CN1760117A - Method for recovering vitriol from waste vitrol containing metal salt - Google Patents
Method for recovering vitriol from waste vitrol containing metal salt Download PDFInfo
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- CN1760117A CN1760117A CN 200510096254 CN200510096254A CN1760117A CN 1760117 A CN1760117 A CN 1760117A CN 200510096254 CN200510096254 CN 200510096254 CN 200510096254 A CN200510096254 A CN 200510096254A CN 1760117 A CN1760117 A CN 1760117A
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Abstract
A process for recovering sulfuric acid from the used sulfuric acid containing metallic salt includes such steps as concentrating to 30-35% for acid concentration, proportionally adding desalting agent, stirring at 70-90 deg.C while desalting, laying aside for educing out salt, cooling, solid-liquid separation, concentrating the filtrate to 70% and cooling.
Description
Technical field
The present invention relates to method with reclaim(ed) sulfuric acid in the sulfur waste acid of containing metal vitriol, particularly to industrial waste sulfuric acid, as: with obtaining sulfur waste acid after the Titanium White Production By Sulfuric Acid Process, perhaps with the waste liquid that obtains behind the sulfuric acid cleaned steel, the method for recycling.
Background technology
With the waste liquid that method for producing gtitanium dioxide with sulphuric acid produced, and contain metal sulfates such as a large amount of sulfuric acid and ferrous sulfate in the waste liquid of cleaning steel.These sulfur waste acid are only discharged through after the simple neutralizing treatment usually, not only cause serious environmental to pollute, and have wasted valuable industrial chemicals simultaneously, and have brought enormous economic loss.Therefore, reclaim(ed) sulfuric acid has just become anxious important topic to be solved with metal sulfate from sulfur waste acid.
The method that present stage, acid recycled to sulfur waste both at home and abroad has following a few class:
1) multistage evaporation method
As U.S. Pat 2960391 and the disclosed method of Chinese patent CN02109098.X.These class methods are that earlier sulfur waste acid heating to be concentrated into concentration be 30～40%, carry out second stage concentration through freeze desalination, hydrochlorate again after separating, and vitriolic concentration reaches back utilization 65% or more.
The deficiency of this treatment process is that metal-salt can be separated out crystallization in the concentration process, forms fouling and blocking pipe on wall, causes to concentrate and can't normally carry out.In addition, the power consumption of this method is higher, take longer, simultaneously lower because of its gained sulfuric acid concentration, to its follow-up use is under some influence.
2) metal sulfate thermal decomposition method
As U.S. Pat 5730590 disclosed methods is with ferric oxide or ironic hydroxide and waste sulfuric acid effect, generates ferric sulfate, after thermolysis makes ferric sulfate be converted into sulfurous gas and sulphur trioxide, prepares sulfuric acid again again.
This treatment process needs specialized apparatus, and facility investment is higher, and entire treatment technology is comparatively complicated, and processing costs is bigger.
3) extraction desalination-concentrate or the dialysis processing
Promptly select suitable organic solvent for use, after the extraction of metal ions such as iron, titanium is removed, concentrate again or the dialysis purification processing.Flat 3-88718, Chinese patent CN94190556.X and Korean Patent KR9604261 are disclosed as Japan's special permission.
The deficiency of this method is to need in treating processes with a large amount of oxygenants and extraction agent, and processing cost is improved.And it is not high that this method is handled the gained sulfuric acid concentration.
Summary of the invention
The invention provides a kind of sulfur waste acid recovery vitriolic novel method, particularly, perhaps use reclaim(ed) sulfuric acid and ferrous sulfate novel method in the sulfuric acid cleaned steel gained industrial waste sulfuric acid from producing the acid of titanium dioxide gained sulfur waste with metal-containing salt.Method of the present invention does not need specific installation, does not produce the deficiency that metal-salt is separated out in concentration process in the prior art, can obtain the black sulfuric acid of higher concentration, can overcome the disadvantage that prior art exists.
Method of the present invention is: earlier industrial waste sulfuric acid is carried out concentration, it is to stop to concentrate in 30～35% o'clock that spent acid is concentrated into acid concentration, in feed liquid in feed liquid: the desalting agent weight ratio is that 1: 0.08～0.3 ratio adds desalting agent, desalting agent described here is meant that acid concentration is greater than 70% sulfuric acid, and this sulfuric acid can be fresh industrial sulphuric acid, it also can be black sulfuric acid through gained of the present invention, under 70～90 ℃ of conditions, system is fully stirred desalination, make the sulfuric acid concentration of system reach 52～60%, after fully stirring, leave standstill, salt is fully separated out, the system for the treatment of is cooled to carry out solid-liquid separation after 40 ℃, and resulting sulfuric acid can satisfy the use of some condition.
Be necessary if desired and can carry out the concentration second time again, after 70%, stop to concentrate,, carry out the solid-liquid separation second time again through fully stirring postcooling etc. sulfuric acid concentration in the system to aforementioned gained black sulfuric acid.
Optimum process controling condition of the present invention be the first time concentration reach at 32～35% o'clock to the acid concentration of system and stop to concentrate, added desalting agent by 1: 0.1, and under 85 ℃ of conditions, system fully stirred desalination, make the acid concentration of system reach 55～58%.
Concentration of the present invention also can adopt distillation under vacuum.
When adopting method of the present invention to carry out the sulfur waste acid treatment, concentration can adopt distillation under vacuum, can cut down the consumption of energy like this, raises the efficiency.
It is desalting agent that the present invention proposes with sulfuric acid first, and it is according to being the ferrous sulfate fact that concentration reduces with the acid concentration increase in sulfuric acid.
Afterwards adding industrial sulphuric acid or black sulfuric acid in the once concentration processing in the treating processes of the present invention is desalting agent, make system carry out advanced desalination, relevant test shows, adopt the metal-salt crystallization more than 96% that can be present in the system after these technical measures to separate out, both can fully obtain useful industrial chemicals, simultaneously can guarantee again not have again metal-salt to separate out in the concentration process, therefore can on wall of container such as reactor, pipeline, not form fouling and stop up, influence the secondary concentration process in the second time.Greater than 70%, can not introduce impurity in the whole technology through the concentration of gained black sulfuric acid of the present invention, foreign matter content is extremely low in the resulting after treatment regenerating acid.And in treating processes, not needing freezingly, time-saving energy-saving does not have the discharging of the three wastes yet.
Embodiment
Show through repeatedly relevant test, when adopting the method that the present invention provides, primary sulfur waste acid concentration should be concentrated to the acid concentration of feed liquid and stop to concentrate in 30～35% o'clock, in feed liquid, add sulfuric acid then as desalting agent, the vitriolic concentration that is added should be greater than 70%, and its add-on is taken off in feed liquid: all can in the proportional range of salt agent=1: 0.08～0.3.System stirs the temperature of desalination should be 70～90 ℃ of conditions, and the sulfuric acid concentration of system can 52～60% after this processing.After fully stirring, leave standstill, the salt in the system is fully separated out.When carrying out separating because of liquid, system temperature can have separating effect preferably after 40 ℃.
Correlation test shows that also its divalent iron of sulfur waste acid that the present invention was suitable for handling should be more than or equal to 95% with the ratio of total iron, and 3 valency iron ratios are too high in spent acid, and its treatment effect is relatively poor.
Several optimum examples of the present invention below is provided:
Embodiment 1
Get the waste sulfuric acid of 2000 gram Titanium White Production By Sulfuric Acid Process, show that by analysis wherein sulfuric acid concentration is 336g/L, total iron content is 41.45g/L.Concentrated through heating, stop heating after making the sulfuric acid concentration of solution reach 35%, treat after the liquid cooling to 100 ℃ under agitation condition by feed liquid: desalting agent (92% sulfuric acid) is that 1: 0.18 (weight ratio) adds desalting agent, and 85 ℃ of maintenance stirrings 2 hours, make the acid concentration of whole system reach 55～60%, the ferrous sulfate crystallization in the separation system of cooling back.Solution is carried out the heating second time again and concentrate, greater than 70%, stop heating until the solution sulfuric acid concentration, naturally cooling spends the night, and then processing obtains black sulfuric acid after filtration.The result is as follows by analysis: black sulfuric acid concentration is 74.5%, and the sulfuric acid yield is 84%, and the total iron content in the system is 0.15%.
Embodiment 2
Get the waste sulfuric acid of 500 gram Titanium White Production By Sulfuric Acid Process, show that by analysis wherein sulfuric acid concentration is 234g/L, total iron content is 51.42g/L.Concentrated through heating, stop heating after making sulfuric acid concentration in the solution reach 35%, treat liquid cooling after～100 ℃ under agitation condition by feed liquid: desalting agent (92% sulfuric acid) is that 1: 0.1 (weight ratio) adds desalting agent, and 85 ℃ of maintenance stirrings 2 hours, make the acid concentration of whole system reach 58%, the ferrous sulfate crystallization in the cooled and filtered separation system.Solution is carried out the heating second time again and concentrate, greater than 70%, stop heating until the solution sulfuric acid concentration, stop heating, naturally cooling spends the night, and then processing obtains black sulfuric acid after filtration.By analysis: black sulfuric acid concentration is 77.5%, and the sulfuric acid yield is 80.2%, and the total iron content in the system is 0.10%.
Embodiment 3
Get the waste sulfuric acid of 1000 gram Titanium White Production By Sulfuric Acid Process, by analysis, sulfuric acid concentration is 234g/L in the spent acid, and total iron content is 51.42g/L.Concentrated through heating, make and stop heating after acid concentration reaches 35% in the solution, treat liquid cooling after～100 ℃ by feed liquid: desalting agent (acid concentration is 72% black sulfuric acid) is after 1: 0.10 (weight ratio) adding system, and in 85 ℃ of stirrings 3 hours, make the acid concentration of system reach 58%, solution is cooled to 30 ℃ of ferrous sulfate crystallizations in the after-filtration separation system.Solution is carried out the heating second time again and concentrate, greater than 70%, stop heating until strength of solution, naturally cooling spends the night, and then processing obtains black sulfuric acid after filtration.By analysis: black sulfuric acid concentration is 75%, and the sulfuric acid yield is 80%, and the total iron content in the system is 0.15%.
Embodiment 4
Condition by the 3rd embodiment repeats test, is concentrating under reduced pressure under the 0.07Mpa condition but concentrate employing for the second time in vacuum tightness,, sulfuric acid concentration reaches 70% in the solution, also can obtain the black sulfuric acid identical with yield with the composition of a last embodiment.
Claims (6)
1, the method of reclaim(ed) sulfuric acid from the industrial waste sulfuric acid of metal-containing salt, earlier industrial waste sulfuric acid is carried out concentration, it is characterized in that it is to stop to concentrate that pending spent acid is concentrated into acid concentration at 30～35% o'clock, in feed liquid in feed liquid: the desalting agent weight ratio is that 1: 0.08～0.3 ratio adds desalting agent, described desalting agent is an acid concentration greater than 70% sulfuric acid, under 70～90 ℃ of conditions, system is fully stirred desalination, make the sulfuric acid concentration of system reach 52～60%, after fully stirring, leave standstill, salt is fully separated out, and the system for the treatment of is cooled to carry out solid-liquid separation after 40 ℃.
2, according to claim 1 from the industrial waste sulfuric acid of metal-containing salt the method for reclaim(ed) sulfuric acid, it is characterized in that will handle gained liquid by claim 1 carries out the concentration second time again, stop to concentrate after 70% etc. sulfuric acid concentration in the system, through fully stirring postcooling.
3, according to claim 2 from the industrial waste sulfuric acid of metal-containing salt the method for reclaim(ed) sulfuric acid, it is characterized in that black sulfuric acid is carried out the solid-liquid separation second time, obtain black sulfuric acid.
4, according to claim 1 or 2 or 3 described from the industrial waste sulfuric acid of metal-containing salt the method for reclaim(ed) sulfuric acid, it is characterized in that concentration can adopt distillation under vacuum.
5, according to claim 1 or 2 or 3 described from the industrial waste sulfuric acid of metal-containing salt the method for reclaim(ed) sulfuric acid, it is characterized in that the acid concentration of system reaches at 32～35% o'clock after the concentration for the first time stops to concentrate, by 1: 0.1 adding desalting agent, and under 85 ℃ of conditions, system is fully stirred desalination, make the acid concentration of system reach 55～58%.
6, according to claim 5 from the industrial waste sulfuric acid of metal-containing salt the method for reclaim(ed) sulfuric acid, it is characterized in that concentration can adopt distillation under vacuum.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100962549A CN100357176C (en) | 2005-10-19 | 2005-10-19 | Method for recovering vitriol from waste vitrol containing metal salt |
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| CNB2005100962549A CN100357176C (en) | 2005-10-19 | 2005-10-19 | Method for recovering vitriol from waste vitrol containing metal salt |
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| CN1760117A true CN1760117A (en) | 2006-04-19 |
| CN100357176C CN100357176C (en) | 2007-12-26 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759158B (en) * | 2009-12-23 | 2011-06-29 | 河南豫光金铅股份有限公司 | Method for regenerating and recovering sulfuric acid from waste acid |
| CN104876194A (en) * | 2015-06-02 | 2015-09-02 | 南京鹳山化工科技有限公司 | Method for recycling sulfuric acid and sulfate by sulfate-containing dilute sulfuric acid |
| CN105315168A (en) * | 2015-11-27 | 2016-02-10 | 常州永和精细化学有限公司 | Environment-friendly preparation process of N-(4-ethoxy carbonyl phenyl)-N'-methyl-N'-phenyl formamidine intermediate |
| CN107010608A (en) * | 2017-05-11 | 2017-08-04 | 梧州圣绿科技有限公司 | A kind of method that utilization titanium white waste acid prepares sulfuric acid |
| CN108046336A (en) * | 2018-01-02 | 2018-05-18 | 张家港洁利环保科技有限公司 | The industrial process of green vitriol crystal |
| CN108147471A (en) * | 2018-01-02 | 2018-06-12 | 张家港洁利环保科技有限公司 | The industrial process of Feromax crystal |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2968877B2 (en) * | 1991-11-08 | 1999-11-02 | 日鉄鉱業株式会社 | Method for recovering sulfuric acid from waste sulfuric acid containing metal sulfate |
| JP2968913B2 (en) * | 1993-07-30 | 1999-11-02 | 日鉄鉱業株式会社 | Method for regenerating waste sulfuric acid containing metal sulfate |
-
2005
- 2005-10-19 CN CNB2005100962549A patent/CN100357176C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759158B (en) * | 2009-12-23 | 2011-06-29 | 河南豫光金铅股份有限公司 | Method for regenerating and recovering sulfuric acid from waste acid |
| CN104876194A (en) * | 2015-06-02 | 2015-09-02 | 南京鹳山化工科技有限公司 | Method for recycling sulfuric acid and sulfate by sulfate-containing dilute sulfuric acid |
| CN105315168A (en) * | 2015-11-27 | 2016-02-10 | 常州永和精细化学有限公司 | Environment-friendly preparation process of N-(4-ethoxy carbonyl phenyl)-N'-methyl-N'-phenyl formamidine intermediate |
| CN105315168B (en) * | 2015-11-27 | 2017-09-15 | 常州永和精细化学有限公司 | N (4 carboethoxyphenyl) N ' methyl Ns ' phenyl formamidine intermediate green preparation process |
| CN107010608A (en) * | 2017-05-11 | 2017-08-04 | 梧州圣绿科技有限公司 | A kind of method that utilization titanium white waste acid prepares sulfuric acid |
| CN108046336A (en) * | 2018-01-02 | 2018-05-18 | 张家港洁利环保科技有限公司 | The industrial process of green vitriol crystal |
| CN108147471A (en) * | 2018-01-02 | 2018-06-12 | 张家港洁利环保科技有限公司 | The industrial process of Feromax crystal |
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| Publication number | Publication date |
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| CN100357176C (en) | 2007-12-26 |
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