CN85108552A - The treatment process of chlorhydric acid pickling waste containing iron - Google Patents
The treatment process of chlorhydric acid pickling waste containing iron Download PDFInfo
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- CN85108552A CN85108552A CN85108552.0A CN85108552A CN85108552A CN 85108552 A CN85108552 A CN 85108552A CN 85108552 A CN85108552 A CN 85108552A CN 85108552 A CN85108552 A CN 85108552A
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- iron trichloride
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 235000011167 hydrochloric acid Nutrition 0.000 title claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000005554 pickling Methods 0.000 title claims abstract description 11
- 230000008569 process Effects 0.000 title claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 84
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 4
- 239000010959 steel Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract 2
- 239000012074 organic phase Substances 0.000 claims description 18
- 150000003512 tertiary amines Chemical class 0.000 claims description 15
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 125000001302 tertiary amino group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 238000005192 partition Methods 0.000 description 9
- -1 2-ethyl Chemical group 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 150000002505 iron Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 235000000396 iron Nutrition 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical class CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- 241000531116 Blitum bonus-henricus Species 0.000 description 1
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- 241001313099 Pieris napi Species 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
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- Extraction Or Liquid Replacement (AREA)
Abstract
The treatment process of chlorhydric acid pickling waste containing iron belongs to the matting field of metal.Solve waste and the pollution problem in the spent acid solution that the hydrochloric acid cleaning is produced is handled of steel or processing component.Characteristics are: the oxidation of divalent in the waste liquid is become ferric iron, tell wherein molysite with extraction agent, remaining acid solution recycles.The extraction liquid water recycles after stripping, and the ferric chloride aqueous solutions that obtains can be made into series product.Oxygenant is with superoxol or chlorine etc., and extraction agent can be C with carbochain
6-C
18Tertiary amine or quarternary ammonium salt (contain-methyl or-ethyl) etc.
Description
The invention belongs to the matting field of metal.
Steel or machined components often need to clean except that removing iron scale with hydrochloric acid before processing, and the processing of the chlorhydric acid pickling waste containing iron that is produced then becomes the problem that must solve thus.The terms of settlement that adopts both at home and abroad mainly contains three types of (Ministry of Metallurgical Industry Building Research General Institute Institute for Environmental Research volume, metallurgical environmental protection information documents-waste acid treatment technology-2,60-98, (1983) at present; The clear 56-5828 of Japan's special permission; US4,248,851): a kind of is large-lot producer's roasting method commonly used, and purpose is to reclaim hydrochloric acid, obtains ferric oxide (Fe thereupon
2O
3), this method energy expenditure is big, to the equipment requirements height, is unsuitable for medium and small sized enterprises and uses; Second kind is, adds that sulfuric acid obtains hydrochloric acid and vitriol is ferrous or add iron powder runs out the hydrochloric acid in the waste liquid, by the system iron trichloride.Though the former can obtain hydrochloric acid again in this method, has consumed sulfuric acid, the present purposes of the ferrous sulfate that obtains is wide not enough; Though the latter can obtain the wider iron trichloride of purposes, has consumed the hydrochloric acid that needs more, and is unfavorable to producing; The third is, neutralization or the discharging of dilution back, and its shortcoming is to have abandoned iron and hydrochloric acid contained in the waste liquid, to discharge 10 tons every day, quite loses each one ton of iron and hydrochloric acid every day, and environment or water source are caused severe contamination.
In view of the foregoing, the present invention is especially at the third above-mentioned method, adopt the extraction treatment method, promptly directly in waste liquid, only add oxygenant, ferrous chloride in the waste liquid is oxidized to iron trichloride, with the extraction system that contains extraction agent it is told from waste liquid, again high-purity ferric chloride product through stripping usefully.Remaining hydrochloric acid recirculation is used, and the extraction system after the reextraction also can be recycled, and this method both can have been avoided environment or contaminated water source, stopped waste again, also obtain product, avoided the unfavorable factor of above-mentioned other treatment processs simultaneously, and equipment is simple, less investment.Concrete scheme is as follows:
Confirm by analysis, aforementioned chlorhydric acid pickling waste containing iron, main component is the ferrous chloride and the hydrochloric acid of higher concentration.If can select suitable extraction agent for use, tell molysite wherein, remaining hydrochloric acid recycles.It is a kind of easy treatment process.But extraction two valency molysite are difficult to find extraction agent cheap and easy to get from strong acid; And by extracting trivalent iron salt in the strong acid, the extraction agent kind that can Gong select for use more (T.Ishinrori etc., JAERI-1047(1967); JAERI-1062(1964); JAERI-1106(1966)), and loading capacity is generally bigger, strips also to be easier to, and can obtain useful iron trichloride product.Therefore the ferrous chloride in the waste liquid being oxidized to iron trichloride and extracting, is attainable solution.The ideal oxygenant is, at normal temperature, normal pressure and do not need both to have played oxygenizement under the condition of specific installation, not giving in the handled waste liquid again increases impurity.
The oxygenant that meets above-mentioned requirements has: air, oxygen, superoxol and chlorine etc., but shown in figure (1), atmospheric oxidation speed is slow, and oxidation is fully difficult, thereby makes system become complicated, unified difficult treatment.The fast oxidation of aqueous hydrogen peroxide solution speed of response is complete, at room temperature, only needs to add the hydrogen peroxide of equivalent, can all be oxidized to ferric iron to ferrous iron.Chlorine oxidation speed is also quite fast, and shown in table (1), when acid concentration was lower than 4N, 1.5～2 hours was oxidable complete, and when acidity was hanged down, speed of response was accelerated.
Oxidation capacity is stronger, can be used for oxidation.
Extract trivalent iron salt from hydrochloric acid soln, available extraction agent kind is more, the research but the extraction of relevant high density trivalent iron salt and selection of Extractant are still needed.Select different types of extraction agent to test among the present invention.Wherein the neutral extraction agent comprises: isopropyl ether, isooctyl alcohol, methyl iso-butyl ketone (MIBK), TRI N BUTYL PHOSPHATE, oxidation trialkyl phosphine; Tart has: (2-ethylhexyl) phosphonic acids (the 2-ethyl is own) ester, di(2-ethylhexyl)phosphate-(2-methyl heptan) ester, di(2-ethylhexyl)phosphate-(the 2-ethyl is own) ester; Also have tertiary amine and quarternary ammonium salt etc. (J.M.White etc., J.Inorg.Nucl.Chem, 16,337(1961); A.D.Nelson etc., J.Inorg.Mucl.Chem, 27,439(1965); O.Lery etc., J.Inorg.Nucl.Chem, 33,551(1971); B.E.Meclellsn etc., Anal.Chem, 36,1985(1964); M.L.Good etc., J.Amer.Chem.Soc, 82,5636(1960)).Shown in figure (2), neutral extraction agent is (6-12N) when acid concentration is big, and higher partition ratio (D) is just arranged; Acidic extractant is when acid concentration is low (1-5N), and partition ratio is also lower; Wherein tertiary amine, quarternary ammonium salt (1-12N) partition ratio in the acid concentration scope of broad is all higher, is more suitable for the extraction of trivalent iron salt, and the structure of described tertiary amine is shown in formula I:
R in the formula
1, R
2, R
3All represent alkyl, the three can be identical, also can be inequality; R
1, R
2, R
3The contained carbonatoms C that can respectively do for oneself respectively
6-C
18; The also mixing tertiary amine of possible constructions such as formula I.
The structure of quarternary ammonium salt is shown in formula II:
R in the formula
4, R
5, R
6All represent alkyl, the three can be identical, also can be inequality; R
4, R
5, R
6The contained carbonatoms C that can respectively do for oneself respectively
6-C
18, R
7Be methyl or ethyl; Or with the mixture of structure such as formula II.For example make extraction agent, shown in table (2), can reach balance in five minutes with above-mentioned tertiary amine:
The starting time table of table 2 tertiary amine extraction iron trichloride
The extraction conditions of result shown in the table is: the acid concentration of ferrous contained hydrochloric acid solution is 4.0N.Iron trichloride concentration is 1.56M.Comparing (R) is 2.40 ℃ of extraction temperature.The composition of extraction system is: tri-n-octyl amine 45%, isooctyl alcohol 35%, kerosene 20%(volume ratio).Extraction agent is used above-mentioned Adogen instead, also can reach balance in five minutes.Shown in figure (3), figure (4), use above-mentioned tertiary amine (20%) and Adogen (30%) to make extraction agent respectively, when acid concentration is high, help the extraction of trivalent iron salt.Table (3) shows, and is when extraction temperature is high, favourable to extracting.
Table 3 temperature is to the influence of extraction
Result's extraction conditions is in the table: the acid concentration of acid solution is 4.0N, and the concentration of iron trichloride is 1.57M.Extraction system is: tertiary amine 45%, isooctyl alcohol 35%, kerosene 20%.Five minutes extraction time.
The concentration height of extraction agent is generally favourable to extracting, but can change extraction agent and the concentration that helps extraction agent within the specific limits as the case may be.The used extraction system of the present invention consists of: extraction agent 10-50%, and isooctyl alcohol or secondary octanol (helping extraction agent) 15-35%, remaining is kerosene (thinner), and listed percentage ratio is all volume ratio, and wherein extraction agent is aforesaid tertiary amine or quarternary ammonium salt.Only need single-stage extraction to get final product in five minutes.The acid solution of telling after extraction can be recycled and reused for and clean steel or processing component.Effect does not have significant difference with fresh acid solution shown in table (4).After repeatedly using, when acid concentration is low, need add hydrochloric acid.
The molten iron tests of table 4 extraction back acid solution
(40 ℃ of temperature of reaction)
Available ortho-water of the reextraction of extraction liquid or redistilled water are made extraction agent, and the reextraction temperature is below 40 ℃, adopt 6-8 level tandem to strip, and residue in the iron trichloride amount in the extraction system, different and different with extraction agent kind and amount.
Extraction system after the reextraction can be recycled and reused for extraction, effect and the new extraction system no significant difference of preparing.Shown in table (5):
The effect of extracting of extraction system after table 5 back extraction
The result is that extraction system is in the table: aforementioned Adogen 20%, isooctyl alcohol 20%, kerosene 60%.The waste liquid acid concentration that is used to extract is 2.0N, and wherein the concentration of iron trichloride is 0.24M.Extraction liquid can be recycled after the water back extraction.Can replenish in case of necessity.
The aqueous solution that reextraction obtains is acid liquor ferri trichloridi, and its emmission spectrometric analysis result shows that gained iron trichloride purity is very high, do not contain former ferrous contained hydrochloric acid hydrochlorate and wash some impurity in the waste liquid, shown in table (6):
The emmission spectrometric analysis of impurity in table 6 hydrochloric acid pickling waste liquor and the stripping aqueous solution
This liquor ferri trichloridi can be made series product as required.
In order to be illustrated more clearly in the present invention, enumerate following example:
Example 1, at room temperature, logical chlorine is one hour in 176 milliliters of chlorhydric acid pickling waste containing irons, and wherein ferrous chloride is oxidized to iron trichloride, and predicting its concentration is 1.56M, and acid concentration is 4.0N.With wherein add 300 milliliters of extraction systems (aforementioned tertiary amine 45%, isooctyl alcohol 35%, kerosene 20% volume ratio.), in 30 ℃ of oscillation extractions five minutes.Separate two-phase liquid, acid recycles mutually; Organic phase knows that after measured it contains iron trichloride concentration is 0.715M(partition ratio 2.02), carry out 8 grades of tandems reextraction (stream was than 2: 1) with ortho-water in 38 ℃, shown in figure (5), the residual iron trichloride concentration of the back organic phase of stripping is 0.021M, accounts for 2.9% before the back extraction.Water contains iron trichloride 1.32M, is used to prepare the series product of iron trichloride, and organic phase recycles.
Example 2 is got 35 milliliters of the chlorhydric acid pickling waste containing irons crossed by chlorine oxidation.Its acid concentration is 2.6N, and the concentration that contains iron trichloride is 1.82M, in wherein adding 70 milliliters of extraction systems (aforementioned tertiary amine 30%, isooctyl alcohol 30%, kerosene 40%, volume ratio), 30 ℃ of following oscillation extractions five minutes.Tell organic phase, wherein contain iron trichloride 0.567M(partition ratio 0.827), water carries out 6 grades of tandems strips (stream was than 2: 1), shown in figure (6).The residual iron trichloride concentration of organic phase is 0.10M after the balance, accounts for 17.6% before the back extraction.Remaining is handled with example 1.
Example 3 is got 50 milliliters of chlorhydric acid pickling waste containing irons behind the logical chlorine oxidation.Its acid concentration is 2.6N, and the concentration that contains iron trichloride is 1.82M, in wherein adding 100 milliliters of extraction systems (aforesaid Adogen 30%, isooctyl alcohol 30%, kerosene 40%, volume ratio), in 30 ℃ of oscillation extractions five minutes, tells organic phase.Wherein the concentration of iron trichloride is 0.625M, and water carries out 6 grades of tandems strips, and shown in figure (7), has reached extraction equilibrium behind back extraction 3 rows, shows that back extraction is very fast on kinetics.After the back extraction in the organic phase concentration of residual iron trichloride be 0.184M, be 29.44% of first three ferric chloride concn of back extraction.Remaining is handled with example 1.
Example 4. is got 110 milliliters of chlorhydric acid pickling waste containing irons behind the logical chlorine oxidation, and its acid concentration is 4.0N, and iron trichloride concentration is 1.56M.In wherein adding 220 milliliters of extraction systems (aforesaid Adogen 40%, isooctyl alcohol or secondary octanol 35%, kerosene 25%, volume ratio), in 30 ℃, oscillation extraction five minutes.Tell organic phase, recording the concentration that wherein contains iron trichloride is 0.72M(partition ratio 6).Water carries out 8 grades of tandems and strips.Shown in figure (8).After the back extraction in the organic phase residual iron trichloride concentration be 0.32M, account for 44.4% of iron trichloride concentration before the back extraction.Remaining is handled with example 1.
The present invention is particularly suitable for medium-sized and small enterprises and adopts. Equipment is simple, easy to operate, energy consumption is low, small investment, makes waste liquid not useless, and all goods and materials are rationally utilized, and can obtain byproduct, have stopped waste, have eliminated the pollution to environment and water source.
Brief Description Of Drawings
Fig. 1. under the different acid concentrations, the ferrous velocity ratio of atmospheric oxidation is.
Fig. 2. use different extraction agents, extract the partition ratio of iron trichloride in the different concentration of hydrochloric acid solution.Extraction agent is respectively:
1. TRI N BUTYL PHOSPHATE.2. positive trioctylamine.
3. isooctyl alcohol.4. oxidation methyl trialkyl ammonium.
5. methyl iso-butyl ketone (MIBK).6.(2-phosphonic acids ethylhexyl)
(the 2-ethyl is own) ester
7. isopropyl ether.8. di(2-ethylhexyl)phosphate-(2-methyl heptan)
Ester.
9. di(2-ethylhexyl)phosphate-(2-ethyl oneself) ester.
Fig. 3. from the solution of different concentration of hydrochloric acid, extract the partition ratio of iron trichloride with tertiary amine.
Fig. 4. from different concentration of hydrochloric acid solution, extract the partition ratio of iron trichloride with Adogen.
Fig. 5. after 8 grades of back extractions of tertiary amine iron content extracted organic phase water, the iron trichloride concentration of organic phase and aqueous phase.
Fig. 6. after 6 grades of back extractions of tertiary amine iron content extracted organic phase water, the iron trichloride concentration of organic phase and aqueous phase.
Fig. 7. after 6 grades of back extractions of Adogen salt iron content extracted organic phase water, the iron trichloride concentration of organic phase and aqueous phase.
Fig. 8. after 8 grades of back extractions of Adogen iron content extracted organic phase water, the iron trichloride concentration of organic phase and aqueous phase.
Claims (3)
1, steel are the spent acid solution of ferrous chloride and hydrochloric acid through hydrochloric acid cleaning generation main component, be referred to as a kind of treatment process of chlorhydric acid pickling waste containing iron, it is characterized in that, directly in waste liquid, only add oxygenant, the ferrous chloride in the waste liquid is oxidized to iron trichloride; With containing extraction agent, helping the extraction system of collection agent and thinner, extraction iron trichloride wherein; Tell organic phase, strip, get iron trichloride; Water after the extraction can be recycled as acid; Extraction system after the reextraction also can be recycled.
2, according to claim 1, it is characterized in that the used oxygenant of oxidation is chlorine or aqueous hydrogen peroxide solution, oxidizing temperature is respectively and is lower than 50 ℃ and in room temperature; Extraction agent is a tertiary amine, and its structure is shown in formula I:
R in the formula
1, R
2, R
3All represent alkyl, the three can be identical, also can be inequality; R
1, R
2, R
3The contained carbonatoms C that can respectively do for oneself respectively
6-C
18; The also mixing tertiary amine of possible constructions such as formula I; Extraction system contains extraction agent 10-50%, isooctyl alcohol or secondary octanol 15-35%, and remaining is kerosene (per-cent is all volume ratio); Strippant is ortho-water or redistilled water.
3, according to claim 2, it is characterized in that described extraction agent is a quarternary ammonium salt, its structure is shown in formula II:
R in the formula
4, R
5, R
6, all representing alkyl, the three can be identical, also can be inequality; R
4, R
5, R
6Contained carbonatoms can be distinguished each C naturally
6-C
18, R
7Be methyl or ethyl; Or be the mixture of structure such as formula II.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85108552 CN1009546B (en) | 1985-11-27 | 1985-11-27 | Treatment of chlorhydric acid pickling waste containing iron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85108552 CN1009546B (en) | 1985-11-27 | 1985-11-27 | Treatment of chlorhydric acid pickling waste containing iron |
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| CN85108552A true CN85108552A (en) | 1987-06-03 |
| CN1009546B CN1009546B (en) | 1990-09-12 |
Family
ID=4796069
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|---|---|---|---|
| CN 85108552 Expired CN1009546B (en) | 1985-11-27 | 1985-11-27 | Treatment of chlorhydric acid pickling waste containing iron |
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-
1985
- 1985-11-27 CN CN 85108552 patent/CN1009546B/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389078C (en) * | 2006-01-24 | 2008-05-21 | 杨淙垣 | Regeneration treatment method of steel sheet pickling waste liquor |
| CN101838073B (en) * | 2009-03-20 | 2012-10-10 | 宝山钢铁股份有限公司 | Silicon steel alkali rinse purification method and device |
| CN103755080A (en) * | 2014-01-03 | 2014-04-30 | 常熟风范电力设备股份有限公司 | Waste acid and wastewater reuse production process for hot galvanizing |
| CN104003451A (en) * | 2014-05-29 | 2014-08-27 | 白晓光 | Preparation method of ferric chloride hexahydrate |
| CN104003451B (en) * | 2014-05-29 | 2016-06-01 | 白晓光 | The preparation method of a kind of ferric chloride (FeCl36H2O) |
| CN106282577A (en) * | 2016-08-31 | 2017-01-04 | 重庆大学 | The recycling of a kind of stainless steel acid cleaning waste water and processing method |
| CN106282577B (en) * | 2016-08-31 | 2018-01-05 | 重庆大学 | The recycling and processing method of a kind of stainless steel acid cleaning waste water |
| CN108408960A (en) * | 2018-03-08 | 2018-08-17 | 湖南大学 | A method of liquid is scrapped in the iron-containing pickling of recovery processing |
| CN110304661A (en) * | 2019-06-20 | 2019-10-08 | 李柏丛 | Soft magnetic ferrite high-performance iron oxide new preparation process |
| CN112661196A (en) * | 2020-12-29 | 2021-04-16 | 斯瑞尔环境科技股份有限公司 | Purification method of ferric trichloride |
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