CN108752005A - The technique that a kind of ardealite and red mud prepare composite ceramic material co-producing sulfuric acid - Google Patents

The technique that a kind of ardealite and red mud prepare composite ceramic material co-producing sulfuric acid Download PDF

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CN108752005A
CN108752005A CN201810712690.1A CN201810712690A CN108752005A CN 108752005 A CN108752005 A CN 108752005A CN 201810712690 A CN201810712690 A CN 201810712690A CN 108752005 A CN108752005 A CN 108752005A
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red mud
ceramic material
composite ceramic
sulfuric acid
ardealite
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陈肖虎
赵平源
唐道文
王丽远
郑凯
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Guizhou University
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Guizhou University
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Abstract

The present invention provides the techniques that a kind of ardealite and red mud prepare composite ceramic material co-producing sulfuric acid, include the following steps：Ardealite, red mud, additive and modifying agent are mixed and ground, raw material are made, is sent into roasting in kiln, clinker is made；Clinker obtained is dissolved out, and is separated by solid-liquid separation；By isolated residue through flotation, sulfide is detached to obtain；The sulfide isolated is processed, sulfuric acid is made；Isolated solution is prepared into high-purity alumina powder；High-purity alumina powder obtained and zirconium silicide, zirconium oxide, titanium nitride, titanium carbide, vanadium carbide, thorium oxide are distinguished and polished mix to obtain ceramic raw material；Ceramic raw material obtained is placed in high temperature sintering furnace and is sintered, Slow cooling obtains composite ceramic material after sintering.The present invention has relieving haperacidity and to prepare composite ceramic material at low cost, and waste residue utilization rate height, acid-making process is simple, prepares the high feature of good physical performance, the quality of composite ceramic material.

Description

The technique that a kind of ardealite and red mud prepare composite ceramic material co-producing sulfuric acid
Technical field
The present invention relates to the techniques that a kind of ardealite and red mud prepare composite ceramic material co-producing sulfuric acid, belong to chemical metallurgy Field.
Background technology
Ardealite refer in phosphoric acid production with sulfuric acid treating phosphorite when the solid slag that generates, main component is sulfuric acid Calcium（CaSO4）, content generally can reach 70-90% or so.In addition, ardealite also contains plurality of impurities：Undecomposed phosphorus ore, Phosphoric acid, calcirm-fluoride, iron, aluminium compound, acid non-soluble substance, organic matter of non-washes clean etc..Ardealite is discharged every year about in China 20000000 tons, add up nearly hundred million tons of discharge capacity.For utilization rate of the ardealite in terms of building materials less than 5%, a large amount of gypsum stacks occupy soil Ground seriously pollutes environment.
Red mud is to refine the waste generated in alumina process with bauxite.It is in crimson color muddy because it is rich in iron And it gains the name.1 ton of aluminium oxide is often produced, 1.0-2.0 tons of red mud is about generated.The year yield of China's red mud is about 1.0 hundred million tons, is tired out It is about 500,000,000 tons to count volume of cargo in storage.
Composite ceramic material has the advantages that good physical performance, quality are high.Composite ceramic material is relative to ceramic material Purposes is also more extensive.It is to use high-purity alumina powder and other originals mostly but in the production of existing composite ceramic material Material processing is prepared, and the complex manufacturing technology of existing high-purity alumina powder, production cost are high, lead to high-purity alumina powder valence Lattice are expensive, greatly increase the production cost of composite ceramic material.
It is now currently, seldom for the technology of the comprehensive utilization of ardealite and red mud, it is substantially focused on building materials and paves the way Traditional field, which results in the waste of a large amount of high value ingredients in ardealite and red mud, added value is very low.And by ardealite and Red mud comprehensively utilizes to prepare composite ceramic material, while the technique of co-producing sulfuric acid, has not been reported.
Goal of the invention
The object of the present invention is to provide the techniques that a kind of ardealite and red mud prepare composite ceramic material co-producing sulfuric acid.This hair Bright have relieving haperacidity and to prepare composite ceramic material at low cost, and waste residue utilization rate height, acid-making process is simple, prepares composite ceramic material Good physical performance, the high feature of quality.
Technical scheme of the present invention
A kind of ardealite and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, include the following steps：
A, ardealite, red mud, additive and modifying agent are mixed and is ground and raw material are made, be sent into roasting in kiln, clinker is made；
B, it is 4-6 clinker made from step A to be consolidated volume ratio with liquid:1 carries out water mill dissolution, and is separated by solid-liquid separation；
C, by residue isolated step B through flotation, sulfide is detached to obtain；
D, the step C sulfide isolated is placed under the oxygen-enriched environment of 30-50%, 3-5h is roasted at 800-1200 DEG C, roasted The flue gas of generation is absorbed using the concentrated sulfuric acid after vanadic anhydride catalysis reaction, sulfuric acid is made；
E, the stirring of calcium oxide constant temperature is added in the isolated solution of step B, filters to obtain high-purity sodium aluminate solution, to it is high-purity partially CO is passed through in sodium aluminate solution2Gas is no longer generated to white precipitate, and aluminium hydroxide is obtained after then filtering out white precipitate；
F, aluminium hydroxide addition hydrochloric acid made from step E is stirred and is washed 3-4 times, then be stirred washing, be washed to filtrate and be in neutrality, High purity aluminium hydroxide is obtained, high purity aluminium hydroxide is roasted, high-purity alumina powder is obtained；
G, by high-purity alumina powder made from step F and zirconium silicide, zirconium oxide, titanium nitride, titanium carbide, vanadium carbide, thorium oxide point It is not polished to mix to obtain ceramic raw material；
H, ceramic raw material obtained in step G is placed in high temperature sintering furnace and is sintered, Slow cooling obtains composite ceramics after sintering Material.
Ardealite and red mud above-mentioned are prepared in the technique of composite ceramic material co-producing sulfuric acid, in step A, the red mud The red mud generated for alumina producing Bayer process；The additive is sodium carbonate, sodium sulphate or caustic soda；The modifying agent is smokeless Coal, carbon or gangue.
Ardealite and red mud above-mentioned are prepared in the technique of composite ceramic material co-producing sulfuric acid, in step A, the raw material In, ardealite and red mud are according to 1:The ratio of 0.8-2 weight ratios mixes, and additive adding proportion presses contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation is 1:1 addition, the mixed proportion of modifying agent are the 10-25% of raw material total weight.
Ardealite and red mud above-mentioned are prepared in the technique of composite ceramic material co-producing sulfuric acid, and in step A, the kiln is work Industry rotary kiln, Industry Tunnel Kiln or industrial shaft kiln.
Ardealite and red mud above-mentioned are prepared in the technique of composite ceramic material co-producing sulfuric acid, are in temperature in step A Roasting time 1-2h at 1000-1350 DEG C.
Ardealite and red mud above-mentioned are prepared in the technique of composite ceramic material co-producing sulfuric acid, in step E, the calcium oxide Dosage be 7-12g/L；Solution isolated step B is wherein added to temperature when analysis carbonate-free lime constant temperature stirs is 80-90 DEG C, mixing time 1.5-2h.
Ardealite and red mud above-mentioned are prepared in the technique of composite ceramic material co-producing sulfuric acid, in step F, the hydrochloric acid A concentration of 40-60g/L, temperature are 40-60 DEG C.
Ardealite and red mud above-mentioned are prepared in the technique of composite ceramic material co-producing sulfuric acid, in step F, the High Purity Hydrogen The calcination temperature of aluminium oxide calcining is 400-600 DEG C, roasting time 2-3h.
Ardealite and red mud above-mentioned are prepared in the technique of composite ceramic material co-producing sulfuric acid, in step G, by weight Meter, the composite ceramic material include 8-12 parts of high-purity alumina powder, 25-28 parts of zirconium silicide, 10-15 parts of zirconium oxide, titanium nitride 15-20 parts, 15-20 parts of titanium carbide, 12-15 parts of vanadium carbide, 5-10 parts of thorium oxide.
Ardealite and red mud above-mentioned are prepared in the technique of composite ceramic material co-producing sulfuric acid, in step H, high temperature sintering furnace It is increased to 750-780 DEG C according to the heating rate of 40-60 DEG C/min, is sintered 2.8-3.2h at such a temperature；According still further to 40-60 DEG C/heating rate of min is warming up to 1125-1155 DEG C, the constant sintering 2-2.3h of temperature is kept, Slow cooling obtains compound after sintering Ceramic material.
The present invention is by by ardealite and red mud reaction, recombination, making utility.The net reaction of principle is：
CaSO4（Ardealite）+ Na2O·SiO2·Al2O3（Red mud）→ Na2O·Al2O3 + CaO·SiO2↓+[sulphur]
From the reaction equation it is found that with the SiO in the CaO and red mud in ardealite2Generate calcium orthosilicate（ CaO·SiO2↓）Afterwards, Obtain soluble fabulous sodium aluminate（Na2O·Al2O3）.[sulphur] in reaction equation refers to by raw material doping and modification Agent technique, the metal sulfide of generation；After leaching the sodium aluminate in clinker, obtained sediment flotation be can be obtained into metal sulphur Compound.
Advantageous effect
1, the present invention and is added after additive and modifying agent by using ardealite and red mud as raw material, in high-temperature roasting Technique under obtain the clinker of main silicate-containing, aluminate and sulfide, and the main component of the aluminate is sodium aluminate, will Sodium aluminate it is water-soluble go out after may be recovered, and after solid residue flotation, obtain sulfide, sulfuric acid prepared using sulfide,
High-purity alumina powder is prepared by the sodium aluminate of recycling, high-purity alumina powder and other raw materials are prepared into composite ceramics material Therefore material is substantially reduced due to mainly using ardealite and red mud as raw material, adding other a small amount of substances in entire technique The cost input of relieving haperacidity and composite ceramic material.The utilization rate for also greatly increasing ardealite and waste red mud residues, to alleviate phosphorus Gypsum and red mud have important contribution to the pollution of environment.
2, the present invention obtains after the solid residue flotation in technique sulfide, sulfuric acid, relieving haperacidity is prepared using sulfide Cost it is low, acid-making process is simple.
3, the present invention by raw material by roasting after, obtained ingredient is clearly demarcated, aluminium mainly with aluminic acid na form exist, profit The characteristic of water is highly soluble in sodium aluminate, can be simple and quick be isolated and be used to prepare high-purity alumina powder, by high pure oxygen Change aluminium powder and other raw materials and prepare composite ceramic material, composite ceramic material good physical performance, quality are high, composite ceramic material at This is low.
Further to prove that the effect of the present invention, inventor have done following experiment.
1, the measurement of composite ceramic material
Inventor will determine its tensile strength, bending strength respectively to the composite ceramic material in following five groups of embodiments and resist Compressive Strength, measurement result are as follows：
By the above measurement result table can be seen that the composite ceramic material draws to stretch intensity, bending strength and compression strength high, Composite ceramic material has the characteristics that good physical performance, quality are high.
Specific implementation mode
With reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
The embodiment of the present invention
Embodiment 1：A kind of ardealite and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, and steps are as follows：
A, ardealite, Bayer red mud, sodium carbonate and anthracite are mixed and is ground and raw material are made, be sent into industrial rotary kiln in temperature Clinker is made in roasting time 1.5h at 1000 DEG C of degree；Wherein, ardealite and Bayer red mud are according to 1:The ratio of 0.8 weight ratio is mixed It closes, sodium carbonate adding proportion presses contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation is 1:1 addition, it is anthracitic mixed Composition and division in a proportion example is the 10% of raw material total weight；
B, clinker made from step A is consolidated into volume ratio as 4 with liquid:1 carries out water mill dissolution, and is separated by solid-liquid separation；
C, by residue isolated step B through flotation, sulfide is detached to obtain；
D, the step C sulfide isolated is placed under 30% oxygen-enriched environment, 5h is roasted at 800 DEG C, roast the flue gas of generation After vanadic anhydride catalysis reaction, is absorbed using the concentrated sulfuric acid, sulfuric acid is made；
E, the stirring of calcium oxide constant temperature is added in the isolated solution of step B, filters to obtain high-purity sodium aluminate solution, to it is high-purity partially CO is passed through in sodium aluminate solution2Gas is no longer generated to white precipitate, and aluminium hydroxide is obtained after then filtering out white precipitate；Wherein The dosage of the calcium oxide is 7g/L；Wherein solution isolated step B is added when analysis carbonate-free lime constant temperature stirs Temperature is 80 DEG C, mixing time 1.5h；
F, aluminium hydroxide addition hydrochloric acid made from step E is stirred and is washed 3 times, then be stirred washing, be washed to filtrate and be in neutrality, obtain High purity aluminium hydroxide roasts high purity aluminium hydroxide, obtains high-purity alumina powder；A concentration of 40g/L of the wherein described hydrochloric acid, temperature It is 40 DEG C；The calcination temperature of the high purity aluminium hydroxide roasting is 400 DEG C, roasting time 2h, and gained alumina powder is high-purity The purity of alumina powder, high-purity alumina powder is 99.99%；
G, by high-purity alumina powder made from step F and zirconium silicide, zirconium oxide, titanium nitride, titanium carbide, vanadium carbide, thorium oxide point It is not polished to mix to obtain ceramic raw material；Wherein by weight, the composite ceramic material includes 8 parts of high-purity alumina powder, 25 parts of zirconium silicide, 10 parts of zirconium oxide, 15 parts of titanium nitride, 15 parts of titanium carbide, 12 parts of vanadium carbide, 5 parts of thorium oxide；
H, ceramic raw material obtained in step G is placed in high temperature sintering furnace, high temperature sintering furnace according to 40 DEG C/min heating Speed is increased to 750 DEG C, is sintered 2.8h at such a temperature；1125 DEG C are increased to according still further to the heating rate of 40 DEG C/min, is kept The constant sintering 2h of temperature, Slow cooling obtains composite ceramic material after sintering.
Embodiment 2：A kind of ardealite and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, and steps are as follows：
A, ardealite, Bayer red mud, sodium sulphate and carbon are mixed and is ground and raw material are made, be sent into industrial rotary kiln in temperature Clinker is made in roasting time 2h at 1200 DEG C；Wherein, ardealite and Bayer red mud are according to 1:The ratio of 1.1 weight ratios mixes, and burns Alkali adding proportion presses contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation is 1:The mixed proportion of 1 addition, carbon is raw material The 15% of total weight；
B, clinker made from step A is consolidated into volume ratio as 5 with liquid:1 carries out water mill dissolution, and is separated by solid-liquid separation；
C, by residue isolated step B through flotation, sulfide is detached to obtain；
D, the step C sulfide isolated is placed under 35% oxygen-enriched environment, 4h is roasted at 900 DEG C, roast the flue gas of generation After vanadic anhydride catalysis reaction, is absorbed using the concentrated sulfuric acid, sulfuric acid is made；
E, the stirring of calcium oxide constant temperature is added in the isolated solution of step B, filters to obtain high-purity sodium aluminate solution, to it is high-purity partially CO is passed through in sodium aluminate solution2Gas is no longer generated to white precipitate, and aluminium hydroxide is obtained after then filtering out white precipitate；Wherein The dosage of the calcium oxide is 9g/L；Wherein solution isolated step B is added when analysis carbonate-free lime constant temperature stirs Temperature is 85 DEG C, mixing time 2h；
F, aluminium hydroxide addition hydrochloric acid made from step E is stirred and is washed 4 times, then be stirred washing, be washed to filtrate and be in neutrality, obtain High purity aluminium hydroxide roasts high purity aluminium hydroxide, obtains high-purity alumina powder；A concentration of 50g/L of the wherein described hydrochloric acid, temperature It is 40 DEG C；The calcination temperature of the high purity aluminium hydroxide roasting is 450 DEG C, roasting time 2.5h, and gained alumina powder is height The purity of pure zirconia aluminium powder, high-purity alumina powder is 99.991%；
G, by high-purity alumina powder made from step F and zirconium silicide, zirconium oxide, titanium nitride, titanium carbide, vanadium carbide, thorium oxide point It is not polished to mix to obtain ceramic raw material；Wherein by weight, the composite ceramic material includes 12 parts of high-purity alumina powder, 25 parts of zirconium silicide, 15 parts of zirconium oxide, 15 parts of titanium nitride, 20 parts of titanium carbide, 12 parts of vanadium carbide, 10 parts of thorium oxide；
H, ceramic raw material obtained in step G is placed in high temperature sintering furnace, high temperature sintering furnace according to 50 DEG C/min heating Speed is increased to 760 DEG C, is sintered 2.9h at such a temperature；1135 DEG C are increased to according still further to the heating rate of 50 DEG C/min, is kept The constant sintering 2.1h of temperature, Slow cooling obtains composite ceramic material after sintering.
Embodiment 3：A kind of ardealite and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, and steps are as follows：
A, ardealite, Bayer red mud, caustic soda and gangue are mixed and is ground and raw material are made, be sent into industrial rotary kiln in temperature Clinker is made in roasting time 1.5h at 1300 DEG C；Wherein, ardealite and Bayer red mud are according to 1:The ratio of 1.4 weight ratios mixes, Sodium carbonate adding proportion presses contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation is 1:1 addition, the mixing ratio of gangue Example is the 20% of raw material total weight；
B, clinker made from step A is consolidated into volume ratio as 6 with liquid:1 carries out water mill dissolution, and is separated by solid-liquid separation；
C, by residue isolated step B through flotation, sulfide is detached to obtain；
D, the step C sulfide isolated is placed under 45% oxygen-enriched environment, 3h is roasted at 1000 DEG C, roast the cigarette of generation Gas is absorbed using the concentrated sulfuric acid after vanadic anhydride catalysis reaction, sulfuric acid is made；
E, the stirring of calcium oxide constant temperature is added in the isolated solution of step B, filters to obtain high-purity sodium aluminate solution, to it is high-purity partially CO is passed through in sodium aluminate solution2Gas is no longer generated to white precipitate, and aluminium hydroxide is obtained after then filtering out white precipitate；Wherein The dosage of the calcium oxide is 11g/L；Wherein solution isolated step B is added when analysis carbonate-free lime constant temperature stirs Temperature is 90 DEG C, mixing time 1.5h；
F, aluminium hydroxide addition hydrochloric acid made from step E is stirred and is washed 3 times, then be stirred washing, be washed to filtrate and be in neutrality, obtain High purity aluminium hydroxide roasts high purity aluminium hydroxide, obtains high-purity alumina powder；A concentration of 60g/L of the wherein described hydrochloric acid, temperature It is 50 DEG C；The calcination temperature of the high purity aluminium hydroxide roasting is 500 DEG C, roasting time 3h, and gained alumina powder is high-purity The purity of alumina powder, high-purity alumina powder is 99.992%；
G, by high-purity alumina powder made from step F and zirconium silicide, zirconium oxide, titanium nitride, titanium carbide, vanadium carbide, thorium oxide point It is not polished to mix to obtain ceramic raw material；Wherein by weight, the composite ceramic material includes 10 parts of high-purity alumina powder, 25 parts of zirconium silicide, 13 parts of zirconium oxide, 15 parts of titanium nitride, 18 parts of titanium carbide, 14 parts of vanadium carbide, 7 parts of thorium oxide；
H, ceramic raw material obtained in step G is placed in high temperature sintering furnace, high temperature sintering furnace according to 60 DEG C/min heating Speed is increased to 770 DEG C, is sintered 3h at such a temperature；1145 DEG C are increased to according still further to the heating rate of 60 DEG C/min, keeps temperature Constant sintering 2.2h is spent, Slow cooling obtains composite ceramic material after sintering.
Embodiment 4：A kind of ardealite and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, and steps are as follows：
A, ardealite, Bayer red mud, sodium carbonate and gangue are mixed and is ground and raw material are made, be sent into industrial rotary kiln in temperature Clinker is made in roasting time 1h at 1350 DEG C of degree；Wherein, ardealite and Bayer red mud are according to 1:The ratio of 1.7 weight ratios mixes, Caustic soda adding proportion presses contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation is 1:1 addition, the mixed proportion of gangue It is the 25% of raw material total weight；
B, clinker made from step A is consolidated into volume ratio as 5 with liquid:1 carries out water mill dissolution, and is separated by solid-liquid separation；
C, by residue isolated step B through flotation, sulfide is detached to obtain；
D, the step C sulfide isolated is placed under 45% oxygen-enriched environment, 3h is roasted at 1200 DEG C, roast the cigarette of generation Gas is absorbed using the concentrated sulfuric acid after vanadic anhydride catalysis reaction, sulfuric acid is made；
E, the stirring of calcium oxide constant temperature is added in the isolated solution of step B, filters to obtain high-purity sodium aluminate solution, to it is high-purity partially CO is passed through in sodium aluminate solution2Gas is no longer generated to white precipitate, and aluminium hydroxide is obtained after then filtering out white precipitate；Wherein The dosage of the calcium oxide is 12g/L；Wherein solution isolated step B is added when analysis carbonate-free lime constant temperature stirs Temperature is 90 DEG C, mixing time 2h；
F, aluminium hydroxide addition hydrochloric acid made from step E is stirred and is washed 4 times, then be stirred washing, be washed to filtrate and be in neutrality, obtain High purity aluminium hydroxide roasts high purity aluminium hydroxide, obtains high-purity alumina powder；A concentration of 45g/L of the wherein described hydrochloric acid, temperature It is 60 DEG C；The calcination temperature of the high purity aluminium hydroxide roasting is 550 DEG C, roasting time 2h, and gained alumina powder is high-purity The purity of alumina powder, high-purity alumina powder is 99.991%；
G, by high-purity alumina powder made from step F and zirconium silicide, zirconium oxide, titanium nitride, titanium carbide, vanadium carbide, thorium oxide point It is not polished to mix to obtain ceramic raw material；Wherein by weight, the composite ceramic material includes 10 parts of high-purity alumina powder, 27 parts of zirconium silicide, 13 parts of zirconium oxide, 18 parts of titanium nitride, 17 parts of titanium carbide, 15 parts of vanadium carbide, 8 parts of thorium oxide；
H, ceramic raw material obtained in step G is placed in high temperature sintering furnace, high temperature sintering furnace according to 50 DEG C/min heating Speed is increased to 760 DEG C, is sintered 3.1h at such a temperature；1150 DEG C are increased to according still further to the heating rate of 50 DEG C/min, is kept The constant sintering 2.1h of temperature, Slow cooling obtains composite ceramic material after sintering.
Embodiment 5：A kind of ardealite and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, and steps are as follows：
A, ardealite, Bayer red mud, sodium sulphate and anthracite are mixed and is ground and raw material are made, be sent into industrial rotary kiln in temperature Clinker is made in roasting time 2h at 1200 DEG C of degree；Wherein, ardealite and Bayer red mud are according to 1:The ratio of 2 weight ratios mixes, and burns Alkali adding proportion presses contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation is 1:1 addition, anthracitic mixed proportion are The 20% of raw material total weight；
B, clinker made from step A is consolidated into volume ratio as 4 with liquid:1 carries out water mill dissolution, and is separated by solid-liquid separation；
C, by residue isolated step B through flotation, sulfide is detached to obtain；
D, the step C sulfide isolated is placed under 50% oxygen-enriched environment, 4h is roasted at 1100 DEG C, roast the cigarette of generation Gas is absorbed using the concentrated sulfuric acid after vanadic anhydride catalysis reaction, sulfuric acid is made；
E, the stirring of calcium oxide constant temperature is added in the isolated solution of step B, filters to obtain high-purity sodium aluminate solution, to it is high-purity partially CO is passed through in sodium aluminate solution2Gas is no longer generated to white precipitate, and aluminium hydroxide is obtained after then filtering out white precipitate；Wherein The dosage of the calcium oxide is 10g/L；Wherein solution isolated step B is added when analysis carbonate-free lime constant temperature stirs Temperature is 85 DEG C, mixing time 1.5h；
F, aluminium hydroxide addition hydrochloric acid made from step E is stirred and is washed 3 times, then be stirred washing, be washed to filtrate and be in neutrality, obtain High purity aluminium hydroxide roasts high purity aluminium hydroxide, obtains high-purity alumina powder；A concentration of 50g/L of the wherein described hydrochloric acid, temperature It is 55 DEG C；The calcination temperature of the high purity aluminium hydroxide roasting is 600 DEG C, roasting time 3h, and gained alumina powder is high-purity The purity of alumina powder, high-purity alumina powder is 99.993%；
G, by high-purity alumina powder made from step F and zirconium silicide, zirconium oxide, titanium nitride, titanium carbide, vanadium carbide, thorium oxide point It is not polished to mix to obtain ceramic raw material；Wherein by weight, the composite ceramic material includes 12 parts of high-purity alumina powder, 28 parts of zirconium silicide, 15 parts of zirconium oxide, 20 parts of titanium nitride, 20 parts of titanium carbide, 15 parts of vanadium carbide, 10 parts of thorium oxide；
H, ceramic raw material obtained in step G is placed in high temperature sintering furnace, high temperature sintering furnace according to 60 DEG C/min heating Speed is increased to 780 DEG C, is sintered 3.2h at such a temperature；1155 DEG C are increased to according still further to the heating rate of 60 DEG C/min, is kept The constant sintering 2.3h of temperature, Slow cooling obtains composite ceramic material after sintering.

Claims (10)

1. the technique that a kind of ardealite and red mud prepare composite ceramic material co-producing sulfuric acid, which is characterized in that include the following steps：
A, ardealite, red mud, additive and modifying agent are mixed and is ground and raw material are made, be sent into roasting in kiln, clinker is made；
B, it is 4-6 clinker made from step A to be consolidated volume ratio with liquid:1 carries out water mill dissolution, and is separated by solid-liquid separation；
C, by residue isolated step B through flotation, sulfide is detached to obtain；
D, the step C sulfide isolated is placed under the oxygen-enriched environment of 30-50%, 3-5h is roasted at 800-1200 DEG C, roasted The flue gas of generation is absorbed using the concentrated sulfuric acid after vanadic anhydride catalysis reaction, sulfuric acid is made；
E, the stirring of calcium oxide constant temperature is added in the isolated solution of step B, filters to obtain high-purity sodium aluminate solution, to it is high-purity partially CO is passed through in sodium aluminate solution2Gas is no longer generated to white precipitate, and aluminium hydroxide is obtained after then filtering out white precipitate；
F, aluminium hydroxide addition hydrochloric acid made from step E is stirred and is washed 3-4 times, then be stirred washing, be washed to filtrate and be in neutrality, High purity aluminium hydroxide is obtained, high purity aluminium hydroxide is roasted, high-purity alumina powder is obtained；
G, by high-purity alumina powder made from step F and zirconium silicide, zirconium oxide, titanium nitride, titanium carbide, vanadium carbide, thorium oxide point It is not polished to mix to obtain ceramic raw material；
H, ceramic raw material obtained in step G is placed in high temperature sintering furnace and is sintered, Slow cooling obtains composite ceramics after sintering Material.
2. ardealite according to claim 1 and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, feature exists In：In step A, the red mud is the red mud that alumina producing Bayer process generates；The additive be sodium carbonate, sodium sulphate or Caustic soda；The modifying agent is anthracite, carbon or gangue.
3. ardealite according to claim 1 and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, feature exists In：In step A, in the raw material, ardealite and red mud are according to 1:The ratio of 0.8-2 weight ratios mixes, and additive adds ratio Example is by contained Na in raw material2O and A12O3+Fe2O3The molecular proportion of summation is 1:The mixed proportion of 1 addition, modifying agent is raw material gross weight The 10-25% of amount.
4. ardealite according to claim 1 and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, feature exists In：In step A, the kiln is industrial rotary kiln, Industry Tunnel Kiln or industrial shaft kiln.
5. ardealite according to claim 1 and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, feature exists In：It is the roasting time 1-2h at 1000-1350 DEG C of temperature in step A.
6. ardealite according to claim 1 and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, feature exists In：In step E, the dosage of the calcium oxide is 7-12g/L；Analysis pure zirconia wherein is added in solution isolated step B Temperature when calcium constant temperature stirs is 80-90 DEG C, mixing time 1.5-2h.
7. ardealite according to claim 1 and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, feature exists In：In step F, a concentration of 40-60g/L of the hydrochloric acid, temperature is 40-60 DEG C.
8. ardealite according to claim 1 and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, feature exists In：In step F, the calcination temperature of the high purity aluminium hydroxide roasting is 400-600 DEG C, roasting time 2-3h.
9. ardealite according to claim 1 and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, feature exists In：In step G, by weight, the composite ceramic material includes 8-12 parts of high-purity alumina powder, 25-28 parts of zirconium silicide, oxygen Change 10-15 parts of zirconium, 15-20 parts of titanium nitride, 15-20 parts of titanium carbide, 12-15 parts of vanadium carbide, 5-10 parts of thorium oxide.
10. ardealite according to claim 1 and red mud prepare the technique of composite ceramic material co-producing sulfuric acid, feature exists In：In step H, be by the way that ceramic raw material is placed in high temperature sintering furnace, high temperature sintering furnace according to 40-60 DEG C/min heating Speed is increased to 750-780 DEG C, is sintered 2.8-3.2h at such a temperature；It is warming up to according still further to the heating rate of 40-60 DEG C/min 1125-1155 DEG C, the constant sintering 2-2.3h of temperature is kept, Slow cooling obtains composite ceramic material after sintering.
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