CN103569971A - Method for preparing sulfuric acid by baking nickel-molybdenum ore in fluidized bed combustion boiler - Google Patents
Method for preparing sulfuric acid by baking nickel-molybdenum ore in fluidized bed combustion boiler Download PDFInfo
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- CN103569971A CN103569971A CN201310547222.0A CN201310547222A CN103569971A CN 103569971 A CN103569971 A CN 103569971A CN 201310547222 A CN201310547222 A CN 201310547222A CN 103569971 A CN103569971 A CN 103569971A
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- sulfuric acid
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Abstract
The invention relates to a method for preparing sulfuric acid by baking nickel-molybdenum ore in a fluidized bed combustion boiler, belonging to the technical field of preparation of the sulfuric acid. The method comprises the following steps: mixing the nickel-molybdenum ore with a sulfur-containing material until the content of S by weight in the mixed material is 20-35 percent and the content of water by weight is 5-15 percent; placing the mixed material in the fluidized bed combustion boiler; introducing rich oxygen and roasting so as to obtain the sulfuric acid. The method has the beneficial effects that the production cost can be reduced, and the industrial sulfuric acid product which meets GB/T1534-2001 national standard is prepared.
Description
Technical field
The invention belongs to the technical field of preparing sulfuric acid, be specifically related to a kind of method that boiling roaster nickel-molybdenum ore is prepared sulfuric acid.
Background technology
The preparation method of industrial sulphuric acid, because adopting the difference of raw material, is mainly divided into metallurgical off-gas acid-making, pyrite-based sulfuric acid production, acid production with sulphur and phosphogypsum relieving haperacidity etc.
1, metallurgical off-gas acid-making
Along with developing rapidly of China's non-ferrous metals industry, the improvement of flue gas during smelting, is mainly the SO utilizing wherein
2produce sulfuric acid, the non-ferrous metal major parts such as copper, lead, zinc, nickel, gold, cobalt, molybdenum, chromium are sulphide oress, in smelting process, because sulphide ores is under pyroreaction, emits and contain SO
2flue gas, its flue gas composition is different with characteristic, composition and the smelting technology of nonferrous metals ore, its SO
2volumetric concentration, 0.05%～25.0%, is considered the SO in this flue gas from environment protection and the utilization of resources
2the overwhelming majority all must be utilized and be reclaimed, and its retrieving arrangement is exactly supporting byproduct engineering.Discharge the SO in flue gas
2the overwhelming majority adopts ordinary method to prepare industrial sulphuric acid, for SO
2flue gas application unstable state conversion process and WSA technique that content is lower are made, for SO
2the flue gas that content is higher is made by LuReeTM technique.For SO
2the high ordinary method that adopts of content, equipment is ripe, and production cost is lower, and for SO
2low unstable state and the WSA processing method of being used in of content, just exists use apparatus expensive, the shortcoming that production cost is high.
2, pyrite-based sulfuric acid production
Sulfurous iron ore is China's homegrown resource, China occupies 72.70% of global total amount, pyrite-based sulfuric acid production has played part not enough outside supplementary metallurgical off-gas acid-making (this is the acid that environmental requirement must be produced) and phosphogypsum relieving haperacidity (making full use of world's phosphogypsum resource), plays Balanceregulation.China is through oneself's research and development and external introduction of decades, and its Technology, equipment level and sulphuric acid plant have approached foreign level.Because 2000 Nian Hou， China bargh production costs progressively raise, in addition after financial crisis in 2007, the progressively atrophy of ，Qi mine manufacturing enterprise that goes way down of industrial sulphuric acid price, economic benefit declines.
3, acid production with sulphur
Before the nineties in 20th century, Sulfur price is low, the whole world mostly adopts acid production with sulphur, large large impact pyrite-based sulfuric acid production enterprise, after 2002, Sulfur price rises suddenly and sharply, industrial sulphuric acid enterprise cost is increased, benefit degradation, its production cost is more much higher than pyrite-based sulfuric acid production on the contrary, and its processing requirement equipment is on the contrary very ripe.
4, nickel-molybdenum ore relieving haperacidity
China's zunyi, guizhou and Zhangjiajie, Hunan Yun are hiding abundant nickel-molybdenum ore resource, but molybdenum nickel grade is very not high, high containing C, and complicated component belongs to difficult choosing, difficult smelting mineral, and the technique of its processing nickel-molybdenum ore is divided into pyrogenic process and wet processing.
A, thermal process: domestic traditional technology is that direct-reduction roasting method is produced dynamax; Or with oxidizing roasting, after sodium-salt calcination, the serial molybdenum products such as molybdic acid, molybdenum oxide or ammonium molybdate are produced in water logging.But the SO that these two kinds of technological processs produce
2flue gas, environmental pollution is large, and product specification is low, and S, C in nickel-molybdenum ore are not utilized, and due to the existence of C, also exist the ropy shortcoming of the vitriol oil of preparation.
B, wet processing: adopt alkaline oxygenated reagent N aCLO+NaOH directly to decompose, or decompose with nitric acid, from leach liquor, produce again the series product such as ammonium molybdate, its production cost is high, subsequent handling is processed numerous and diverse, S, C are not wherein utilized yet, and due to the existence of C, also exist the ropy shortcoming of the vitriol oil of preparation.
Summary of the invention
The object of this invention is to provide a kind of boiling roaster nickel-molybdenum ore and prepared the method for sulfuric acid, tooling cost is low, and gained sulfuric acid is superior in quality.
The technical solution used in the present invention is a kind of method that boiling roaster nickel-molybdenum ore is prepared sulfuric acid, the method comprises the following steps: nickel-molybdenum ore and sulfide containing material are mixed, to the weight content of S in mixture be 20%～35%, the weight content of water is 5%～15%, then this mixture is placed in fluidizing furnace, pass into oxygen-enriched air roasting, obtain.
As preferably, the blending ratio of described nickel-molybdenum ore and sulfide containing material is 1:0～5.
As preferably, described sulfide containing material is selected from a kind of in containing sulfur minerals, sulphur or sulfurous gas or their mixture.
As preferably, described oxygen enrichment is that oxygen level is 20%～40%(volume ratio) air.
As preferably, when roasting, the fluidized layer temperature in described fluidizing furnace is 650 ℃～900 ℃, and the pressure of fluidizing furnace bottom is 900mmHg～1300mmHg, and the temperature out of fluidizing furnace is 450 ℃～660 ℃.
In the present invention, the C content of nickel-molybdenum ore is 10% left and right, and every mole of C of its combustion heating amount is equivalent to 3 moles of S thermal values.By controlling S content and the moisture content of roasting material, passing into the common roasting of oxygen enrichment, not only make full use of S and C in mineral, also overcome the impact of C on relieving haperacidity process in raw ore, its sulfuric acid of preparing gained meets national standard completely, residual sulphur weight ratio very low (lower than 4%) in the calcining of gained after roasting, for the production of follow-up nickel, molybdenum product provides good condition.
In the present invention, nickel-molybdenum ore is called again metallic nickel molybdenum, carbon sulphur molybdenum ore, Jiao Liukuang and bone coal.
Beneficial effect of the present invention is: (1) utilizes preparation method's gained sulfuric acid quality of the present invention to meet national standard.(2) by passing into oxygen-enriched air roasting, adopting nickel-molybdenum ore and sulfide containing material to mix uses, sulphur and the carbon that can make full use of in raw ore participate in reaction, overcome and can not utilize the technical barrier of sulphur and carbon in prior art, effectively reduced production cost, solve the pollution to environment, there is good economic benefit and social benefit.(3) utilize the tail gas of this preparation method discharge, meet national environmental protection comprehensive discharge standard.
Embodiment
For making those skilled in the art understand in detail production technique of the present invention and technique effect, with concrete production instance, further introduce application of the present invention and technique effect below.
Embodiment mono-:
Getting 100kg nickel-molybdenum ore and 300kg containing sulfur minerals mixes, after testing, in mixture, the weight content of S is 28%, the weight content of water is 10%, then this mixture is placed in to fluidized bed roasting in fluidizing furnace, to passing into oxygen level in fluidizing furnace, be 30%(volume ratio) air jointly carry out roasting, must contain the furnace gas of sulfur dioxide gas.This furnace gas, through dedusting, after purification, adopts contact process, obtains sulfuric acid.
Wherein, during roasting, the fluidized layer temperature in fluidizing furnace is 750 ℃, and the pressure of fluidizing furnace bottom is 1000mmHg, and the temperature out of fluidizing furnace is 500 ℃.
After testing, in furnace gas, the concentration of sulfurous gas is 8%.Sulfuric acid meets national standard.
Embodiment bis-:
Getting 100kg nickel-molybdenum ore and 10kg sulphur mixes, after testing, in mixture, the weight content of S is 27%, the weight content of water is 8%, then this mixture is placed in to fluidized bed roasting in fluidizing furnace, to passing into oxygen level in fluidizing furnace, be 20%(volume ratio) air jointly carry out roasting, must contain the furnace gas of sulfur dioxide gas.This furnace gas, through dedusting, after purification, adopts contact process, obtains sulfuric acid.
Wherein, during roasting, the fluidized layer temperature in fluidizing furnace is 650 ℃, and the pressure of fluidizing furnace bottom is 1300mmHg, and the temperature out of fluidizing furnace is 450 ℃.
After testing, in furnace gas, the concentration of sulfurous gas is 6.8%.Sulfuric acid meets national standard.
Embodiment tri-:
Getting 100kg nickel-molybdenum ore mixes, after testing, in material, the weight content of S is 20%, the weight content of water is 5%, then this mixture is placed in to fluidized bed roasting in fluidizing furnace, to passing into oxygen level in fluidizing furnace, be 40%(volume ratio) air jointly carry out roasting, must contain the furnace gas of sulfur dioxide gas.This furnace gas, through dedusting, after purification, adopts contact process, obtains sulfuric acid.
Wherein, during roasting, the fluidized layer temperature in fluidizing furnace is 900 ℃, and the pressure of fluidizing furnace bottom is 900mmHg, and the temperature out of fluidizing furnace is 660 ℃.
After testing, in furnace gas, the concentration of sulfurous gas is 5.8%.Sulfuric acid meets national industrial sulphuric acid primary standard.
Embodiment tetra-:
Getting 100kg nickel-molybdenum ore, 20kg containing sulfur minerals and 10kg sulphur mixes, after testing, in mixture, the weight content of S is 26%, the weight content of water is 15%, then this mixture is placed in to fluidized bed roasting in fluidizing furnace, to passing into oxygen level in fluidizing furnace, be 35%(volume ratio) air jointly carry out roasting, must contain the furnace gas of sulfur dioxide gas.This furnace gas, through dedusting, after purification, adopts contact process, obtains sulfuric acid.
Wherein, during roasting, the fluidized layer temperature in fluidizing furnace is 800 ℃, and the pressure of fluidizing furnace bottom is 1100mmHg, and the temperature out of fluidizing furnace is 550 ℃.
After testing, in furnace gas, the concentration of sulfurous gas is 6.4%.Sulfuric acid meets national standard.
Through test, in above-described embodiment, in furnace gas, the transformation efficiency of sulfur dioxide gas is greater than 98%, and can effectively make Sulphur Dioxide is sulfuric acid.The concentration of its sulfuric acid is 93%-98%.
Finally it should be noted that, above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to above-described embodiment, those skilled in the art are to be understood that, still can modify or be equal to replacement the present invention, and not departing from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in claim scope of the present invention.
Claims (5)
1. a boiling roaster nickel-molybdenum ore is prepared the method for sulfuric acid, it is characterized in that: the method comprises the following steps: nickel-molybdenum ore and sulfide containing material are mixed, to the weight content of S in mixture be 20%～35%, the weight content of water is 5%～15%, then this mixture is placed in fluidizing furnace, pass into oxygen-enriched air roasting, obtain.
2. boiling roaster nickel-molybdenum ore according to claim 1 is prepared the method for sulfuric acid, it is characterized in that: the blending ratio of described nickel-molybdenum ore and sulfide containing material is 1:0～5.
3. boiling roaster nickel-molybdenum ore according to claim 1 and 2 is prepared the method for sulfuric acid, it is characterized in that: described sulfide containing material is selected from a kind of in containing sulfur minerals, sulphur or sulfurous gas or their mixture.
4. boiling roaster nickel-molybdenum ore according to claim 1 is prepared the method for sulfuric acid, it is characterized in that: described oxygen enrichment is that oxygen level is 20%～40%(volume ratio) air.
5. boiling roaster nickel-molybdenum ore according to claim 1 is prepared the method for sulfuric acid, it is characterized in that: when roasting, fluidized layer temperature in described fluidizing furnace is 650 ℃～900 ℃, the pressure of fluidizing furnace bottom is 900mmHg～1300mmHg, and the temperature out of fluidizing furnace is 450 ℃～660 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106834703A (en) * | 2017-03-30 | 2017-06-13 | 中南大学 | A kind of leaching method of waste lithium ion cell anode active material |
| CN110902656A (en) * | 2019-12-12 | 2020-03-24 | 南京乾盛化工科技有限公司 | Production method for preparing sulfuric acid from molybdenum concentrate |
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| CN101245409A (en) * | 2008-03-31 | 2008-08-20 | 昆明理工大学 | Method for producing iron ore concentrate with high arsenic ferro-sulphur ore concentrate |
| CN102199710A (en) * | 2011-05-06 | 2011-09-28 | 中南大学 | Method for extracting and separating nickel and molybdenum from nickel-molybdenum-containing coal gangue |
| CN102268538A (en) * | 2011-07-27 | 2011-12-07 | 中南大学 | Boiling furnace device used for roasting nickel-molybdenum concentrate and method for roasting nickel-molybdenum concentrate |
| CN103088210A (en) * | 2013-01-18 | 2013-05-08 | 中南大学 | Method for selectively leaching nickel and molybdenum from nickel-molybdenum ore |
-
2013
- 2013-11-06 CN CN201310547222.0A patent/CN103569971B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245409A (en) * | 2008-03-31 | 2008-08-20 | 昆明理工大学 | Method for producing iron ore concentrate with high arsenic ferro-sulphur ore concentrate |
| CN102199710A (en) * | 2011-05-06 | 2011-09-28 | 中南大学 | Method for extracting and separating nickel and molybdenum from nickel-molybdenum-containing coal gangue |
| CN102268538A (en) * | 2011-07-27 | 2011-12-07 | 中南大学 | Boiling furnace device used for roasting nickel-molybdenum concentrate and method for roasting nickel-molybdenum concentrate |
| CN103088210A (en) * | 2013-01-18 | 2013-05-08 | 中南大学 | Method for selectively leaching nickel and molybdenum from nickel-molybdenum ore |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106834703A (en) * | 2017-03-30 | 2017-06-13 | 中南大学 | A kind of leaching method of waste lithium ion cell anode active material |
| CN106834703B (en) * | 2017-03-30 | 2019-04-26 | 中南大学 | A kind of leaching method of waste lithium ion cell anode active material |
| CN110902656A (en) * | 2019-12-12 | 2020-03-24 | 南京乾盛化工科技有限公司 | Production method for preparing sulfuric acid from molybdenum concentrate |
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