CN1006222B - Recovery of calcium chloride from waste liquid of - Google Patents
Recovery of calcium chloride from waste liquid of Download PDFInfo
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- CN1006222B CN1006222B CN86104840.7A CN86104840A CN1006222B CN 1006222 B CN1006222 B CN 1006222B CN 86104840 A CN86104840 A CN 86104840A CN 1006222 B CN1006222 B CN 1006222B
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- calcium chloride
- waste liquid
- liquid
- calcium
- hydrochloric acid
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Abstract
The present invention relates to an improvement of a China patent with the patent application number '85102768', which is proposed to solve the problem of the drainage of calcium chloride waste liquid in hydrochloric acid acidolysis phosphate ore technology for liquid extraction of organic solvent liquid. The present invention is also suitable for solving the problem of the drainage of the calcium chloride waste liquid in hydrochloric acid acidolysis phosphate ore technology for producing calcification. The method of the present invention is circular processes in which no waste liquid is drained. The present invention is characterized in that hydrochloric acid is added into the calcium chloride waste liquid; by using a hydrochloric acid salting-out principle, calcium chloride is crystallized, separated out and separated; mother liquid is returned to a decomposing tank to decompose phosphate ore; thus, the circular processes in which no waste liquid is drained are formed.
Description
The decomposing phosphate rock by chlorhydric acid system of the present invention relates to phosphoric acid or in and the recovery and utilization technology of the heavy calcium post chlorization calcium wasting liquid of legal system.
The hydrochloric acidolysis phosphorus ore has and is swift in response, and the rate of decomposition height to advantages such as mineral are overcritical, prepares in the research of phosphoric acid at decomposing phosphate rock by chlorhydric acid, and what have the production meaning is the organic solvent liquid-liquid extraction method.The flow process of Israel " IMI " company can be used as the representative of this method.Inventor class Neil [1] the human C4 alcohol such as [2] of this method is extraction agent, and phosphoric acid is come together into organic phase, makes calcium chloride stay water and reaches the two isolating purpose.Phosphoric acid water back extraction in the organic phase obtains dilute phosphoric acid, removal of impurities can obtain phosphoric acid product after concentrating, and aqueous phase contains the muriate of a large amount of calcium chloride and small amounts of iron magnalium and be dissolved in the C4 alcohol of aqueous phase, and water reclaims C4 alcohol through stripping, and the water behind the stripping enters the sea.The phosphoric acid quality that " IMI " flow process is produced can reach the level of thermal phosphoric acid, and production cost method of specific heat phosphoric acid is low.But its flow process is longer, and a large amount of waste solution of calcium chloride dischargings are arranged.
Another staple product of decomposing phosphate rock by chlorhydric acid is heavy calcium, this method is carried out more research and production [3] both at home and abroad, and generally the method for Cai Yonging is two step neutralisations.In the decomposed solution of decomposing phosphate rock by chlorhydric acid, drop into lime slurry and make PH=3～3.5, produce secondary calcium phosphate (heavy calcium) precipitation this moment, a large amount of fluorine form Calcium Fluoride (Fluorspan) and precipitate simultaneously, together with white residue filter the heavy calcium of fertilizer grade, in the first step and after mother liquor fluorine-containing very low, continue with lime slurry PH=5.5～6 that neutralize, filter and obtain fluorine-containingly sinking calcium in the feed grade 0.2% below.At last, the waste liquid that contains calcium chloride is had to discharging, and one ton of heavy calcium of every production need discharge 8～9 tons of waste solution of calcium chloride.
No matter the salt acid system produces the still heavy calcium of phosphoric acid, and they have the emission problem of waste solution of calcium chloride jointly.The waste solution of calcium chloride problem already causes investigator's attention.Israel handles waste solution of calcium chloride [4] with white lime, regulates PH=6.5, separates and removes impurity such as Al, Fe, F, Si, calcium chloride brine and CO
2, the MgO counter current contact, remove CaCO
3, again with MgCl
2The salt solution thermal degradation becomes MgO and HCl.People (5) suggestion NH is also arranged
3And CO
2Handle CaCl
2Waste liquid obtains NH
4Cl and CaCO
3Precipitation, American scholar (6,7) is then avoided CaCl
2The appearance of waste liquid, the suggestion nitration mixture decomposing phosphate rock of hydrochloric acid and phosphoric acid.
The present invention is the continuation of Chinese patent application number " 85102768 ", aim at and overcome the waste solution of calcium chloride emission problem that exists in hydrochloric acidolysis phosphorus ore organic solvent fluid-liquid extraction process and propose, but it is suitable for solving the waste solution of calcium chloride emission problem in the heavy calcium technology of hydrochloric acidolysis phosphorus ore production equally, and this method is the circulation process of a no discharging of waste liquid.The core of method is to have added hydrogenchloride in waste solution of calcium chloride, utilizes the hydrochloric acid principle of saltouing, and crystallization of calcium chloride is separated, and mother liquor returns the decomposer decomposing phosphate rock, forms no discharging of waste liquid circulation process.The present invention has become waste solution of calcium chloride into the calcium chloride solid phase prod, has solved contaminated wastewater, has reduced production cost, has simplified liquid-liquid extraction technology.Accompanying drawing is that the present invention prepares phosphoric acid and do not have discharging of waste liquid circulation process skeleton diagram, is described as follows:
Rock Phosphate (72Min BPL) and hydrochloric acid are (strictly speaking, be the whole mother liquor that contains hydrochloric acid) be reflected in the decomposer (1) and carry out, full mistake 40 orders of ore, temperature of reaction 40-60 ℃, reaction times 10-30 minute, slip heat filtering in strainer (2) is removed impurity such as white residue, decomposed solution can be at this step defluorination, and defluorinating agent is a sodium-chlor, and consumption is the 1.5-3% that decomposes liquid measure, also defluorination not allows fluorine take in the calcium chloride.The extractor group is three grades of cross-flows, the stripper group also is three grades of cross-flows, organic phase after extraction is being washed in the calcium groove (4) and is being washed calcium, enter the middle back extraction of stripper group (6) again and obtain dilute phosphoric acid, organic solvent behind the separation dilute phosphoric acid returns extractor group (3) and recycles, the water that comes out from extractor group (3) imports absorbing hydrogen chloride the suction acid tank (8), in cold analysis groove (9), analyse calcium chloride again, filter (10) and isolate the solid calcium chloride hexahydrate, the whole mother liquor that contains hydrogenchloride is got back to decomposing phosphate rock in the decomposer (1), and additional a certain amount of dilute hydrochloric acid or water are regulated the condition that whole mother liquor makes its suitable decomposing phosphate rock requirement before whole mother liquor enters decomposer in case of necessity.The present invention adopts bigger Rock Phosphate (72Min BPL) granularity, and high acidity is decomposed fast, makes impurity such as iron aluminium discharge system with white residue morely.The present invention is a circulation process, must with phosphoric acid all collection go into organic phase, must stripping do not reclaim the organic solvent of aqueous phase yet.
Example one
Rock Phosphate (72Min BPL) is formed: P
2O
5: 34.18% CaO:49.35% MgO:3.02%
Fe
2O
3：1.05% Al
2O
3：0.79%
Acid non-soluble substance: 2.40% F:2.98% Pb:12ppm
As：1ppm CO
2：6.00%
Except that the first time, throw 100 parts in ore deposit at every turn, temperature of reaction 40-50 ℃, reaction times 3-5 minute.The extraction agent propyl carbinol, three grades of cross-flows of extraction progression compare 1: 1(weight), wash calcium water and form 1%H
3PO
4With the 5%HCl mixed solution, wash the calcium water than 0.25: 1(weight), extraction temperature 28-40 ℃, 5 minutes extraction time, back extraction compares 1: 1(weight), and back extraction temperature: room temperature, three grades of cross-flows of back extraction progression.The acidity of saltouing 15-28%, salt eutectoid temperature-4-+5 ℃.
Dilute phosphoric acid is analyzed %
Cycle index dilute phosphoric acid weight P
2O
5CaO MgO Fe
2O
3Al
2O
3F
(part)
Product-free, circulation is not set up complete
3 416 8.22 0.62 0.21 0.31 do not detect
4 408 7.10 0.42 0.17 0.24 do not detect 0.027
5 407 7.77 0.32 0.11 0.38 0.07 0.027
6 397 8.14 0.37 0.16 0.27 do not detect 0.024
7 411 8.06 0.26 0.14 0.26 do not detect 0.022
Calcium chloride (6 water) is analyzed %
Cycle index calcium chloride weight Ca Mg F P
2O
5
(part)
1 170 14.12 0.21 1.37 0.91
2 236 15.07 0.23 1.57 1.07
3 213 14.86 0.20 1.46 0.68
4 218 15.01 0.19 1.31 0.46
5 208 14.97 0.20 1.55 0.50
6 216 14.36 0.24 1.29 0.47
7 222 14.58 0.17 1.38 0.81
Example two
Phosphorus ore is formed: with example one.
Except that the first time, throw 50 parts in ore deposit, whole mistake 20 orders of ore, temperature of reaction 50-60 ℃, 5 minutes reaction times at every turn.Use the sodium-chlor defluorinate, the sodium-chlor consumption is the 2-3% of decomposition liquid measure, natural subsidence 2 hours, and the extraction agent propyl carbinol, three grades of cross-flows of extraction progression, compare 1: 1(weight), extraction temperature 26-40 ℃, 5 minutes extraction time, washing calcium water is 2%H
3PO
4With the 5%HCl mixed solution, wash the calcium water than 0.25: 1, strip and compare 1: 1(weight), three grades of cross-flows of back extraction progression, back extraction temperature room temperature, 5 minutes back extraction time, the acidity of saltouing 4-32% salt eutectoid temperature-16～+ 8 ℃.
Dilute phosphoric acid is analyzed %
Cycle index dilute phosphoric acid weight P
2O
5CaO MgO Fe
2O
3Al
2O
3F
(part)
Product-free, circulation is not set up complete
3 210 7.94 0.33 0.11 0.30 do not detect 0.011
4 213 8.12 0.31 0.12 0.27 do not detect 0.012
5 216 8.17 0.26 0.11 0.34 do not detect 0.014
6 199 8.08 0.29 0.13 0.28 do not detect 0.010
Calcium chloride (6 water) is analyzed %
Cycle index calcium chloride weight (part) Ca Mg F P
2O
5
1 89 14.67 0.14 0.22 0.61
2 130 15.31 0.13 0.19 0.47
3 22 15.42 0.13 0.17 0.41
4 102 15.20 0.12 0.24 0.53
5 141 14.66 0.18 0.21 0.88
6 78 16.33 0.09 0.19 0.39
Example three
Phosphorus ore is formed: P
2O
5: 24.13% CaO:32.73% MgO:2.37%
Fe
2O
3：1.81% Al
2O
3：2.45%;
Acid non-soluble substance: 31.44% F:2.22%
100 parts in each * ore deposit, full mistake 40 orders of ore, temperature of reaction 50-60 ℃, reaction times 2-5 minute, heat filtering, decomposed solution salt defluorination, the salt add-on is for decomposing 5% of liquid measure, and natural subsidence 1 hour removes by filter villiaumite.Use 50%CaCO
3(toothpaste level) once in and about PH=3, filter and to obtain the wet product of the heavy calcium of fertilizer grade, filtrate neutralizes about PH=6 with 20% lime slurry secondary again, filter, eluriate, the heavy calcium of the feed product that wets.Filtrate and 1,2 time are eluriated wash water and are merged and feed an amount of hydrogenchloride, keep the acidity 10-32% that saltouts, salt eutectoid temperature-12～+ 4 ℃.
In the secondary and back mother liquor is formed %
Cycle index P
2O
5Ca Mg Fe Al F
1 0.67 7.30 0.22 0.09 0.07 0.013
2 0.60 6.94 0.26 0.06 0.04 0.011
3 0.53 7.28 0.18 slight 0.010
4 0.57 7.47 0.27 0.01 little 0.011
5 0.36 7.03 0.21 slight 0.016
Calcium chloride is analyzed (6 water) %
Cycle index Ca Mg P
2O
5
1 15.79 0.10 is little
2 15.35 0.11 is little
3 16.23 0.09 is little
4 16.14 0.10 is little
5 15.34 0.13 is little
Reference
〔1〕《Phosphorus ＆ Potassium》1983.No125，29-33，
〔2〕“phosphoric acid by liquid-liquid extraction”A.Banil《British Chemical Engineering》，1959.223-224.
(3) " the domestic and international general situation of development of salt acid system precipitated superphosphate " Zhejiang chemical institute, " Zhejiang chemical industry ", 1973.5,1-24.
〔4〕Israeli P.32291（1972），CA77，154569u.
〔5〕u.s.p，3，092，488（1963）.
〔6〕u.s.p，3，652，206（21）791，944〔72〕.
〔7〕“The Chlorophate process For dicelcium phosphate”，E.J.FOX and K.C.Clark，《Ind，Eng·Chem.》，35，1264-68（1943）。
Claims (4)
1, the recoverying and utilizing method of waste solution of calcium chloride in a kind of salt acid system decomposing phosphate rock is characterized in that:
1.1 after the decomposing phosphate rock by chlorhydric acid liquid-liquid extraction prepares phosphoric acid or contain behind the heavy calcium of neutralisation preparation in the waste liquid of calcium chloride and add hydrogenchloride, calcium chloride salt is separated out,
The salt acidacidity of calcium chloride is 4%-32% 1.2 saltout, temperature-16～8 ℃,
Recycling Mother Solution decomposing phosphate rock 1.3 saltout behind the separation calcium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86104840.7A CN1006222B (en) | 1986-07-12 | 1986-07-12 | Recovery of calcium chloride from waste liquid of |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86104840.7A CN1006222B (en) | 1986-07-12 | 1986-07-12 | Recovery of calcium chloride from waste liquid of |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86104840A CN86104840A (en) | 1987-07-22 |
| CN1006222B true CN1006222B (en) | 1989-12-27 |
Family
ID=4802619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86104840.7A Expired CN1006222B (en) | 1986-07-12 | 1986-07-12 | Recovery of calcium chloride from waste liquid of |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006222B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380062B (en) * | 2008-08-26 | 2011-07-20 | 武汉凌派化工科技有限公司 | Method for producing feedstuff calcium hydrogen phosphate by decomposition of medium-low grade phosphate ore using hydrochloric acid |
| CN102992296A (en) * | 2012-11-09 | 2013-03-27 | 凯恩德利(北京)科贸有限公司 | Process for producing phosphoric acid through hydrochloric acid method |
| CN105603215B (en) * | 2015-12-30 | 2017-12-19 | 武汉工程大学 | One kind efficiently leaches K, Ca, Mg, P method using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals |
| CN111003699A (en) * | 2019-12-30 | 2020-04-14 | 龙蟒大地农业有限公司 | Method for producing feed-grade calcium hydrophosphate and co-producing industrial-grade calcium chloride by hydrochloric acid method |
| CN112299591A (en) * | 2020-09-24 | 2021-02-02 | 昆明理工大学 | Method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology |
-
1986
- 1986-07-12 CN CN86104840.7A patent/CN1006222B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN86104840A (en) | 1987-07-22 |
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