CN105236446A - Method for recycling waste hydrochloric acid - Google Patents
Method for recycling waste hydrochloric acid Download PDFInfo
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- CN105236446A CN105236446A CN201510828569.1A CN201510828569A CN105236446A CN 105236446 A CN105236446 A CN 105236446A CN 201510828569 A CN201510828569 A CN 201510828569A CN 105236446 A CN105236446 A CN 105236446A
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- hydrochloric acid
- ammonia
- waste hydrochloric
- waste
- reactor
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Abstract
The invention belongs to the field of environmental protection and particularly relates to a method for recycling waste hydrochloric acid, in particular to a method for recycling waste diluted hydrochloric acid in the titanium slag leaching process. The method for recycling waste hydrochloric acid comprises the following steps: a step a of filtering waste hydrochloric acid and then leading the waste hydrochloric acid into a reactor, recording the volume v/L of the added waste hydrochloric acid and the concentration c/mol.L<-1> of chloride ions therein; a step b of leading ammonia into the reactor, causing the flow velocity of the ammonia to be not lower than causing the total led-in amount of the ammonia to be 1.8-2.2 v*c/mol; a step c of filtering the mixture in the reactor in 40-60 min after the leading in of ammonia, taking filtrate, causing the filtrate to undergo evaporative crystallization, and obtaining ammonium chloride crystal. According to the method, an external heat source is not needed, the product is free of pollution, the process is short, and the operation is simple. Waste of the waste hydrochloric acid and the ammonia is reduced, the production cost of nitrogenous fertilizer can be reduced, and the waste hydrochloric acid recycling additional value is improved.
Description
Technical field
The invention belongs to field of Environment Protection, be specifically related to a kind of recycling method of waste hydrochloric acid, particularly relate to the reuse method of waste and old dilute hydrochloric acid in titanium slag leaching process.
Background technology
At present, the artificial rutile prepared by titanium slag or rich titanium material have become the main production raw material of titanium dioxide.Titanium slag needs the removal being realized impurity component in titanium slag by acidleach after series of preprocessing, thus improves the titanium dioxide taste of product further.The rutile content leached in end post-modification titanium slag will reach or more than 90%, the rutile substantially close to target product is sampled.Leach and terminate a large amount of waste and old dilute hydrochloric acid of rear generation, this part concentration of hydrochloric acid is low, and dopant species is many, and content is high, mainly FeCl
2, MgCl
2, CaCl
2, AlCl
3deng muriate, directly cannot utilize, be in environmental factors and consider, also cannot directly discharge.Current industrial widely used waste hydrochloric acid recovery method is spray roasting and fluiddized-bed roasting technique, and its principle is substantially identical, is all by pyrohydrolysis and oxidation, realizes decomposition and the recovery of hydrochloric acid in muriate.
But no matter be spray roasting or fluiddized-bed roasting, all clearly, first, in order to realize the recovery of hydrochloric acid, the facility investment of whole processing line is very large for shortcoming; Secondly, the maintenance of reaction needs to consume a large amount of heats; In addition, operation of equipment is complicated, and added value of product is low, and cost of investment cannot reclaim within considerable time.
Current waste hydrochloric acid reclaims also exists following problem: technique initial cost is large, the problems such as operation cost is high, and recycling rate is not high.
Summary of the invention
Therefore, technical problem to be solved by this invention is to provide the preparation method of the waste hydrochloric acid that a kind of cost recovery is low, recovery utilization rate is high.
A kind of waste hydrochloric acid recycling of the present invention method, comprises the following steps:
A, will waste hydrochloric acid filter after pass in reactor, record the concentration c/molL of waste hydrochloric acid volume ν/L of adding and wherein chlorion
-1;
B, in reactor, pass into ammonia, start to pass into ammonia flow velocity and be
afterwards with
speed reduce logical ammonia speed, the flow velocity of ammonia must not be lower than
total intake of ammonia is 1.8 ν * c ~ 2.2 ν * c/mol; Wherein, γ is logical ammonia pipeline radius,
for logical ammonia length of pipe;
C, ammonia stop passing into rear 40 ~ 60min, are filtered by mixture in reactor, get filtrate, by filtrate evaporative crystallization, obtain ammonia chloride crystal.
A kind of waste hydrochloric acid recycling method described above, wherein in a step, waste hydrochloric acid is the one in the waste hydrochloric acid of acidleach in Iron And Steel Industry, non-ferrous metals industry, pickling generation.
Further, a kind of waste hydrochloric acid recycling method described above, wherein in a step, waste hydrochloric acid is the waste hydrochloric acid that in Iron And Steel Industry, titanium slag acidleach produces.
A kind of waste hydrochloric acid recycling method described above, the ammonia wherein passed in b step is the ammonia that diamine technique produces.
A kind of waste hydrochloric acid recycling method described above, ammonia chloride crystal purity >=99% wherein obtained in step c.
Present method can be coupled nitrogen fertilizer production technique, utilize the spent acid that titanium slag etc. leaches, in conjunction with hydrazine technique, original equipment can be used, substantially without the need to the facility investment outside supplements, technique is improved a little, can the higher nitrogenous fertilizer of production added value, without the need to outer supplying heat source, product is pollution-free, flow process is short, simple to operate; Both can reduce the waste of waste hydrochloric acid and ammonia, avoid the pollution of environment, the production cost of nitrogenous fertilizer can have been reduced again, improve the added value that waste hydrochloric acid reclaims.
Embodiment
A kind of waste hydrochloric acid recycling of the present invention method, comprises the following steps:
A, will waste hydrochloric acid filter after pass in reactor, record the concentration c/molL of waste hydrochloric acid volume ν/L of adding and wherein chlorion
-1;
B, in reactor, pass into ammonia, start to pass into ammonia flow velocity and be
afterwards with
speed reduce logical ammonia speed, the flow velocity of ammonia must not be lower than
total intake of ammonia is 1.8 ν * c ~ 2.2 ν * c/mol; Wherein, γ is logical ammonia pipeline radius,
for logical ammonia length of pipe;
C, ammonia stop passing into rear 40 ~ 60min, are filtered by mixture in reactor, get filtrate, by filtrate evaporative crystallization, obtain ammonia chloride crystal.
A kind of waste hydrochloric acid recycling method described above, the ammonia wherein passed in b step can be converted into the liquefied ammonia of equivalent.
A kind of waste hydrochloric acid recycling method described above, wherein in a step, waste hydrochloric acid is the one in the waste hydrochloric acid of acidleach in Iron And Steel Industry, non-ferrous metals industry, pickling generation.
Further, a kind of waste hydrochloric acid recycling method described above, wherein in a step, waste hydrochloric acid is the waste hydrochloric acid that in Iron And Steel Industry, titanium slag acidleach produces.
The waste hydrochloric acid that the present invention utilizes titanium slag etc. to leach gained produces the method for nitrogenous fertilizer, and mainly make itself and ammonia gas react realize, its ultimate principle is as follows:
HCl+NH
3＝NH
4Cl
Contingent side reaction:
FeCl
2+ NH
3+ H
2o+O
2=NH
4cl+Fe (OH)
3↓ (thermopositive reaction, spontaneous carry out)
FeCl
3+ NH
3+ H
2o=NH
4cl+Fe (OH)
3↓ (thermopositive reaction, spontaneous carry out)
MgCl
2+ NH
3+ H
2o=NH
4cl+Mg (OH)
2↓ (thermopositive reaction, spontaneous carry out)
CaCl
2+ NH
3+ H
2o=NH
4cl+Ca (OH)
2↓ (thermopositive reaction, spontaneous carry out)
AlCl
3+ NH
3+ H
2o=NH
4cl+Al (OH)
3↓ (thermopositive reaction, spontaneous carry out)
MnCl
2+ NH
3+ H
2o=NH
4cl+Mn (OH)
2↓ (thermopositive reaction, spontaneous carry out)
Because ammonia solubleness in water is very large, main reaction is the character of acid-base reaction, so the utilization ratio of ammonia is very high, in addition, foreign ion contained in waste hydrochloric acid is converted into precipitation by the generation of various side reaction substantially, realizes the separation of material, because ammonia is weakly alkaline gas, even if pass into the excessive various alkali being converted into precipitation that also can not make again to dissolve, so separation efficiency is high, the ammonium chloride solution purity obtained is very high.
The present invention, in step a, first needs to carry out filtration treatment to waste and old hydrochloric acid, and the impurity in removing hydrochloric acid, prevents blocking pipeline.Afterwards waste hydrochloric acid is passed in reactor, the concentration c/molL of waste hydrochloric acid volume ν/L that record adds and wherein chlorion
-1.
A kind of waste hydrochloric acid recycling method described above, the ammonia wherein passed in b step is the ammonia that diamine technique produces.
The present invention in stepb, utilizes the bulging ammonia system of hydrazine technique to pass in reactor by ammonia, regulates ammonia flow, uninterrupted and drum ammonia pipe radius γ and length of pipe
relevant, the flow velocity of ammonia must not be lower than
flow control principle is first quick and back slow, passes into too fast, and ammonia is easily oxidized, and pass into speed comparatively slow, liquid return leads in ammonia pipeline.The design of this flow velocity lower bound can ensure to there will not be liquid return ammonia pipeline in logical ammonia process.
The method of waste hydrochloric acid recycling of the present invention, in step c, stops continuing to pass into ammonia after ammonia blasts certain hour, total intake of ammonia should control between 1.8 ν * c ~ 2.2 ν * c/mol, blast too much, cause waste, blast ammonia deficiency and the chlorine rate of recovery will be caused seriously to reduce.
The method of waste hydrochloric acid of the present invention recycling, in steps d, filters after the logical ammonia 40 ~ 60min of stopping, realizing being separated of filtrate and solid sediment.Filtrate is injected in reservoir, by the method for evaporative crystallization, ammonium chloride is crystallized out from solution, obtain the ammonia chloride crystal of purity >=99%.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
Embodiment 1
Get the waste and old dilute hydrochloric acid that certain enterprise's titanium slag leaching process produces, the chloride ion content detecting is wherein 4.22mol/L, the waste hydrochloric acid getting 2L is placed in reaction flask, the amount of the ammonia passed in system is monitored by under meter, initial Ventilation Rate is 100ml/s, reduce gradually afterwards, by regulating ammonia flow, should prevent from passing into too fast, ammonia is oxidized, prevent passing into speed again slower, liquid return leads in ammonia pipeline, total logical ammonia amount is 360L (16mol=1.9 ν * c), after logical ammonia terminates, wait for 60min, afterwards system is filtered, filtration terminates rear collection filtrate, by the method crystallization ammonium chloride of evaporative crystallization, through inspection, gained purity of ammonia chloride is 99.62%.
Embodiment 2
Get the waste and old dilute hydrochloric acid that certain enterprise's titanium slag leaching process produces, the chloride ion content detecting is wherein 4.57mol/L, the waste hydrochloric acid getting 2L is placed in reaction flask, the amount of the ammonia passed in system is monitored by under meter, initial Ventilation Rate is 120ml/s, reduce gradually afterwards, by regulating ammonia flow, should prevent from passing into too fast, ammonia is oxidized, prevent passing into speed again slower, liquid return leads in ammonia pipeline, total logical ammonia amount is 409L (18.28mol=2.0 ν * c), after logical ammonia terminates, wait for 45min, afterwards system is filtered, filtration terminates rear collection filtrate, by the method crystallization ammonium chloride of evaporative crystallization, through inspection, gained purity of ammonia chloride is 99.75%.
Embodiment 3
Get the waste and old dilute hydrochloric acid that certain iron and steel enterprise's cold-reduced sheet acid cleaning process produces, the chloride ion content detecting is wherein 4.2mol/L, the waste hydrochloric acid getting 2L is placed in reaction flask, the amount of the ammonia passed in system is monitored by under meter, initial Ventilation Rate is 140ml/s, reduce gradually afterwards, by regulating ammonia flow, should prevent from passing into too fast, ammonia is oxidized, prevent passing into speed again slower, liquid return leads in ammonia pipeline, total logical ammonia amount is 376L (16.8mol=2.0 ν * c), after logical ammonia terminates, wait for 40min, afterwards system is filtered, filtration terminates rear collection filtrate, by the method crystallization ammonium chloride of evaporative crystallization, through inspection, gained purity of ammonia chloride is 99.43%.
Embodiment 4
Get the waste and old dilute hydrochloric acid that the rust cleaning of certain iron and steel enterprise produces line gained, the chloride ion content detecting is wherein 4.7mol/L, the waste hydrochloric acid getting 2L is placed in reaction flask, the amount of the ammonia passed in system is monitored by under meter, the total intake of ammonia is 463L (20.68mol=2.2 ν * c), after logical ammonia terminates, wait for 50min, afterwards system is filtered, filtration terminates rear collection filtrate, by the method crystallization ammonium chloride of evaporative crystallization, through inspection, gained purity of ammonia chloride is 99.57%.
Claims (5)
1. a waste hydrochloric acid recycling method, is characterized in that: comprise the following steps:
A, will waste hydrochloric acid filter after pass in reactor, record the concentration c/molL of waste hydrochloric acid volume ν/L of adding and wherein chlorion
-1;
B, in reactor, pass into ammonia, start to pass into ammonia flow velocity and be
afterwards with
speed reduce logical ammonia speed, the flow velocity of ammonia must not be lower than
total intake of ammonia is 1.8 ν * c ~ 2.2 ν * c/mol; Wherein, γ is logical ammonia pipeline radius, and l is logical ammonia length of pipe;
C, ammonia stop passing into rear 40 ~ 60min, are filtered by mixture in reactor, get filtrate, by filtrate evaporative crystallization, obtain ammonia chloride crystal.
2. a kind of waste hydrochloric acid recycling method according to claim 1, is characterized in that: in a step waste hydrochloric acid be acidleach in Iron And Steel Industry, non-ferrous metals industry, one in the waste hydrochloric acid that produces of pickling.
3. a kind of waste hydrochloric acid recycling method according to claim 2, is characterized in that: in a step, waste hydrochloric acid is the waste hydrochloric acid that in Iron And Steel Industry, titanium slag acidleach produces.
4. a kind of waste hydrochloric acid recycling method according to any one of claims 1 to 3, is characterized in that: the ammonia passed in b step is the ammonia that diamine technique produces.
5. a kind of waste hydrochloric acid recycling method according to claim 1, is characterized in that: ammonia chloride crystal purity >=99% obtained in step c.
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|---|---|---|---|
| CN201510828569.1A CN105236446B (en) | 2015-11-24 | 2015-11-24 | A kind of recycling method of waste hydrochloric acid |
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|---|---|---|---|
| CN201510828569.1A CN105236446B (en) | 2015-11-24 | 2015-11-24 | A kind of recycling method of waste hydrochloric acid |
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| CN105236446B CN105236446B (en) | 2017-12-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107161951A (en) * | 2017-07-07 | 2017-09-15 | 天津市职业大学 | The method of recycling treatment iron-contained industrial waste hydrochloric acid |
| CN112265964A (en) * | 2020-11-06 | 2021-01-26 | 丁佐琳 | Industrial waste hydrochloric acid recycling treatment method |
Citations (4)
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|---|---|---|---|---|
| CA2373402A1 (en) * | 2001-02-27 | 2002-08-27 | Russian National Aluminium And Magnesium Institute (Vami) | Method of production of magnesium and chlorine from magnesium chloride solutions containing ammonium chloride |
| CN102107890A (en) * | 2011-01-21 | 2011-06-29 | 刘松林 | Treatment method and application of mother liquor in production process of sodium bicarbonate |
| CN103785263A (en) * | 2014-02-14 | 2014-05-14 | 赣州华茂钨材料有限公司 | Ammonia-containing tail gas treatment recycling method |
| CN104893147A (en) * | 2015-05-27 | 2015-09-09 | 福建工程学院 | Method for safely dechlorinating waste polyvinyl chloride and preparing high-purity ammonia chloride |
-
2015
- 2015-11-24 CN CN201510828569.1A patent/CN105236446B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2373402A1 (en) * | 2001-02-27 | 2002-08-27 | Russian National Aluminium And Magnesium Institute (Vami) | Method of production of magnesium and chlorine from magnesium chloride solutions containing ammonium chloride |
| CN102107890A (en) * | 2011-01-21 | 2011-06-29 | 刘松林 | Treatment method and application of mother liquor in production process of sodium bicarbonate |
| CN103785263A (en) * | 2014-02-14 | 2014-05-14 | 赣州华茂钨材料有限公司 | Ammonia-containing tail gas treatment recycling method |
| CN104893147A (en) * | 2015-05-27 | 2015-09-09 | 福建工程学院 | Method for safely dechlorinating waste polyvinyl chloride and preparing high-purity ammonia chloride |
Non-Patent Citations (1)
| Title |
|---|
| 刘永生: "从含盐酸废液中制取氯化铵的研究", 《有色金属（冶炼部分）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107161951A (en) * | 2017-07-07 | 2017-09-15 | 天津市职业大学 | The method of recycling treatment iron-contained industrial waste hydrochloric acid |
| CN107161951B (en) * | 2017-07-07 | 2019-04-19 | 天津市职业大学 | The method of recycling treatment iron-contained industrial waste hydrochloric acid |
| CN112265964A (en) * | 2020-11-06 | 2021-01-26 | 丁佐琳 | Industrial waste hydrochloric acid recycling treatment method |
| CN112265964B (en) * | 2020-11-06 | 2021-05-14 | 龙南鸿宇泰科技有限公司 | Industrial waste hydrochloric acid recycling treatment method |
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| Publication number | Publication date |
|---|---|
| CN105236446B (en) | 2017-12-15 |
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