CN1003909B - A kind of novel liquid extraction agent and extracting process thereof of phosphoric acid extraction - Google Patents
A kind of novel liquid extraction agent and extracting process thereof of phosphoric acid extraction Download PDFInfo
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- CN1003909B CN1003909B CN86106453.4A CN86106453A CN1003909B CN 1003909 B CN1003909 B CN 1003909B CN 86106453 A CN86106453 A CN 86106453A CN 1003909 B CN1003909 B CN 1003909B
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Abstract
The invention provides a kind of novel liquid extraction agent C that extracting and separating phosphoric acid is used from hydrochloric acidolysis phosphorus ore gained acid hydrolysis solution
6101-C
6121.Its chemical constitution is hexalin (C
6h
12o) 40-64%, pimelinketone (C
6h
10o) 35-60%, lightweight oil 0.1-0.6%.This extraction agent source is abundant, and strong to phosphoric acid extraction ability, selectivity is better, is easy to reclaim, stable chemical performance, toxicity and corrodibility are very low, and reusability is good, under normal temperature, do not solidify, can at normal temperatures or a little more than carrying out extracting operation under normal temperature, whole technological process be simple.Its key technical indexes of the phosphoric acid product being isolated with this extraction agent reaches or approaches food grade, in rationally utilizing, low-grade phosphate ore produces meticulous phosphorous chemical industry series product-provide the approach of chlorine as foodstuff additive, scavenging agent, feed phosphate etc.
Description
The invention belongs to from hydrochloric acidolysis phosphorus ore gained acid hydrolysis solution the novel liquid extraction agent of the use of extracting and separating phosphoric acid.
With decomposing phosphate rock by chlorhydric acid, its acid hydrolysis solution extracts with organic solvent, and the impurity such as calcium chloride are retained in water, thereby reaches the object that phosphoric acid is separated with other impurity.This be modern age phosphoric acid and Phosphate Fertilizer Industry in a kind of novel process.Hydrochloric acidolysis phosphorus ore solvent extration, though existing application in the world, its technology is delivered mainly with patent form greatly, and the screening that a lot of problem is still in exploration and raising stage, particularly best organic extractant is wide studying a question.Decomposing phosphate rock by chlorhydric acid solvent extration, the extraction agent of leading that appeared in the newspapers mainly contains:
(1) C
4-C
5fatty alcohol is as (U.S.Patent No.I such as propyl carbinol, different the eleventh of the twelve Earthly Branches alcohol, 929441,929442, B.Helferich, U.Baumann, Chem.Ber.85461(1952), Brit.Patent No.805517, Israel.Patent No.9660,9539, Brit Chem.Eng.4.223(1959), ж.
х н м .35.No1,190(1962), 36, No8,1702-1710(1963), 37, No, 4,874-880(1964))
(2) diisopropyl ether and tributyl phosphate composite extractant (ChemEngProg, 78, No.3,35-39(1982))
(3) the oxidized naphthenic hydrocarbon of hexanaphthene one class, methylcyclohexane, hexalin, methyl-cyclohexanol (U.S.Patent No.1968544(1934)).
(4) thioether (U.S.Patent No.2443915(1950))
(5) methyl alcohol, ethanol, acetone, tetrahydrofuran (THF) etc. use separately or mix and use (U.S.Patent No.4108957(1978), No.4141958(1979), CEP174, No11,6265(1979), GerPatent No.884358(1956)).
(6) S
34e (chemical fertilizer industry (1) (1984)).
(7) DBSO(dibutyl sulfoxide) (Journal of Chemical Industry and Engineering (4) (1982)).
, there is following problem in the extraction agent of above-mentioned reported seven types: 1. source is not abundant to some extent.Countries as a lot of in DBSO not yet produce.2. in water, solubleness is larger, and the rate of recovery is not high; 3. price is more expensive; 4. under normal temperature, there is solidification phenomenon or viscosity is larger, need to add thinner, or service temperature is higher; 5. the partition ratio to phosphoric acid and large not to the separation factor of impurity.
The present invention be directed to above-mentioned shortcoming, a kind of novel liquid extraction agent that is main body by hexalin and pimelinketone that screens and be mixed with from petrochemicals (VCC legal system is made the intermediates caprolactam production line).Its code name is (C
0101-C
0121).
Consisting of of this novel liquid extraction agent: ring bar alcohol (C
6h
12o) 40-64%, pimelinketone (C
6h
10o) 35-60%, lightweight oil 0.1-0.6%, its best proportioning is ring bar alcohol (C
6h
12o) 53.52% pimelinketone (C
6h
10o) 46.35%, lightweight oil 0.13%.
Novel liquid extraction agent provided by the present invention principle main points of extracting and separating phosphoric acid from hydrochloric acidolysis liquid are: the main functional group working in extraction agent component is-OH, > C=0, on Sauerstoffatom, there are two pairs of not bonding electronss, electric density is large, and some component ionic compound in system is had to certain binding ability.Conventionally this kind of extractants has two kinds to the extraction mechanisms of some component: one is to form solvation neutral complex and be extracted, and this solvation process is divided again solvation and secondary solventization two classes.When metal ion is directly combining and is being called a solvation (or claiming the first coordination sphere) with dative bond with extractant molecules.If extractant molecules is not directly to combine with metal ion, but is combined with the first coordination sphere molecule by hydrogen bond, be called secondary solvent.Another kind of extraction mechanisms in high acidity water with ionic association
salt mechanism is carried out.Because extraction agent and the oxonium ion entering in organic phase mineral acid are combined into
salt cation.Form complex anion and be extracted component positively charged ion with suitable anion binding, then complex anion with
salt ion associates and forms ion pair and be extracted and enter organic phase.
In organic phase because common extraction effect contains the impurity such as a small amount of calcium chloride, should wash calcium with a small amount of dilute phosphoric acid (containing HCl), due to phosphoric acid and the hydrochloric acid of existing certain content in water, therefore, it is that significantly this phenomenon just becomes the basis of washing calcium process that calcium chloride is shifted than phosphoric acid to water (washing calcium agent) by organic phase.
Organic phase, after washing calcium, then is carried out multistage reextraction with deionized water, obtains dilute phosphoric acid (containing P
2o
5more than 70 grams per liters), through evaporative distillation operation, obtain high density pure phosphoric acid, approach thermal phosphoric acid purity.
Remaining phosphoric acid in raffinate (calcium chloride solution), with milk of lime or precipitated superphosphate processing, can pay product precipitated superphosphate through defluorinate, can make drink additive and use after arsenic removal.
(the C using in extraction process
g101-C
g121) extraction agent, through reclaim and retrieval system in recycle, the results show, (C
g101-C
g121) after more than ten times recycle, there is not the phenomenons such as obvious qualitative change, degeneration, reusability is fine, and the rate of recovery is more than 99.8%.
This novel liquid extraction agent using method is to take solvent extration.
Solvent extration is to extract from the liquid phase of not dissolving each other mutually with it by means of organic solvent and the method for separate substance.Utilize the difference of same substance partition ratio in immiscible two-phase to reach the object of separation.The partition ratio of extraction process characterizes with the ratio of something analytical concentration in organic phase and water conventionally.Extraction agent is larger to the partition ratio of phosphoric acid, illustrates that the extracting power of extraction agent is stronger.
The composition that the chaste tree that we test use is assisted phosphorus ore and acid hydrolysis solution thereof is as table 1,2 listed.
Table 1 chaste tree is assisted phosphorus ore composition
| Composition | P 2O 5 | CaO | MgO | Fe 2O 3 | Al 2O 3 | CO 2 | F | Calcination loss | Acid non-soluble substance |
| Content (%) | 22.30 | 41.40 | 1.30 | 1.68 | 1.86 | 3.42 | 2.30 | 9.96 | 18.95 |
With proportion 1.52, the hydrochloric acid that content of hydrochloric acid is 30% is phosphorus ore acidolysis under definite processing condition, gained solution while hot suction filtration, obtain clarification its composition of acid hydrolysis solution as shown in table 2.
Table 2 acid hydrolysis solution composition
Experiment acid hydrolysis solution is than composition (grams per liter) remarks
Sequence number heavy (25 ℃)
P
2o
5hCl trip CaO MgO Fe
2o
3mnO
1 1.318 100.00 31.00 145.51 5.957 2.021 0.138 breezes are not
2 1.310 92.14 57.37 105.13 6.090 2.271 0.147 through roasting
3 1.350 103.68 56.80 163.98 8.460 2.230 0.185
4 1.320 102.00 69.00 147.00 5.900 2.280 /
5 1.325 104.34 58.09 130.83 / 2.640
P in the composition of acid hydrolysis solution
2o
5content be subject to the impact of the factors such as phosphorus ore grade, concentration of hydrochloric acid, foreign matter content.CaO/P in its group
2o
5be 1.4～1.602, with the CaO/P in ore
2o
5=1.856 is close.
The extracting power of more various extraction agents to phosphoric acid under the same conditions, as shown in table 3:
The partition ratio D of table 3 different solvents to phosphoric acid
| sequence number | solvent title or code name | distribution system D | remarks | ||
| 1 | propyl carbinol Pentyl alcohol primary isoamyl alcohol equal-volume propyl carbinol and primary isoamyl alcohol mixed solvent butanone-2-isopropylcarbinol ［ C g102～C g121methyl isopropyl Ketone hexone | 0.79200.57100.55000.67110.50200.62300.97200.10800.0350 | experiment condition (No. 1-9) 1. acid hydrolysis solution consists of in table 2, and 40 ℃ of 3. two-phase 4min4. duration of contact of sequence number 42. service temperature compares that (organic phase/water is 1: 1 | ||
| 2 | |||||
| 3 | |||||
| 4 | |||||
| 5 | |||||
| 6 | |||||
| 7 | |||||
| 8 | |||||
| 9 | |||||
| 10 | s 34eDBSO(dibutyl sulfoxide) petrolenum sulfoxide | 0.9061.2200.279 | 1. offer the current domestic product-free supply of data DBSO in " chemical fertilizer industry " 1 phase P5-6 in 1984 for quoted passage No. 10-12. | ||
| 11 | |||||
| 12 | |||||
Extraction agent (C as shown in Table 3
g101～C
g101) partition ratio be only second to DBSO extraction agent.
Extraction process is not only and a certain component will be extracted from water, the more important thing is various impurity is separated, and in order to characterize the complexity separating between component and component, conventionally represents with separation factor β:
The partition ratio of the partition ratio/impurity of β=phosphorus.
Require extraction agent should there is high selectivity to phosphoric acid, a little less than the common extraction effect of other impurity being tried one's best, can reach phosphoric acid separating-purifying object, (C
6101～C
g121) as shown in table 4 to the separation factor β of each component in acid hydrolysis solution:
Table 4 (C
6101～C
6121) separation factor β to each component
As can be seen from Table 4, (C
6101～C
6121) extraction agent is to Ca
2+, Mg
2+impurity has good separating effect, under similar experiment condition than propyl carbinol to Ca
2+β value 17.05, the β value 57.50 of primary isoamyl alcohol, S
34the β value 56.63 of E is large, but to iron ion almost without separating effect.
Extraction agent (C
6101～C
6121) in extraction process, there is relation with following factors:
1 (C
6101～C
6121) partition ratio D and the relation of temperature: experimental result is as shown in table 5:
Table 5 D and temperature relation
| Temperature | 30 | 40 | 50 | 60 | 70 | Experiment condition: 1. compare 1: 1,2. in table 2 No. 4 acid hydrolysis solutions 3. duration of contact 4min | |
| D value | 1.05 | 0.98 | 0.88 | 0.768 | 0.672 | ||
Experimental result shows (C
6101-C
6121) phosphoric acid partition ratio D is almost linearly declined with temperature rise, illustrate that extraction process is heat release, can improve D value therefore carry out extracting operation under low temperature or normal temperature, reduce energy consumption and make easy and simple to handle, but suitably elevated temperature can promote mass transfer and point phase velocity, heat effect and extraction temperature are also depended in the position of line of balance, therefore selection operation temperature is advisable at 20 ℃-50 ℃.
2. (C
6101-C
6121) extracting power in different phosphate acid system:
Impure more in hydrochloric acidolysis phosphorus ore gained acid hydrolysis solution, and nearly all muriate is water-soluble.Calcium chloride is the major impurity in acid hydrolysis solution.Although (C
6101-C
6121) to Ca
2+common extraction effect not serious, but in acid hydrolysis solution the more metallic salt of content, will certainly produce salting-out effect, extraction equilibrium is had to larger impact.
Table 6 (C
6101-C
g121) partition ratio to phosphoric acid in different phosphate acid system
| P 2O 5Grams per liter | HCl grams per liter | CaCl 2Grams per liter | Partition ratio D | Remarks | ||
| 134 | 0 | 0 | 0.168 | Experiment condition: 1, phosphoric acid used, hydrochloric acid, calcium chloride be analytical pure (AR) 2, be in a ratio of 1: 13,40 ℃ of temperature, 4 minutes duration of contact of two-phase | ||
| 134 | 8.42 | 0 | 0.189 | |||
| 134 | 8.42 | 260 | 0.429 | |||
Table 6 experimental data shows, to pure phosphoric acid system (C
6101-C
6121) be only 0.168 to the partition ratio of pure phosphorus phosphorus, and at the H having under a large amount of calcium chloride existence
3pO
4-HCl-CaCl
2in system, its partition ratio is at identical P
2o
5content under, increase to 0.429.
Table 7 (C
g101-C
g121) at different P
2o
5partition ratio in the acid hydrolysis solution of content:
| p 2o grams per liter | hCl grams per liter | partition ratio | |
| d pO | d hCl | ||
| 113.84 | 48.69 | 0.900 | 2.201 |
| 91.25 | 47.21 | 0.753 | 1.401 |
| 75.65 | 46.75 | 0.601 | 1.060 |
| 64.14 | 46.75 | 0.486 | 0.862 |
| experiment condition: 1. HCl46.75～48.69 grams per liter in acid hydrolysis solution used, Fe 2o 33.4 grams per liters, CaO139.68 grams per liter, MgO6.10 grams per liter, MnO0.2 grams per liter.2. be in a ratio of 1: 1, temperature: 35 ℃, duration of oscillation 5 minutes. | |||
Table 7 experimental result explanation: at more positively charged ion Ca
2+, Mg
2+, Fe
3+, Al
3+deng (C in the acid hydrolysis solution existing
6101-C
6121) partition ratio of phosphoric acid is increased more significantly.And D value is with P in acid hydrolysis solution
2o
5the increase of content and increasing, this is obviously due to due to salting-out effect, when there is a large amount of ionogen in acid hydrolysis solution, H
3pO
4ionization equilibrium make H
3pO
4exist mainly with molecularity, hydrochloric acid is strong acid, and dissociation goes out H
+also can suppress H
3pO
4dissociation, due to the H of molecularity
3pO
4be soluble in organic solvent, so improved partition ratio D value.P in acid hydrolysis solution
2o
5content (that is H
3pO
4content) higher H
3pO
4ionize more weakly, exist mainly with molecularity, be soluble in organic phase, cause D value increase.In addition also have the impact of other factors, as the formation of solvate, and attracted a large amount of free water molecules, thereby the effective concentration of water molecules has greatly been reduced (the corresponding raising of the concentration of phosphoric acid in other words), cause the partition ratio D of phosphoric acid to increase.
3. determining of duration of contact:
The extraction process of acid hydrolysis solution and distillation, the unit processes such as absorption are similar, are mass transfer processes between phase border.In this process, be also often accompanied by complicated chemical reaction, so be one of important process condition of extraction the duration of contact of two-phase in extraction process.Its experimental result is as shown in table 8:
Table 8 experimental result duration of contact
| Sequence number | Duration of oscillation (min) | The phase-splitting time (min) | Partition ratio | Appendix | |
| 1 | 1.15〃 | 1.30〃 | 0.805 | Experiment condition: 1. in temperature ℃ 2. duration of oscillation 4min 3. use tables 2, No. 4 acid hydrolysis solutions 4. are compared 1: 1 | |
| 2 | 1.30〃 | 1.30〃 | 0.890 | ||
| 3 | 1.50〃 | 1.30〃 | 0.928 | ||
| 4 | 2.0 | 1.30〃 | 0.968 | ||
| 5 | 3.0 | 1.30〃 | 0.960 | ||
| 6 | 4.0 | 1.30〃 | 0.972 | ||
| 7 | 5.0 | 1.30〃 | 0.976 | ||
Use as shown in Table 8 (C
g101-C
6121) when the phosphoric acid of extraction in acid hydrolysis solution, suitable two-phase is chosen as 2 minutes to 5 minutes duration of contact.
4. compare (solvent: acid hydrolysis solution) experiment:
Table 9 difference is compared partition ratio D and the P under condition
2o
5percentage extraction η P
2o
5
| Sequence number | Compare organic phase/water | Duration of contact (minute) | P in extraction phase 2O 5g/l | P in extracting phase 2O 5g/l | Partition ratio (D) | Percentage extraction (%) η P 2O 5 |
| 1 | 0.5∶1 | 4 | 50.69 | 69.27 | 0.841 | 30.12 |
| 2 | 1∶1 | 4 | 37.45 | 40.86 | 0.916 | 47.21 |
| 3 | 1.5∶1 | 4 | 30.20 | 32.60 | 1.008 | 59.81 |
| 4 | 2∶1 | 4 | 28.20 | 28.50 | 1.010 | 74.79 |
| 5 | 2.5∶1 | 4 | 25.00 | 24.60 | 1.015 | 79.04 |
| 6 | 3∶1 | 4 | 21.40 | 22.20 | 0.964 | 81.53 |
| 7 | 4∶1 | 4 | 16.90 | 18.50 | 0.914 | 86.67 |
| 8 | 5∶1 | 4 | 12.70 | 16.30 | 0.789 | 90.61 |
Experimental result by table 9 is found, with (C
6101-C
6121) when the phosphoric acid of extraction in acid hydrolysis solution, when the beginning of its partition ratio D value, be to increase along with the increase of comparing.Be in a ratio of between 1.5-2, partition ratio D has extreme value, continues to increase while comparing, and D value declines with the increase of comparing again.And P
2o
5percentage extraction to be less than the amplitude that 3 scope increases with the increase of comparing large comparing.Bring up to 2.5 when above, η P when comparing
2o
5the amplitude increasing with the increase of comparing diminishes.The appearance of this regular phenomenon, its reason can be summed up two aspects: first salting-out effect, it two is competitions of producing under certain condition of other components in acid hydrolysis solution and squeezes effect.Compare and be less than at 3 o'clock, salting-out effect is with comparing increase, extraction agent dissolves P
2o
5the factors such as ability also increases play a leading role.The component that plays salting out in acid hydrolysis solution is not generally to be extracted or to be seldom extracted, but free hydrochloric acid and FeCl in acid hydrolysis solution
3deng different, they are by (C
6101-C
6121) extraction ability much larger than P
2o
5the ability being extracted.They and extraction agent generate complex compound, and the acidity of the free HCl in acid hydrolysis solution is greatly reduced, even if the ionogen in acid hydrolysis solution greatly reduces, have produced P
2o
5extraction competition and squeeze effect.Moreover compare and excessively also can make each concentration of component in whole extraction system be diluted, so also can be to P
2o
5partition ratio raising has a negative impact.
The phosphoric acid making by extracting and separating of the present invention, through mass analysis: H
3pO
465-85%; Fe
2o
30.36%; Al
2o
30.0168%; CaO 0.046%; MgO 0.0187%; As 3-10ppm; F 2-5ppm;
Heavy metal (in Pb) 10-15ppm.
The purity of visible product phosphoric acid is higher, and main art skill index reaches or approaches food grade.
By (C noted earlier
6101-C
6121) extraction agent also has the following advantages; Source abundant (petrochemical complex intermediates), domestic supply is guaranteed, and inexpensive, and toxicity is very little, stable chemical nature, strong to the extracting power of phosphoric acid, selectivity is good, and the rate of recovery is high, flash point is high, under normal temperature, does not solidify, can be at normal temperature or respectively higher than carrying out extracting operation under normal temperature.
Embodiment: get 4mol extraction agent, the proportioning of this extraction agent is hexalin 53.52%, pimelinketone 46.35%, lightweight oil 0.13% mixes this extraction agent with No. 4 acid hydrolysis solutions of same volume in table 2, vibrate 4 minutes, and service temperature is 30 ℃, after 10 minutes, phase-splitting finishes, recording extraction agent is 0.98 to phosphoric acid partition ratio, organic phase is washed to calcium with a small amount of dilute phosphoric acid (containing HCl), then carries out multistage reextraction with deionized water, gained dilute phosphoric acid, through distillation, evaporation operation, obtains high dense pure phosphoric acid.Product is analyzed, recorded wherein and contain: H
3pO
483%; Fe
2o
30.36%; Al
2o
30.0168%; CaO 0.046%; MgO 0.0187%; As 4ppm; F 2ppm; Heavy metal (in Pb) 11ppm.
Claims (5)
1, a liquid extraction agent for phosphoric acid extraction, is characterized in that being mixed and being formed by hexalin, pimelinketone and lightweight oil, and the content of hexalin is 40-64%, and the content of pimelinketone is 35-60%, and the content of lightweight oil is 0.1-0.6%.
2, extraction agent according to claim 1, is characterized in that the optimum content of hexalin, pimelinketone and lightweight oil is: hexalin: 53.52%, and pimelinketone: 46.35%, lightweight oil: 0.13%.
3, a method for phosphoric acid extraction from the acid hydrolysis solution of hydrochloric acidolysis phosphorus ore, is characterized in that extraction conditions is: be in a ratio of 0.5-3.0, extraction temperature is 20-50 ℃, and two-phase duration of contact is 4-7 minute, and the phase-splitting time is 10-30 minute.
4, method according to claim 3, is characterized in that the optimum process condition of extraction is for comparing: 2.0, and extraction temperature: 35 ℃, two-phase duration of contact: 6 minutes, the phase-splitting time: 20 minutes.
5, method according to claim 3, the processing step that it is characterized in that extraction is that this extraction agent is mixed with the acid hydrolysis solution of same volume, after vibration phase-splitting finishes, organic phase is washed to calcium with a small amount of dilute phosphoric acid (containing HCl), carry out multistage reextraction with deionized water again, gained dilute phosphoric acid, through distillation, evaporation operation, obtains high dense pure phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86106453.4A CN1003909B (en) | 1986-09-19 | 1986-09-19 | A kind of novel liquid extraction agent and extracting process thereof of phosphoric acid extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86106453.4A CN1003909B (en) | 1986-09-19 | 1986-09-19 | A kind of novel liquid extraction agent and extracting process thereof of phosphoric acid extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86106453A CN86106453A (en) | 1988-04-06 |
| CN1003909B true CN1003909B (en) | 1989-04-19 |
Family
ID=4803216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86106453.4A Expired CN1003909B (en) | 1986-09-19 | 1986-09-19 | A kind of novel liquid extraction agent and extracting process thereof of phosphoric acid extraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1003909B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094111C (en) * | 1999-12-30 | 2002-11-13 | 清华大学 | Alternate extraction-counter extraction process of producing phosphate |
| CN106348273B (en) * | 2016-08-17 | 2018-01-09 | 湖北三宁化工股份有限公司 | A kind of extractant and its extracting process of hydrochloric acid legal system industrial phosphoric acid |
| CN114835094B (en) * | 2022-03-17 | 2024-04-26 | 中国科学院过程工程研究所 | Method for preparing wet-process phosphoric acid and calcium sulfate by acidolysis and in-situ extraction of phosphorus from phosphorus ore |
-
1986
- 1986-09-19 CN CN86106453.4A patent/CN1003909B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN86106453A (en) | 1988-04-06 |
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