CN100551833C - The technology of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore - Google Patents
The technology of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore Download PDFInfo
- Publication number
- CN100551833C CN100551833C CNB2005102007063A CN200510200706A CN100551833C CN 100551833 C CN100551833 C CN 100551833C CN B2005102007063 A CNB2005102007063 A CN B2005102007063A CN 200510200706 A CN200510200706 A CN 200510200706A CN 100551833 C CN100551833 C CN 100551833C
- Authority
- CN
- China
- Prior art keywords
- exhaust gas
- chlorine contained
- contained exhaust
- sulfate slag
- absorption tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Treating Waste Gases (AREA)
Abstract
The invention provides a kind of technology of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore, is raw material with the sulfate slag and the chlorine contained exhaust gas of iron-holder 30%～60%, reaction in the absorption tower and getting; Compared with prior art, the present invention administers two cover technologies with the comprehensive recovery of sulfate slag and chlorine contained exhaust gas and unites two into one, and has reached the purpose of " treatment of wastes with processes of wastes against one another, the comprehensive regulation, turn waste into wealth "; Sulfate slag ore pulp and chlorine contained exhaust gas are good in absorption tower internal reaction condition, react more thorough, have overcome the problem that chemical reaction is more single in the prior art, flow process is long; Saved chlorination, oxidation operation that traditional iron trichloride is produced, saved resource, and solved the source problem that comes of hydrochloric acid; The specific absorption of chlorine contained exhaust gas reaches more than 90% in the inventive method, can realize qualified discharge, has realized free of contamination cleaner production.
Description
Technical field:
The present invention relates to a kind of technology of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore, belong to the category of environmental technology field.
Background technology:
Sulfate slag is to be the waste residue (also claiming sulfate cinder) of being discharged in the raw material production sulfuric acid process with the sulfurous iron ore, and its iron-holder (massfraction) is about 30%～60%, so abandoning in a large number of sulfate slag caused the waste and the loss of iron ore deposit.According to statistics, present domestic every year because of the burning quantity of slag of producing sulfuric acid and discharging greatly about 1,200 ten thousand tons, except that 30% was utilized, all the other were stored up as waste, in case therefore blowing and raining just pollutes farmland, pond and rivers.Traditional sulfate slag method of comprehensive utilization has:
1. be directly used in ironmaking: sulfate slag can be used for ironmaking as a kind of main iron-bearing material, but has following two problems in actual applications, and first iron grade is low and fluctuation is big; It two is ironmaking detrimental impurity sulphur, arsenic, silicone content height.Therefore, burning slag ore dressing in advance handles and can smelt iron.
2. adopting in high temperature, the middle temperature chloridizing roasting reclaim(ed) sulfuric acid slag has valency non-ferrous metal such as gold and silver etc., but these methods are big to the selectivity of raw material, and usage range is wideless.
3. using sulfated burning slag is produced material of construction: burn slag brick as do jointing compound production with lime, the burning slag after high-temperature roasting itself there is no cementing power, but it can do aggregate in burning slag brick, and all the other can combine with lime and form consolidating material.Or do binding agent production with cement and burn slag brick: with the pyrite cinder is main raw material, and cement is binding agent, mixes little amount of catalyst again, compression moulding.
The comprehensive utilization technique of these sulfate slags, ubiquity a series of problems such as cost is higher, the cycle is long, iron recovery added value low, byproduct is low.
And the discharging of a large amount of chlorine contained exhaust gas is all arranged in the titanium sponge production, chlorine industry production process, and be example with titanium sponge production, the tail gas main component of chlorination furnace is CO, CO in the chlorination production process
2, O
2, N
2, Cl
2, TiCl
4And a spot of HCl, traditional improvement method at first will be carried out the milk of lime dechlorination, washes absorption then and finally obtains low-concentration hcl, and low-concentration hcl can be used as the cleaning of equipment etc.This technology can solve the qualified discharge of chlorination waste gas, and recovery part TiCl
4, but this technology is high to the solidity to corrosion requirement of equipment, and storing up of low-concentration hcl has sizable environmental risk.
Iron trichloride is mainly used in sewage disposal, circuit board etching, Corrosion of Stainless Steel and mordant, and main products has two kinds of solid iron trichloride and liquid ferrous trichlorides, and wherein the high-purity type of HPFCS is used for the cleaning and the etching of electron trade high request.Liquid ferrous trichloride is the efficient cheap flocculation agent of municipal effluent and Industrial Wastewater Treatment, have effects such as significant precipitation of heavy metals and sulfide, decolouring, deodorization, oil removing, sterilization, dephosphorization, reduction water outlet COD and BOD, at present the good market prospects of iron trichloride flocculation agent.
Traditional iron trichloride production method mainly contains following several:
1, chlorination process-iron filings at high temperature with chlorine reaction.
2, salt acid system-iron filings and hydrochloric acid boil altogether, generate iron protochloride, feed chlorine oxidation again and generate iron trichloride.
3, an one-step chlorination method-chlorine is directly fed in the water that soaks iron filings, a step generates iron trichloride.
These methods all are that to adopt chlorine, hydrochloric acid and iron filings be raw material, in process of production, have chlorine and hydrogen chloride gas to overflow, serious environment pollution and influence enterprise employee health, disposal of three wastes investment greatly, simultaneously to the solidity to corrosion and the sealing requirements height of equipment.Therefore study new iron trichloride technology, particularly free of contamination process for cleanly preparing is very important.
Application number is that 89101216.8 patent adopts industrial waste acid to react with iron filings as the spent pickle liquor of steel-making to produce iron protochloride, and then carries out oxidation and produce iron trichloride.Application number is iron-containing dust and the hydrochloric acid reaction that 88109015.8 patent adopts smelting iron and steel, and makes iron trichloride through peroxidation.It is oxygenant and catalyzer that these technology adopt nitrite, or uses hydrogen peroxide or chlorine to be oxygenant, easily form secondary pollution in force, and cost is higher.In application number is 96102186.1 patent, directly adopt iron ore and hydrochloric acid reaction to prepare ferric chloride in aqueous solution, but this method is very strong to the selectivity of iron ore, requires Fe in the iron ore
2O
3At least to equal 90%, preferably use iron-holder to be higher than 95% rhombohedral iron ore, can not use magnetite, limonite.Application number is that 94190358.3 patented technologies adopt hydrochloric acid and iron filings reaction at first to make iron protochloride, uses O then
2Or air carries out oxidation and obtains iron(ic) chloride, and this method can reduce the cost of catalysis and oxidation to a certain extent and reduce and pollute, but this technology speed of response is very slow.
Summary of the invention:
The objective of the invention is to: the technology that a kind of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore is provided, the production of iron trichloride and the improvement of chlorine contained exhaust gas are combined, chlorination, oxidation operation that traditional iron trichloride is produced have not only been saved, save a large amount of resources, solved the source problem that comes of hydrochloric acid simultaneously; Present method also makes the chlorine contained exhaust gas governing problem be solved, and the specific absorption of chlorine contained exhaust gas reaches more than 90%, can realize qualified discharge, has realized the resource utilization of chlorine contained exhaust gas, innoxious and minimizing.
The present invention is achieved in that the technology of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore; Sulfate slag and chlorine contained exhaust gas with iron-holder 30%～60% are that raw material reaction gets.
Concrete is: sulfate slag and water are mixed with ore pulp, under the effect of recycle pump, enter the absorption tower by the jet apparatus in pulp tank, circulating line and the absorption tower, spray downwards from nozzle, scatter on the top of tower; Chlorine contained exhaust gas enters from the bottom, absorption tower, in Ta Nei and the reaction of sulfate slag ore pulp counter current contact, chlorine, hydrogenchloride is removed; Mixture after the reaction flows out from the absorption tower, and after filtration, filtrate purifies, removal of impurities and removal heavy metal, and then filters and promptly get liquor ferri trichloridi, and solution can get the solid iron trichloride through concentrated.
Among the present invention, with sulfate slag sieve, less than 60 orders, the liquid-solid ratio of getting the sulfate slag ore pulp that minus mesh and water is mixed with is 3～10: 1.
Sulfate slag ore pulp and chlorine contained exhaust gas 85～95 ℃ of internal recycle in the absorption tower absorb 3～4 hours, are to filter after 40～60 to the degree Beaume of solution.
To degree Beaume is that 40～60 filtrates purify, and removes impurity and a spot of heavy metal, refilters and can obtain liquid ferrous trichloride solution, further carries out condensing crystal again and can obtain the solid iron trichloride.
The method that the present invention prepares iron trichloride is the process of neutralization reaction and oxidation-reduction reaction, and metal oxides such as the Fe in the sulfate slag, Ca, Mg all can react with chlorine contained exhaust gas.Principal reaction has:
Fe
2O
3+6HCl＝2FeCl
3+3H
2O (1)
FeO+2HCl＝FeCl
2+H
2O (2)
2FeCl
2+Cl
2＝2FeCl
3 (3)
MgO+2HCl＝MgCl
2+H
2O (4)
CaO+2HCl＝CaCl
2+H
2O (5)
Calculate according to " thermodynamic data " handbook, when 298.15K, the standard Gibbs free energy Δ G of principal reaction (1)
θ=-275.699KJ.mol
-1, visible reaction (1) can not only spontaneously be carried out, and can carry out very thoroughly.
Compared with prior art, the present invention has following advantage:
1, the comprehensive recovery of sulfate slag and chlorine contained exhaust gas are administered two cover technologies and unite two into one, changed the mode of traditional end treatment, reached the purpose of " treatment of wastes with processes of wastes against one another, the comprehensive regulation, turn waste into wealth ".
2, the reaction carried out in the absorption tower of sulfate slag ore pulp and chlorine contained exhaust gas is the gas, liquid, solid heterogeneous reactions, and reaction conditions is good, reacts more thorough, has overcome the problem that chemical reaction is more single in the prior art, flow process is long.
3, present method has been saved chlorination, the oxidation operation that traditional iron trichloride is produced, and has saved a large amount of resources, has solved the source problem that comes of hydrochloric acid simultaneously.
4, the specific absorption of chlorine contained exhaust gas reaches more than 90% in the inventive method, can realize qualified discharge, has realized free of contamination cleaner production.
5, the prepared product iron trichloride of present method can make liquid ferrous trichloride after treatment, also can make the solid iron trichloride.
Description of drawings:
Fig. 1 is the process flow sheet of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore.
Embodiment:
Embodiments of the invention 1: get sulfate slag (iron content 47.25%, cross 60 orders) 320 grams and 1.6 premium on currency, be mixed with the sulfate slag ore pulp, enter the absorption tower of Φ 80 * 400mm by the jet apparatus in pulp tank, circulating line and the absorption tower (zone of action), spray downwards from nozzle, scatter on the top of tower; (100L/h, contain hydrogenchloride and amount of chlorine is 356mg/m to chlorine contained exhaust gas
3) enter from the reaction tower bottom, with sulfate slag ore pulp counter current contact, circulation absorbs 3 hours, Cl in the flue gas in the time of 90 ℃ in the absorption tower
2With HCl and sulfate slag reaction, with Cl
2Remove with HCl, the mixture of being made up of iron trichloride, sulfate slag and water that obtains flows out from the absorption tower, can realize separating of water miscible iron trichloride and slag after filtration, obtain water miscible iron trichloride, then liquor ferri trichloridi is purified and removes heavy metal, and then filter and obtain 1.45 liters of (FeCl in the solution of more purified liquor ferri trichloridi
3=40.6%, free HCl=0.221%), solution can get the solid iron trichloride through evaporation concentration.The chlorinity of tail gas is 52.6mg/m
3, being lower than discharging standards, can directly discharge.
Embodiments of the invention 2: get sulfate slag (iron content 30%, cross 60 orders) 320 grams and 2.56 premium on currency, be mixed with the sulfate slag ore pulp, enter the absorption tower of Φ 80 * 400mm by the jet apparatus in pulp tank, circulating line and the absorption tower (zone of action), spray downwards from nozzle, scatter on the top of tower; (100L/h, contain hydrogenchloride and amount of chlorine is 356mg/m to chlorine contained exhaust gas
3) enter from the reaction tower bottom, with sulfate slag ore pulp counter current contact, circulation absorbs 3 hours, Cl in the flue gas in the time of 95 ℃ in the absorption tower
2With HCl and sulfate slag reaction, with Cl
2Remove with HCl, the mixture of being made up of iron trichloride, sulfate slag and water that obtains flows out from the absorption tower, can realize separating of water miscible iron trichloride and slag after filtration, obtain water miscible iron trichloride, then liquor ferri trichloridi is purified and removes heavy metal, and then filter and obtain 1.40 liters of (FeCl in the solution of more purified liquor ferri trichloridi
3=41.6%, free HCl=0.210%), solution can get the solid iron trichloride through evaporation concentration.Tail gas can directly discharge.
Embodiments of the invention 3: get sulfate slag (iron content 60%, cross 60 orders) 320 grams and 3.2 premium on currency, be mixed with the sulfate slag ore pulp, by the jet apparatus in pulp tank, circulating line and the absorption tower (zone of action) enter Φ 80 * 400mm the absorption tower (, spray downwards from nozzle, scatter on the top of tower; (100L/h, contain hydrogenchloride and amount of chlorine is 356mg/m to chlorine contained exhaust gas
3) enter from the reaction tower bottom, with sulfate slag ore pulp counter current contact, circulation absorbs 4 hours, Cl in the flue gas in the time of 85 ℃ in the absorption tower
2With HCl and sulfate slag reaction, with Cl
2Remove with HCl, the mixture of being made up of iron trichloride, sulfate slag and water that obtains flows out from the absorption tower, can realize separating of water miscible iron trichloride and slag after filtration, obtain water miscible iron trichloride, then liquor ferri trichloridi is purified and removes heavy metal, and then filter and obtain 1.43 liters of (FeCl in the solution of more purified liquor ferri trichloridi
3=41.1%, free HCl=0.212%), solution can get the solid iron trichloride through evaporation concentration.Tail gas can directly discharge.
Embodiments of the invention 4: get sulfate slag (iron content 30%, cross 60 orders) 320 grams and 960 ml waters, be mixed with the sulfate slag ore pulp, enter the absorption tower of Φ 80 * 400mm by the jet apparatus in pulp tank, circulating line and the absorption tower (zone of action), spray downwards from nozzle, scatter on the top of tower; (100L/h, contain hydrogenchloride and amount of chlorine is 356mg/m to chlorine contained exhaust gas
3) enter from the reaction tower bottom, with sulfate slag ore pulp counter current contact, circulation absorbs 3 hours, Cl in the flue gas in the time of 95 ℃ in the absorption tower
2With HCl and sulfate slag reaction, with Cl
2Remove with HCl, the mixture of being made up of iron trichloride, sulfate slag and water that obtains flows out from the absorption tower, can realize separating of water miscible iron trichloride and slag after filtration, obtain water miscible iron trichloride, then liquor ferri trichloridi is purified and removes heavy metal, and then filter and obtain 0.80 liter of (FeCl in the solution of more purified liquor ferri trichloridi
3=41.6%, free HCl=0.210%), solution can get the solid iron trichloride through evaporation concentration.Tail gas can directly discharge.
Claims (4)
1. the technology of a preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore, it is characterized in that: sulfate slag and chlorine contained exhaust gas with iron-holder 30%～60% are raw material, sulfate slag and water are mixed with ore pulp, under the effect of recycle pump, enter the absorption tower by the jet apparatus in pulp tank, circulating line and the absorption tower, spray downwards from nozzle, scatter on the top of tower; Chlorine contained exhaust gas enters from the bottom, absorption tower, in Ta Nei and the reaction of sulfate slag ore pulp counter current contact, chlorine, hydrogenchloride is removed; Mixture after the reaction flows out from the absorption tower, and after filtration, filtrate purifies, removal of impurities and removal heavy metal, and then filters and promptly get liquor ferri trichloridi, and solution can get the solid iron trichloride through concentrated.
2. according to the technology of the described preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore of claim 1, it is characterized in that: sulfate slag is carried out 60 purposes sieve, the liquid-solid mass ratio of getting the sulfate slag ore pulp that minus mesh and water is mixed with is 3～10: 1.
3. according to the technology of the described preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore of claim 1, it is characterized in that: sulfate slag ore pulp and chlorine contained exhaust gas 85～95 ℃ of internal recycle in the absorption tower absorb 3～4 hours, filter after the degree Beaume of solution is 40～60 degree.
4. according to the technology of the described preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore of claim 3, it is characterized in that: to degree Beaume is that 40～60 filtrates purify, remove impurity and a spot of heavy metal, refilter and to obtain liquid ferrous trichloride solution, further carry out condensing crystal again and can obtain the solid iron trichloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005102007063A CN100551833C (en) | 2005-11-16 | 2005-11-16 | The technology of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005102007063A CN100551833C (en) | 2005-11-16 | 2005-11-16 | The technology of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1760134A CN1760134A (en) | 2006-04-19 |
| CN100551833C true CN100551833C (en) | 2009-10-21 |
Family
ID=36706381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005102007063A Expired - Fee Related CN100551833C (en) | 2005-11-16 | 2005-11-16 | The technology of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100551833C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445186B (en) * | 2017-09-01 | 2023-06-27 | 河北正润环境科技有限公司 | Recycling device and method for steel finishing pickling waste liquid |
-
2005
- 2005-11-16 CN CNB2005102007063A patent/CN100551833C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 硫铁矿烧渣湿法制备铁系产品的原理和途径分析. 郑雅杰等.环境污染治理技术与设备，第2卷第1期. 2001 |
| 硫铁矿烧渣湿法制备铁系产品的原理和途径分析. 郑雅杰等.环境污染治理技术与设备，第2卷第1期. 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1760134A (en) | 2006-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101811792B (en) | Processing method of stainless steel cold rolling pickling wastewater | |
| CN104310647B (en) | Recycling method for treating stainless steel pickling acid pickle and wastewater | |
| CN101538652A (en) | Method for separating and recovering vanadium and chrome from vanadium and chrome-containing waste | |
| CN102730877A (en) | Technology and device for treating mixed waste water produced by cold-rolling pickling of stainless steel and carbon steel | |
| CN105502609A (en) | Method for treating wastewater containing hypochlorite | |
| CN109913659A (en) | A kind of method of antimony smelting arsenic alkali slag and flue gas during smelting comprehensive treatment | |
| CN107619068A (en) | A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing | |
| CN113149263A (en) | Method for treating acidic wastewater by resource utilization of sodium-based desulfurized fly ash | |
| CN101863516B (en) | Method for recovering ferrite containing chromium and nickel in stainless steel pickling waste water sludge | |
| CN109485133A (en) | A method of the dechlorination of waste acid containing chlorine | |
| CN109988902B (en) | Method for dealkalizing iron-reinforced red mud and separating and recovering iron | |
| CN101760646A (en) | Leaching method of magnesium-containing ore | |
| CN103290214A (en) | Method for depositing iron from ferruginous zinc sulfate solution | |
| CN108793652B (en) | Pickling sludge recycling treatment device and technology | |
| CN101760637B (en) | Leaching technology of magnesium-containing ore | |
| CN107188292A (en) | A kind of utilization silver extraction by cyanidation waste residue purifies the method containing arsenic waste solution | |
| CN105347546A (en) | Treatment method and system of waste water produced by acid preparation from pyrite | |
| CN101760638B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN100551833C (en) | The technology of preparing ferric chloride through absorbing chlorine contained exhaust gas by burnt ore | |
| CN1254023A (en) | Leaching-out method for extracting vanadium from vanadium-containg ore calcines and its application in stone-coal calcination-direct vanadium-extracting process | |
| CN101049978A (en) | Method for preparing polymerized iron chloride by using cinder of sulfur iron ore | |
| CN207987329U (en) | A kind of system that nickelous carbonate is extracted in the waste mixed acid from acid-washing stainless steel | |
| CN112499815A (en) | Stainless steel cold rolling sludge recovery treatment method | |
| CN105439345A (en) | Recycling method for removing lead from acid cleaning waste liquid of lead-containing steel wire ropes | |
| CN1122559C (en) | Method for processing SO2 containing fume |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091021 Termination date: 20151116 |
|
| EXPY | Termination of patent right or utility model |