follows: anhydrous calcium sulphoaluminate, dicalcium silicate, tetra calcium aluminoferrite, part of sulfuric acid calcium decomposes the sulfur dioxide generated when firing, and 93% or 98% sulfuric acid is made through two turns of acid-scrubbing cleaning suctions in the sulfur dioxide concentration 4-6% in flue gas.Based on present invention process by aluminium ash, desulfurized gypsum, carbide slag, red mud rational proportion, the sulphoaluminate cement clinker of production can be used for preparing the additive of special cement or traditional cements, the sulfuric acid of coproduction can achieve the quality requirement of extraordinary acid, realize the energy saving purpose of low temperature calcination.
Description
Technical field
The invention patent relates to chemical industry, building material technique and calcium sulphate-based comprehensive utilizations of resources and ring with the iron-based solid waste of sial
Protect improvement field in border, and in particular to a kind of system and method using Industrial Solid Waste production sulphate aluminium cement co-producing sulfuric acid.
Background technique
In the today's society that land resource day is becoming tight, environmental protection is increasingly important, Chinese Ministry of Industry and Information is " " 12th Five-Year Plan " is big
Ancestor's industrial solid wastes comprehensively utilize ad hoc planning " in by tailing, gangue, flyash, metallurgical slag, pair from five big industries
It produces gypsum and red mud is classified as large Industrial Solid Waste, as the main object of processing.Red mud, aluminium ash, desulfurized gypsum are more next
More by several typical industry solid wastes paid close attention to.
Red mud be in aluminum oxide industry production process after bauxite ore alumina purifying generated large industrial waste
Object, 1 ton of aluminium oxide of every production can produce 0.8-1.8 tons of red muds, Chinese aluminium oxide yield reaches 47,770,000 tons within 2014, phase
The red mud discharge amount answered should be at 60,000,000 tons or so, and the comprehensive utilization ratio of red mud is only 4% at present, containing a large amount of in red mud
Silica, calcium oxide, di-iron trioxide, aluminium oxide, sodium oxide molybdena, titanium dioxide etc. are the raw materials for manufacturing building materials.It is a large amount of red
Mud is placed in a manner of storing up, and red mud pilling does not only take up a large amount of soils and farmland, expends more stockyard construction and dimension
Shield expense, while the high-alkali composition in red mud can cause underground water pollution to subsurface wastewater infiltration system, pollution depth up to 200-700 meters,
In addition, the dust that the red mud dried is formed is flown upward everywhere, ring ecological environment is broken, causes seriously to pollute.
Due to containing the cement minerals ingredients such as a large amount of dicalcium silicate in red mud, so red mud can be used to produce cement.
But alkalinity is high in red mud, red mud proportion is limited by cement index containing alkali, it is difficult to produce low alkali cement.The dealkalize of red mud
Method has lime hydro-thermal method, normal pressure lime dealkalize method, lime pure alkali sintering process, salt lixiviation process etc., but these methods is de-
Alkali cost is very high, and dealkalize rate not only increases manufacture of cement cost, and be not suitable for producing generally in 70-80% or so
Certain low alkali cements.
Desulfurized gypsum is the by-product that flue gas desulfurization generates in industrial production, and main component is crystalline sulfuric acid calcium (CaSO4·
2H2O) moisture content is generally in 10%-20%, and color is in faint yellow, and particle is thinner, and pH value is suitable with the natural gypsum, sulfuric acid
The mass fraction of calcium and calcium sulphate dihydrate is generally 90% or more, the calcium sulfate and calcium sulphate dihydrate mass fraction one of the natural gypsum
As in 70%-80%.Desulfurized gypsum purity is higher, stable components, and the major impurity contained is not reacted calcium oxide and Asia
Calcium sulfate, compared with the natural gypsum, the main distinction is that moisture content is higher, and granularity is more small, and containing water-soluble salt is more.Desulfurization
The kenel of gypsum is affected by temperature larger, and desulfurized gypsum loses the crystallization water since 135 DEG C, the crystallization whole to 185 DEG C of removings
Water, the desulfurized gypsum main mineral constituent dried under the conditions of 140 DEG C become semi-hydrated gypsum by dihydrate gypsum.With China's base
Infrastructure constantly improve, and the demand of electric power is constantly aggravated, and 80% that the thermoelectricity generated energy in China accounts for total power generation is left
The right side, according to nearly 10 years corresponding thermal power outputs and thermal power generation fire coal average sulfur content and desulfurization equipment mean efficiency of desulfurization, in advance
Estimate existing industrial by-product desulfurized gypsum and has reached 600,000,000 tons, if cannot comprehensively utilize will occupy a large amount of land pollution environment,
Only simple required soil amount of stacking then reaches 50,000 mu.Due to containing there are many be detrimental to health and the nocuousness of biological growth
Impurity wastes valuable Sulphur ressource, and can pollute ring so not only taking up a large amount of soils while desulfurized gypsum is stacked
Border is endangered to zoology.
Carbide slag be calcium carbide hydrolysis obtain acetylene gas after with calcium hydroxide waste residue as main component.1t calcium carbide adds water can
More than 300 kilograms of acetylene gas are generated, while generating the industrial wastes of 10t solid content about 12%, are commonly called as calcium carbide screenings.In calcium carbide screenings
Containing a large amount of water, there are band filters pressing half wet process technique, wet-milling currently with the method that carbide slag can replace lime cement made of stones
Dry combustion method technique, prebake dry grinding dry combustion method technique, wet grinding and dry burning new dry process technique and directly enter mill dry grind dry combustion method new dry process,
But all there is the higher problem of energy consumption in these methods, the drying of contained humidity is carbide slag as manufacture of cement in calcium carbide screenings
The a great problem of raw material.
In recent years, sulphate aluminium cement becomes the new direction of domestic and international cement industry research and development, and clinker has
A series of superiority such as heat consumption is low, early strength is high, setting time is short, fabulous freeze-thaw resistance required for production, basicity is low
Energy.Existing sulphate aluminium cement have high-strength sulphate aluminium cement, self-stress aluminum sulfate cement, quick hardening sulphoaluminate cement,
5 cement types such as low-alkalinity sulphoaluminate cement, expansion sulphate aluminium cement, since existing sulphate aluminium cement advantage is aobvious
It writes, A wide selection of colours and designs, is now widely used in repairing, rush construction engineering, winter construction engineering, anticorrosive engineering.Apply stone in China
Cream decomposes co-producing cement and sulfuric acid this technology is started late, at present mature technology be granular material after drying with it is other
Raw material cooperation enters hollow rotary kiln through grinding and carries out decomposition calcination, and kiln atmosphere is difficult to control, and is easy to produce oxygen content in kiln
With oxygen combustion reaction, carbon needed for causing gypsum decomposition reaction occur for the problems such as higher with making the carbon part being added in raw material
Deficiency, resolution ratio and desulfurization degree reduce.
China's Industrial Solid Waste volume of cargo in storage is huge, and using difficulty height, while Sulphur ressource is short, and natural gypsum mine is utilized to produce sulphur
The higher cost of acid, country's sulfuric acid is usually to be produced using imported sulphur at present, and rising steadily for imported sulphur price leads to state
Interior sulfuric acid price rises steadily, and improves the use cost of sulfuric acid.
Summary of the invention
For above-mentioned the technical problems existing in the prior art, it is raw using Industrial Solid Waste that the object of the present invention is to provide a kind of
The system and method for producing sulphate aluminium cement co-producing sulfuric acid, the system and method can comprehensively utilize aluminium ash, desulfurized gypsum, calcium carbide
The Industrial Solid Wastes such as slag, red mud, raw material materials are extensive, cheap, produce high-performance sulphoaluminate cement clinker, the sulphur aluminium of production
Acid salt cement clinker can produce the additive of special cement or traditional cements, now be widely used in repairing, rush construction work
Journey, winter construction engineering, anticorrosive engineering etc..While producing sulphoaluminate cement clinker, the sulfuric acid of coproduction can be with
Reach the quality requirement of extraordinary acid, it can be in chemical industry, food, pharmaceuticals industry.
In order to solve problem above, the technical solution of the present invention is as follows:
A kind of system using Industrial Solid Waste production sulphate aluminium cement co-producing sulfuric acid, including balancing reservoir, filter press, drying
Device, flour mill, rotary kiln, cement grinding machine, cement storage tank, deduster, converter and absorption tower；Wherein, red mud, aluminium ash and electricity
Stone screenings adjusts dealkalize in balancing reservoir, and the slurry after dealkalize enters filter press filters pressing, baker drying, obtains dry material；It is de-
Sulphur gypsum enters baker heating, is changed into semi-hydrated gypsum；
After active carbon, semi-hydrated gypsum and the dry material mix in specific proportions, into flour mill grinding, mixture is sent
To flour mill grinding, the mixture after grinding, which is delivered in rotary kiln, to be calcined, and the pulverized coal conveying into rotary kiln；What calcining obtained
After sulfoaluminate clinker mixes in specific proportions with desulfurized gypsum, the grinding in cement grinding machine, obtained sulphate aluminium cement
It is delivered to cement storage tank storage；
The obtained gas containing sulfur dioxide is calcined in rotary kiln by deduster dedusting, is conveyed into being catalyzed in converter
Oxidation, obtained SO3Into absorbing in absorption tower, sulfuric acid is made.
Using solid waste aluminium ash, desulfurized gypsum, calcium carbide screenings and red mud etc. in the system, solid waste is both realized
The processing of object, and a kind of high performance material and sulfuric acid has been prepared, while reducing the production cost of sulfuric acid.
In calcination process, the addition of active carbon makes desulfurized gypsum can achieve enough resolution ratios and desulfurization degree.
Preferably, waste heat recovery apparatus, the flue gas pair discharged in rotary kiln are connected between the rotary kiln and deduster
Water heating in waste heat recovery apparatus, obtained high-temperature steam are passed through in the baker as heat medium, cigarette after cooling
Gas enters deduster dedusting.
Waste heat recovery apparatus is similar to heat exchanger, using the waste heat in flue gas to the liquid in waste heat recovery apparatus, such as water, into
Row heating, while obtaining high-temperature steam, reduces the temperature of flue gas, lower flue-gas temperature (300 DEG C) is to subsequent dedusting
Device and catalysis oxidation fixed bed not will cause biggish damage, extend the service life of follow-up equipment.Obtained high-temperature steam
Aluminium ash and desulfurized gypsum can be thermally dried.Two water desulfurized gypsums are changed into half water desulfurization stone due to needing to control
Cream, so needing the temperature of strict control heat medium.The temperature of high-temperature steam is much smaller than the temperature of flue gas, is convenient for technique
Control.
It is further preferred that after the high-temperature steam inflow baker heats material, then be passed through in balancing reservoir, it is right
Slurry in balancing reservoir is heated.
Various material needs are adjusted to slurry in balancing reservoir, and the adjusting of slurry needs higher temperature, if using
Other heat sources heat slurry, will cause a large amount of consumption of the energy, and herein, high-temperature steam is utilized twice,
The energy in the flue gas of rotary kiln discharge is utilized significantly, it is therefore prevented that the waste of energy, while reducing energy consumption.
Preferably, back water pump is additionally provided between the balancing reservoir and waste heat recovery apparatus, back water pump will be in balancing reservoir
Extra water is recycled in waste heat recovery apparatus.
Since the temperature of water in balancing reservoir is higher, when the water in balancing reservoir is recycled to waste heat recovery apparatus, to temperature
Higher water is heated, and can generate a large amount of high-temperature steam, and then provide enough heats to the drying of material for baker.
Meanwhile recycling water, recycling for water is realized, the waste of water resource is reduced.
Preferably, pickling dust-extraction unit and drying device are additionally provided between the converter and deduster.Pickling dedusting
Device can carry out pickling dedusting to the flue gas containing sulfur dioxide, reduce the quantity of suspended particulate in flue gas, improve two
The purity for the sulfuric acid being prepared can be improved in the purity of sulfur oxide.Drying device can be dried flue gas, can be improved
The concentration for the sulfuric acid being prepared, and then the sulfuric acid of high concentration and high-purity is prepared.
A method of sulphate aluminium cement co-producing sulfuric acid being produced using Industrial Solid Waste, is included the following steps:
1) red mud, aluminium ash, carbide slag and water to be put into balancing reservoir by setting ratio, is adjusted to slurry, heating is homogenized,
Homogenising time is 2-4 hours；
2) by material filters pressing, the drying after homogenizing, mixed material is obtained；By desulfurized gypsum thermal dehydration, it is changed into it
Semi-hydrated gypsum；
3) by the mixed material, active carbon and semi-hydrated gypsum after matching mixing twice, grinding is carried out；
4) material after grinding is calcined, when calcining, sulphur coal is put into mixture, burnt, obtain sulphur aluminic acid
Salt cement clinker and contain sulfur dioxide flue gas；
5) flue gas containing sulfur dioxide passes through dedusting, catalysis oxidation, absorption, and sulfuric acid is made；
Wherein, the mass ratio of active carbon, red mud, aluminium ash, carbide slag and desulfurized gypsum are as follows: 0.5-1:20-25:17-20:
20-25:23-25.
Calcium carbide screenings, red mud and the mixing of aluminium ash, industry water is added thereto, is prepared into slurry, then heat to slurry
Dealkalize, so the amount for the industry water for needing to add is less, has saved the use of water due to containing a large amount of moisture in calcium carbide screenings
Amount.Red mud, which is added in calcium carbide screenings, occurs hydration reaction, when the quality of active carbon, red mud, aluminium ash, carbide slag and desulfurized gypsum
Than are as follows: the Na in CaO and magma red mud when 0.5-1:20-25:17-20:20-25:23-25, in carbide slag2O mass ratio
In 3-4:1, hydration time is 2-4 hours for control, can be by most of Na in red mud2O removing, makes it be changed into NaOH and is dissolved in
In water, while the presence of aluminium ash plays facilitation to the dealkalize of red mud, so that carrying out dealkalize to red mud using this method, takes off
Alkali content is up to 90% or more.And slurry passes through the washing of water, can remove solvable in slurry (red mud, carbide slag and aluminium ash)
Property impurity, reduces impurity to the adverse effect of cement.
In addition, the dealkalize of red mud, the dehydration of calcium carbide screenings and the removal of impurities of material are saved work in one herein
Sequence reduces production cost.
Inventor, which imagines, replaces lime stone using more desulfurized gypsum part, but if when only with desulfurized gypsum,
It is calcined in rotary kiln, CaSO4It decomposes at 1250-1300 DEG C, but still has and be partially retained in internal desulfurization stone
Cream is not decomposed, causes the decomposition of desulfurized gypsum insufficient, in 3CaO3Al2O3·CaSO4Formation stages provide CaO
Amount it is insufficient, influence the quality of sulphate aluminium cement being prepared.CaSO4It could occur more thoroughly at 1350-1400 DEG C
Decomposition, a large amount of calcium oxide can be provided, and be also up to 3CaO3Al at this time2O3·CaSO4Decomposition temperature, produce
Raw impurity, can not prepare the sulphate aluminium cement of high quality.
So preparation is big while how replacing lime stone to prepare a large amount of sulphate aluminium cements using desulfurized gypsum part
The sulfur dioxide of amount, and be a urgent problem needed to be solved.
Inventor pass through validation trial, when in the feed be added active carbon when, with partial desulfurization gypsum can compared with
Redox reaction occurs under low temperature, and works as the mass ratio of active carbon, red mud, aluminium ash, carbide slag and desulfurized gypsum are as follows: 0.5-
1:20-25:17-20:20-25:23-25, and replaced using sulphur coal as a large amount of desulfurized gypsum when fuel, can be used
Quick lime prepares a large amount of sulphate aluminium cement, and provides a large amount of sulfur dioxide, for the preparation of sulphur provides raw material,
Energy consumption is also reduced simultaneously, reduces the production cost of cement.
Preferably, in step 1), adjust balancing reservoir in solid-to-liquid ratio be 1:3-4, aquation after red mud is mixed with carbide slag,
Na in CaO and red mud in carbide slag2The mass ratio of O is 3-4:1, hydration time 2-4 hours, obtains alkali-containing slurry.
Preferably, in step 1), the temperature in balancing reservoir after slurry heating is 60-70 DEG C.
In a heated state, filtering stock can remove the Na in the soluble impurity and former red mud in material2O and K2O,
When the solid-to-liquid ratio in slurry is 1:3-4, the alkaline matter in red mud and carbide slag more can be fully dissolved out.It will
Slurry after dealkalize carries out filter-press dehydration, the recycle of alkali liquor containing NaOH, and the solid matter after obtaining filters pressing can make dealkalize efficiency
Reach 90% or more.
Preferably, in step 2), the temperature that desulfurized gypsum thermal dehydration is changed into half water desulfurized gypsum is 140-150 DEG C.
Preferably, in step 3), the rate value of the cement slurry after grinding are as follows: basicity factor Cm0.95-0.98, alumina silica ratio:
2-3, aluminium-sulfur ratio: 3-4.
Preferably, in step 3), the granularity after grinding is less than 8 μm.
The grain composition of current more generally accepted cement optimum performance are as follows: 3-32 μm, because 3-32 μm of particle increases intensity
Length plays a major role, and especially 3-8 μm of particle is particularly important to cement performance, and content is more, and performance is better.
Preferably, in step 4), the temperature of calcining is 1250-1300 DEG C, calcination time 30-60min, coal dust firing
Excess air coefficient < 1.05.
Control is weak oxide atmosphere in rotary kiln, prevents reacting for active carbon and extra oxygen, guarantees dividing for desulfurized gypsum
Solution rate and desulfurization degree prepare the sulphoaluminate cement clinker of compound standard.
Preferably, in step 4), the chemical composition of the sulphoaluminate cement clinker includes: SiO23-10 parts by weight,
Al2O328-40 parts by weight, CaO 36-43 parts by weight, SO38-15 parts by weight, Fe2O31-3 parts by weight.
It is further preferred that in step 4), the mineral composition of the sulphoaluminate cement clinker are as follows:55-75 weight
Measure part, C2S 15-30 parts by weight, C4AF 3-6 parts by weight.
Preferably, in step 4), the sulphoaluminate cement clinker is with calcium sulphoaluminate (3CaO3Al2O3·CaSO4), silicon
Sour dicalcium (2CaOSiO2) and iron phase be main mineral facies, proportion is respectively 30-50%, 25-45% and 15-35%.
Preferably, in step 4), further include being heated using containing sulfur dioxide flue gas to water, obtain the step of high-temperature steam
Suddenly, the high-temperature steam is used as the heat medium to material and desulfurized gypsum progress heating, drying after homogenizing in step 2).
It is further preferred that in step 4), after the high-temperature steam is to the material and desulfurized gypsum heating, drying after homogenizing,
It is passed through the outside of the balancing reservoir in step 1), the slurry in balancing reservoir is heated, obtains cooling liquid, and will cooling liquid
It is recycled to high-temperature steam and obtains process.
Water is recycled, the waste of water is avoided, while having maximally utilised the cigarette discharged in rotary kiln
Heat in gas reduces the energy consumption of drying materials, solves the problems, such as that carbide slag drying cost is high.
Preferably, in step 4), sulfur content is greater than 6% in the coal dust.High-sulfur coal dust it is cheap, reduce coproduction
Cost, and the sulphur simple substance in coal dust reacts with oxygen and generates sulfur dioxide, and sulfur dioxide enters in flue gas, be used as preparing sulphur
The raw material of acid, improves the yield of sulfuric acid.
Advantageous effects of the invention are as follows:
(1) production technology of the invention prepares cement connection with independent red mud dealkalization technique, desulphurization gypsum calcination
It produces sulfur process to compare, there is biggish advantage.Red mud dealkalization carries out slurries with former red mud using carbide slag and mixes, adopts simultaneously
The method for reheating slurries with UTILIZATION OF VESIDUAL HEAT IN makes dealkalize efficiency reach 90% or more, and conventional red mud dealkalization, and efficiency peak is not
To 85%.Different from previous production producing sulfuric acid and jointly technology of producing cement, cement products prepared by the present invention belong to sulphur aluminic acid
Salt cement, rather than conventional portland cement.Sulphate aluminium cement mineralogical composition is with calcium sulphoaluminate (3CaO3Al2O3·
CaSO4), dicalcium silicate (2CaOSiO2) and iron phase be main mineral, the easy fired at 1250-1350 DEG C is a kind of
Early strong, high-strength, fast hard cementitious material, has the excellent characteristics such as high-impermeable, high anti-freezing, corrosion-resistant and low alkalinity；
(2) in environmental protection and the improvement of Industrial Solid Waste, the solution of essence has been obtained, in the link of cement burning,
Due to not using lime stone as the raw material of offer calcium base, when producing clinker co-producing sulfuric acid with traditional desulfurized gypsum,
CaO content is usually 64-67% in ordinary portland cement clinker, and sulphoaluminate cement clinker is only 38-48%, calcium content
Difference mean the CO discharged by calcination of calcium carbonate2It reduces；Along with firing temperature is 150-200 lower than portland cement
DEG C, energy consumption low energy further decreases CO2Discharge；Application life cycles evaluation theory obtains production of units clinker and is discharged
CO2Discharge amount is only the 40% of conventional Portland clinker.
(3) production has ease for operation, when producing sulfuric acid co-production portland cement with gypsum raw material, because can not
Make to contain higher SO in clinker3, the resolution ratio of strict control gypsum is needed, needs to add reducing agent and controls calcination process and be
Otherwise weakly reducing atmosphere will result in kiln condition shakiness or the underproof problem of clinker quality；And when coproduction sulphate aluminium cement, because
For the more demanding SO of clinker itself3Content, so not needing deliberately to control calcination atmosphere, the operability then produced is significantly
It improves.
(4) since calcining sulphoaluminate cement clinker required temperature is to be lower than burning silicate water between 1250-1300 DEG C
100 DEG C of the temperature of mud installs waste heat recovery utilizing equipment additional in the tail portion of rotary kiln, dries to the raw material for entering kiln, larger
Amplitude reduce coal, electric energy usage amount, so as to fundamentally realize it is energy-saving.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
The present invention is made in the following with reference to the drawings and specific embodiments further.
Embodiment 1
As shown in Figure 1, aquation after magma red mud, aluminium ash and carbide slag are mixed, solid-to-liquid ratio 1:4 obtain alkali-containing slurry, benefit
Alkali-containing slurry is heated with the waste heat of waste heat equipment recycling kiln gas, alkali-containing slurry temperature is made to maintain 60-70 DEG C, is made former red
The alkalinity of mud be reduced to original 10% hereinafter, ingredient slurries after filters pressing moisture be 43% (wt%), by drying naturally,
Moisture is down to 18% (wt%).Raw material after drying are sent into baker, and in terms of the solid matter after drying, red mud is accounted for
24.46 parts by weight, desulfurized gypsum account for 24.87 parts by weight, and carbide slag accounts for 25 parts by weight, and aluminium ash accounts for 19 parts by weight, and active carbon accounts for 1 weight
Measure part.It directly transports in hollow kiln, and puts into the high-sulfur coal calcination after grinding, firing temperature is 1270 DEG C, and calcination time is
60 minutes.The high-temperature kiln gas of generation passes through waste heat recovery apparatus, the high-temperature steam and hot water of by-product, to filters pressing material and desulfurized gypsum
Carry out indirect drying.The kiln gas of waste heat recovery apparatus out, gas temperature be reduced to 300 DEG C hereinafter, through dedusting, except wet purification,
It supplements air conditioning oxygen sulphur ratio and enters converter after drying, be SO through catalysis oxidation3, absorbed to obtain sulfuric acid with concentrated acid.Firing
The main object of clinker afterwards is mutually calcium sulphoaluminate, dicalcium silicate and iron phase, and proportion is respectively 50%, 30% and 15%, is belonged to
High-silicon high swage sulphate aluminium cement.(GB/T 17671-1999) is tested through cement standard cement mortar strength, 3 days and resistance to compression in 28 days
Intensity is respectively 31.4Mpa and 60.2Mpa.
Embodiment 2
Aquation after magma red mud, aluminium ash and carbide slag are mixed, solid-to-liquid ratio 1:3 obtain alkali-containing slurry, utilize waste heat equipment
The waste heat of recycling kiln gas heats alkali-containing slurry, so that alkali-containing slurry temperature is maintained 60-70 DEG C, makes the alkalinity of former red mud
Original 10% is reduced to hereinafter, ingredient slurries moisture after filters pressing is 30% (wt%), by drying naturally, moisture is down to
15% (wt%).Raw material after drying are sent into baker, and in terms of the solid matter after drying, red mud accounts for 24.46 weights
Part is measured, desulfurized gypsum accounts for 23 parts by weight, and carbide slag accounts for 20 parts by weight, and aluminium ash accounts for 17 parts by weight, and active carbon accounts for 1 parts by weight.Directly
It is conveyed into hollow kiln, and puts into the high-sulfur coal calcination after grinding, firing temperature is 1300 DEG C, and calcination time is 50 minutes.It produces
Raw high-temperature kiln gas passes through waste heat recovery apparatus, and the high-temperature steam and hot water of by-product carry out filters pressing material and desulfurized gypsum indirect
Drying.The kiln gas of waste heat recovery apparatus out, gas temperature be reduced to 300 DEG C hereinafter, through dedusting, except wet purification, supplement air
It adjusts oxygen sulphur ratio and enters converter after drying, be SO through catalysis oxidation3, absorbed to obtain sulfuric acid with concentrated acid.Clinker after firing
Main object is mutually calcium sulphoaluminate, dicalcium silicate and iron phase, and proportion is respectively 40%, 40% and 15%, belongs to high silicon high iron
Type sulphate aluminium cement.(GB/T 17671-1999) is tested through cement standard cement mortar strength, 3 days and 28 days compression strength difference
For 28.5Mpa and 56Mpa.
Embodiment 3
Aquation after magma red mud, aluminium ash and carbide slag are mixed, solid-to-liquid ratio 1:3 obtain alkali-containing slurry, utilize waste heat equipment
The waste heat of recycling kiln gas heats alkali-containing slurry, so that alkali-containing slurry temperature is maintained 60-70 DEG C, makes the alkalinity of former red mud
Original 10% is reduced to hereinafter, ingredient slurries moisture after filters pressing is 33% (wt%), by drying naturally, moisture is down to
13% (wt%).Raw material after drying are sent into baker, and in terms of the solid matter after drying, red mud accounts for 20 weight
Part, desulfurized gypsum accounts for 24 parts by weight, and carbide slag accounts for 23 parts by weight, and aluminium ash accounts for 19 parts by weight, and active carbon accounts for 0.8 parts by weight.Directly
It is conveyed into hollow kiln, and puts into the high-sulfur coal calcination after grinding, firing temperature is 1300 DEG C, and calcination time is 50 minutes.It produces
Raw high-temperature kiln gas passes through waste heat recovery apparatus, and the high-temperature steam and hot water of by-product carry out filters pressing material and desulfurized gypsum indirect
Drying.The kiln gas of waste heat recovery apparatus out, gas temperature be reduced to 300 DEG C hereinafter, through dedusting, except wet purification, supplement air
It adjusts oxygen sulphur ratio and enters converter after drying, be SO through catalysis oxidation3, absorbed to obtain sulfuric acid with concentrated acid.Clinker after firing
Main object is mutually calcium sulphoaluminate, dicalcium silicate and iron phase, and proportion is respectively 45%, 40% and 15%, belongs to high silicon high iron
Type sulphate aluminium cement.(GB/T 17671-1999) is tested through cement standard cement mortar strength, 3 days and 28 days compression strength difference
For 30.5Mpa and 64Mpa.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to invention protection scope
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
It is still within the scope of the present invention to make the creative labor the various modifications or changes that can be made.
Claims (9)
1. a kind of method using Industrial Solid Waste production sulphate aluminium cement co-producing sulfuric acid, characterized by the following steps:
1) red mud, aluminium ash, carbide slag and water are put into balancing reservoir by setting ratio, is adjusted to slurry, heating homogenizing, homogenizing
Temperature in pond after slurry heating is 60-70 DEG C, and the solid-to-liquid ratio adjusted in balancing reservoir is 1:3-4, and red mud is mixed with carbide slag
Aquation afterwards, Na in the CaO and red mud in carbide slag2The mass ratio of O is 3-4:1, hydration time 2-4 hours, obtains starching containing alkali
Liquid；
2) by material filters pressing, the drying after homogenizing, mixed material is obtained；By desulfurized gypsum thermal dehydration, it is made to be changed into half water
Gypsum；
3) by the mixed material, active carbon and semi-hydrated gypsum after matching mixing twice, grinding is carried out；
4) material after grinding is calcined, when calcining, sulphur coal is put into mixture, burnt, obtain aluminium sulfate water
Mud clinker and contain sulfur dioxide flue gas；
5) flue gas containing sulfur dioxide passes through dedusting, catalysis oxidation, absorption, and sulfuric acid is made；
Wherein, the mass ratio of active carbon, red mud, aluminium ash, carbide slag and desulfurized gypsum are as follows: 0.5-1:20-25:17-20:20-25:
23-25。
2. according to the method described in claim 1, it is characterized by: in step 3), the rate value of the cement slurry after grinding are as follows: alkali
Spend coefficient Cm0.95-0.98, alumina silica ratio: 2-3, aluminium-sulfur ratio: 3-4.
3. being forged according to the method described in claim 1, the temperature of calcining is 1250-1300 DEG C it is characterized by: in step 4)
The burning time is 30-60min, excess air coefficient < 1.05 of coal dust firing.
4. according to the method described in claim 1, it is characterized by: in step 4), the chemistry of the sulphoaluminate cement clinker
Composition includes: SiO23-10 parts by weight, Al2O328-40 parts by weight, CaO 36-43 parts by weight, SO38-15 parts by weight,
Fe2O31-3 parts by weight.
5. according to the method described in claim 1, it is characterized by: the sulphoaluminate cement clinker is in step 4) with sulphur aluminium
Sour calcium, dicalcium silicate and iron phase are main mineral facies, and proportion is respectively 30-50%, 25-45% and 15-35%.
6. according to the method described in claim 1, it is characterized by: further including using containing sulfur dioxide flue gas pair in step 4)
The step of water is heated, and high-temperature steam is obtained, the high-temperature steam are used as to the material and desulfurization stone after being homogenized in step 2
The heat medium of cream progress heating, drying.
7. according to the method described in claim 6, it is characterized by: the high-temperature steam is to the material after homogenizing in step 4)
After desulfurized gypsum heating, drying, it is passed through the outside of the balancing reservoir in step 1), the slurry in balancing reservoir is heated, is obtained
Cooling liquid, and cooling liquid is recycled to high-temperature steam and obtains process.
8. according to the method described in claim 1, it is characterized by comprising balancing reservoir, filter press, baker, flour mill, revolutions
Kiln, cement grinding machine, cement storage tank, deduster, converter and absorption tower；Wherein, red mud, aluminium ash and carbide slag are in balancing reservoir
Dealkalize is adjusted, the slurry after dealkalize enters filter press filters pressing, baker drying, obtains dry material；Desulfurized gypsum enters baker
Heating, is changed into semi-hydrated gypsum；
After active carbon, semi-hydrated gypsum and the dry material mix in specific proportions, into flour mill grinding, mixture is sent to powder
Grinding machine grinding, the mixture after grinding, which is delivered in rotary kiln, to be calcined, and the pulverized coal conveying into rotary kiln；Calcine obtained sulphur aluminium
After hydrochlorate clinker mixes in specific proportions with desulfurized gypsum, the grinding in cement grinding machine, obtained sulphate aluminium cement conveying
It is stored to cement storage tank；
The obtained gas containing sulfur dioxide is calcined in rotary kiln by deduster dedusting, is conveyed into being catalyzed oxygen in converter
Change, obtained SO3Into absorbing in absorption tower, sulfuric acid is made.
9. according to the method described in claim 8, it is characterized by: connecting the recycling that has surplus heat between the rotary kiln and deduster
Equipment, the flue gas discharged in rotary kiln heat the water in waste heat recovery apparatus, and obtained high-temperature steam is passed through the baker
Middle to be used as heat medium, flue gas after cooling enters deduster dedusting.
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| CN113683333B (en) * | 2021-07-22 | 2022-09-23 | 山东大学 | Desulfurized gypsum retarder, preparation method and application thereof in sulphoaluminate cement |
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| CN101343047B (en) * | 2008-08-26 | 2011-06-08 | 山东鲁北企业集团总公司 | Improved preparation technique for preparing sulphuric acid and cement with gypsum |
| CN103922622B (en) * | 2014-03-20 | 2015-11-04 | 山东大学 | A kind of technique utilizing aluminium ash to produce aluminosulfate cement |
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