CN105967216A - Production method of barium chloride - Google Patents

Production method of barium chloride Download PDF

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Publication number
CN105967216A
CN105967216A CN201610510636.XA CN201610510636A CN105967216A CN 105967216 A CN105967216 A CN 105967216A CN 201610510636 A CN201610510636 A CN 201610510636A CN 105967216 A CN105967216 A CN 105967216A
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Prior art keywords
barium
barium chloride
solution
chloride
hopper
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CN201610510636.XA
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CN105967216B (en
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丁淑暖
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SHENZHEN JIAXIN CHEMICAL CO., LTD.
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丁淑暖
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/20Halides
    • C01F11/24Chlorides

Abstract

The invention discloses a method for producing barium chloride from barium residues of barium sulfate. The method for producing the barium chloride from the barium residues of the barium sulfate comprises the following steps of S100: grinding the barium residues together with water or a dilute barium chloride solution to be slurry by utilizing a ball grinder; S200: adding hydrochloric acid into an obtained slurry material, carrying out a reaction to obtain a barium chloride mixed solution, and controlling a terminal PH (Potential of Hydrogen) value to be 6.5 to 7.5; S300: filtering and separating the obtained mixed solution, discarding residues, then recycling the resides, using washing water for the ball grinder, and using a mixed clear solution for a next working procedure; S400: adding hydrogen peroxide into the solution obtained in step S300, carrying out oxidization to convert vulcanized sulfate ions and sulfite ions into sulfate ions to be removed, and oxidizing ferrous ions to be ferric irons. By using the production method of the barium chloride, the barium residues are effectively utilized; the prepared barium chloride is high in purity.

Description

Method for producing barium chloride
Technical field
The invention belongs to chemical field, particularly to a kind of method for producing barium chloride.
Background technology
The barium slag of Present Domestic barium salt industry is substantially scene storage, or landfill, part brickmaking, controlling the water circulation mud. Wherein contain the acid-soluble barium of a great deal of, do not recycle the waste causing resource.From currently barium slag method being produced Paper and the patent of barium chloride are seen, the most general theoretical discussion, to by the impurity brought in slag, grain Son, the separation such as calcium, magnesium, sulphite, thiosulfate etc. proposes method, implements putting into production Feasibility brings difficulty.
Summary of the invention
For the defect of prior art, the invention provides a kind of method for producing barium chloride, comprise the following steps: S100: utilize ball mill that together with water or dilute barium chloride solution, barium slag is ground pulping;S200: starch at gained Adding hydrochloric acid in material, react to obtain barium chloride mixed solution, terminal pH value controls at 6.5-7.5;S300: will Gained mixed solution filters and separates, the recycling that slag is abandoned, and wash water is used for ball mill, and mixing clear solution is used for Subsequent processing;S400: in step S300 gained solution add hydrogen peroxide, oxidation make sulfuration sulfate ion, Sulfurous acid ion changes into sulfate ion and removes, and oxidation of divalent iron ion becomes ferric ion, adds hydrogen Barium monoxide or sodium hydroxide remove iron ion, the barium chloride solution filtering limpid;S500: by step S400 Gained barium chloride solution evaporation and concentration, obtains barium chloride crystallization, and Recycling Mother Solution uses to chloride containing calcium 350g/L-390g/L;S600: by step S500 gained barium chloride crystallization carry out re-dissolved, temperature 90 DEG C with On, concentration 400g-350g/L, add hydrogen peroxide, barium hydroxide, adjust pH value 7-7.5, carry out deferrization, sulfur, Filtering for crystallizing;S700: by crystallization centrifugal filtration, washing, dry to obtain barium chloride, Recycling Mother Solution is used in molten Solve barium chloride, when mother solution calcium chloride concentration reaches 100-90g/L, return evaporization process evaporation.
Optionally, described barium slag mechanization conveyer device, including hoisting ring 2.1, mobile inner bag 2.2, moves Filtering table 2.3, hydrolysis hopper 2.4 and shell 2.5, described hydrolysis hopper 2.4 is arranged in shell 2.5 Bottom, described in be moved through filter disc 2.3 be arranged on hydrolysis hopper 2.4 on, described mobile inner bag 2.2 passes through Suspension ring chain 2.6 is suspended on hoisting ring 2.1 and is positioned at the top of hydrolysis hopper 2.4;Described mobile inner bag 2.2 Bottom be made up of two base plates 2.7 being provided with balance pivot, the outboard end of base plate 2.7 is all by moving Spacing flange 2.8 on inner bag 2 limits and moves on it, and the medial end of two base plates 2.7 is connected to same In rotating shaft 2.9, the side of described hydrolysis hopper 2.4 is provided with filtrate (liquid 2.10.
Optionally, described filtering drying integrated reactor includes that kettle 3.1, the top of described kettle 3.1 set It is equipped with charging aperture 3.2, electric rotating machine 3.3, lifting motor 3.4 and high temperature and high pressure steam air inlet, kettle 3.1 Bottom be provided with leakage fluid dram 3.6, the side of kettle 3.1 is provided with solid material outlet 3.7, in kettle 3.1 under Portion's level is provided with drainage screen 3.8, and the position that drainage screen 3.8 is arranged is at described solid material outlet 3.7 and leakage fluid dram Between 3.6, described electric rotating machine 3.3 and lifting motor 3.4 are connected by connecting shaft 3.9 material scraper 3.10, Described material scraper 3.10 can move up and down inside the kettle 3.1 above drainage screen 3.8 and rotate.
The invention has the beneficial effects as follows: the present invention can be used for the barium slag of barium sulfate industry and produces barium chloride or carbonic acid The barium slag of barium industry produces barium chloride etc., reclaims acid-soluble barium salt therein and economizes on resources.By wet grinding, solve Certainly dry milling processes pulverizes dust problem and uneven mixed problem;By oxidant removal thiosulfate, sulfurous Hydrochlorate ferrum, use evaporative crystallization, crude crystals re-refine de-magging, calcium, ferrum etc. qualified products.The present invention Mobile inner bag the barium slag driving hydrolyzed can be transported to automatic discharging support, and by gravity automatic discharging, And can quickly change filtering layer, replace hand digging, improve the machine automatization of whole hydrolysis barium slag conveying Change degree.Filtering drying integrated reactor integrates filtration and dries, its device structure and operation all phases The simplest for prior art, eliminate the intermediate equipment on a large amount of production line, the equipment that decreases is to product Pollution, improve product quality, saved equipment purchasing cost.
Accompanying drawing explanation
Fig. 1 is the flow chart of method for producing barium chloride of the present invention;
Fig. 2 is the structural representation of barium slag conveyer device of the present invention;
Fig. 3 is the structural representation of filtering drying reactor in the present invention.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, the most right The detailed description of the invention of the present invention is described in detail, and makes the above and other purpose of the present invention, feature and excellent Will definitely become apparent from.The part that reference instruction identical in whole accompanying drawings is identical.The most deliberately by than Example draws accompanying drawing, it is preferred that emphasis is illustrate the purport of the present invention.
Referring to Fig. 1, the barium sulfate barium slag of the present invention produces the method for barium chloride and comprises the following steps:
S100: by barium slag conveyer device, barium slag is sent into ball mill, utilize ball mill by barium slag and water or dilute Barium chloride solution grinds pulping together;Referring to Fig. 2, described barium slag mechanization conveyer device, including hoisting ring 2.1, move inner bag 2.2, be moved through filter disc 2.3, hydrolysis hopper 2.4 and shell 2.5, described hydrolysis hopper 2.4 are arranged on the bottom in shell 2.5, described in be moved through filter disc 2.3 be arranged on hydrolysis hopper 2.4 on, institute State mobile inner bag 2.2 be suspended on hoisting ring 2.1 by lifting loop chain 2.6 and be positioned at hydrolysis hopper 2.4 Top;The bottom of described mobile inner bag 2.2 is made up of two base plates 2.7 being provided with balance pivot, base plate 2.7 Outboard end be all to be limited shifting it on by the spacing flange 2.8 on mobile inner bag 2, two base plates 2.7 Medial end is connected in same rotating shaft 2.9, and the side of described hydrolysis hopper 2.4 is provided with filtrate (liquid 2.10.Described hoisting ring 2.1 is connected on two base plates 2.7 as lever by lifting loop chain 2.6 At fulcrum.Groove in described hydrolysis hopper 2.4 tilts to a side of filtrate (liquid 2.10.On conveyer device The barium slag driving hydrolyzed can be transported on automatic discharging support by gravity automatic discharging by mobile inner bag, Gravity can also be leaned on driving handling movable filter dish to discharging support when hopper needs to change filtering layer when hydrolyzing Automatic discharging, it is achieved quickly, changes filtering layer automatically, replaces hand digging.
S200: adding hydrochloric acid in gained slurry, concentration of hydrochloric acid, at 3.5-4.0mol/L, reacts to obtain barium chloride Mixed solution, terminal pH value controls at 6.5-7.5;This mixed solution be containing barium chloride, calcium chloride, The mixed solution of magnesium chloride, thiosulfate, sulphite, calcium chloride, secondary slag etc..Concentration of hydrochloric acid mistake Height, owing to salt effect, the aluminium ion leached in solution and silicon ion are combined the inclined aluminum of generation with the hydrion of excess Hydrochlorate colloid and siliceous colloid, be wrapped in barium solid impurity particle surface, will hinder the leaching of each ion, concentration of hydrochloric acid Too low meeting causes barium ions not leach completely, applicants experimentally found that concentration of hydrochloric acid exists 3.5-4.0mol/L time its ion leaching rate maximum.
S300: filtered by gained mixed solution and separate, the recycling that slag is abandoned, wash water is used for ball mill, mixing Clear solution is used for subsequent processing.
S400: add hydrogen peroxide or other oxidants in step S300 gained solution, oxidation makes sulfuration sulphuric acid Radical ion, sulfurous acid ion change into sulfate ion and remove, and oxidation of divalent iron ion becomes ferric ion, Adding barium hydroxide or sodium hydroxide removes iron ion, (barium chloride contains the barium chloride solution filtering limpid Amount 150-200g/L, Ca, Mg amount to calcium chloride 80-50g/L, sodium chloride 1-3g/L).
S500: concentrated by step S400 gained solution evaporation, obtains barium chloride crystallization, and Recycling Mother Solution uses to containing Calcium chloride 350g/L-390g/L goes to manufacture calcium chloride operation.
S600: step S500 gained barium chloride is crystallized (crystallization is containing calcium chloride about about 1%), carries out Re-dissolved, controls temperature more than 90 DEG C, concentration 400g-350g/L, adds hydrogen peroxide, barium hydroxide, adjusts PH Value 7-7.5, carries out deferrization, sulfur, filtering for crystallizing.
S700: crystallization be centrifuged, sends into filtering drying integrated reactor and carries out filtering, washs, dries Qualified products, Recycling Mother Solution is used in dissolving barium chloride, when mother solution calcium chloride concentration reaches 100-90g/L, Return evaporization process evaporates.
Fig. 3 shows an embodiment of filtering drying integrated reactor: a kind of filtering drying integration is anti- Answer still, including kettle 3.1, the top of described kettle 3.1 be provided with charging aperture 3.2, electric rotating machine 3.3, Lifting motor 3.4 and high temperature and high pressure steam air inlet, the bottom of kettle 3.1 is provided with leakage fluid dram 3.6, kettle The side of 3.1 is provided with solid material outlet 3.7, and the lower horizontal in kettle 3.1 is provided with drainage screen 3.8, drainage screen 3.8 positions arranged export between 3.7 and leakage fluid dram 3.6 at described solid material, described electric rotating machine 3.3 and liter Fall motor 3.4 has material scraper 3.10 by connecting shaft 3.9 connection, and described material scraper 3.10 can be at drainage screen Kettle 3.1 above in the of 3.8 is internal to be moved up and down and rotates.Described material scraper 3.10 has more than two, respectively It is fixed on the position of differing heights in rotary shaft 3.9.The edge of described drainage screen 3.8 is provided with raised line, still Be provided with the raised line position place of adapting in body 3.1 locking groove, raised line and groove can prevent can filter screen 3.8 with Material rotates together with material scraper 3.10.After the solid compound of the water of mixing enters into reactor, by reaction The high temperature and high pressure steam air inlet at still top passes through high temperature and high pressure steam, carries out pressing and stoving and filtration, when mixed The liquid of compound material is got rid of from leakage fluid dram 3.6 after being filtered by drainage screen 3.8, when aneroid again in mixed material After body filters out, open solid material outlet 3.7, allow material scraper by electric rotating machine 3.3 and lifting motor 3.4 3.10 rotate from top to bottom, solid material is released material outlet 3.7 admittedly, is then carried by material by auger It is directly entered storehouse.
Elaborate a lot of detail in the above description so that fully understanding the present invention.But more than retouch Stating is only presently preferred embodiments of the present invention, and the present invention can be to be much different from other side described here Formula is implemented, and therefore the present invention is not limited by disclosed above being embodied as.The most any it is familiar with this area Technical staff, without departing under technical solution of the present invention ambit, may utilize method and the skill of the disclosure above Technical solution of the present invention is made many possible variations and modification by art content, or be revised as equivalent variations etc. Effect embodiment.Every content without departing from technical solution of the present invention, according to the present invention technical spirit to more than Any simple modification, equivalent variations and the modification that embodiment is done, all still falls within technical solution of the present invention protection In the range of.

Claims (1)

1. a method for producing barium chloride, it is characterised in that comprise the following steps: S100: by barium slag machine Barium slag is sent into ball mill by tool conveyer device, utilizes ball mill by barium slag together with water or dilute barium chloride solution Grind pulping;Described barium slag mechanization conveyer device, including hoisting ring (2.1), mobile inner bag (2.2), It is moved through filter disc (2.3), hydrolysis hopper (2.4) and shell (2.5), described hydrolysis hopper (2.4) Be arranged on the bottom in shell (2.5), described in be moved through filter disc (2.3) be arranged on hydrolysis hopper (2.4) On, described mobile inner bag (2.2) is suspended in hoisting ring (2.1) by lifting loop chain (2.6) and above and is positioned at The top of hydrolysis hopper (2.4);The bottom of described mobile inner bag (2.2) is provided with balance pivot by two Base plate (2.7) is constituted, and the outboard end of base plate (2.7) is all by the limit convex on mobile inner bag (2.2) Plate (2.8) limits and moves on it, and the medial end of two base plates (2.7) is connected to same rotating shaft (2.9) On, the side of described hydrolysis hopper (2.4) is provided with filtrate (liquid (2.10);S200: in gained slurry Adding hydrochloric acid, react to obtain barium chloride mixed solution, terminal pH value controls at 6.5-7.5;S300: by gained Mixed solution filters and separates, and mixing clear solution is for subsequent processing;S400: in step S300 gained solution Middle addition hydrogen peroxide, oxidation makes sulfuration sulfate ion, sulfurous acid ion change into sulfate ion removing, Oxidation of divalent iron ion becomes ferric ion, adds barium hydroxide or sodium hydroxide removes iron ion, filter Obtain limpid barium chloride solution;S500: by step S400 gained barium chloride solution evaporation and concentration, obtain barium chloride Crystallization, Recycling Mother Solution uses to chloride containing calcium 350g/L-390g/L;S600: by the gained chlorination of step S500 Barium crystallizes and carries out re-dissolved, temperature more than 90 DEG C, concentration 400g-350g/L, addition hydrogen peroxide, barium hydroxide, Adjust pH value 7-7.5, carry out deferrization, sulfur, filtering for crystallizing;S700: crystallization is sent into filtering drying integration Reactor is centrifuged filtering, washs, dries to obtain barium chloride, and Recycling Mother Solution is used in dissolving barium chloride, when When mother solution calcium chloride concentration reaches 100-90g/L, return evaporization process evaporation.
CN201610510636.XA 2016-07-01 2016-07-01 Method for producing barium chloride Active CN105967216B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106145174A (en) * 2016-07-04 2016-11-23 深州嘉信化工有限责任公司 A kind of barium sulfate barium slag produces the method for industrial chlorinating titanate
CN107177733A (en) * 2017-06-05 2017-09-19 中南大学 A kind of method of barite deposit refining and edulcoration synthetical recovery calcium and magnesium
CN113754160A (en) * 2020-06-01 2021-12-07 中冶长天国际工程有限责任公司 Method and system for cleanly recovering calcium chloride from acidic flue gas washing wastewater

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Publication number Priority date Publication date Assignee Title
CN101654274A (en) * 2009-09-15 2010-02-24 赖成文 Barium chloride production technology
CN102628105A (en) * 2012-04-18 2012-08-08 青海省安全生产科学技术中心 Method for comprehensively recycling and using baric waste slag in refined aluminum production process
CN103374662A (en) * 2012-04-18 2013-10-30 青海省安全生产科学技术中心 Device for recycling waste residues containing barium comprehensively during refined aluminum production process
CN104085781A (en) * 2014-07-16 2014-10-08 中建三局第一建设工程有限责任公司 Earth loading and transporting device
CN203889909U (en) * 2014-05-28 2014-10-22 广州港集团有限公司 Bottom-opening cargo hopper lifting appliance for bulk cargo loading operation
CN105271347A (en) * 2015-10-16 2016-01-27 重庆市川渝矿业有限责任公司 Method for preparing high-purity barium salt by using witherite-barytocalcite industrial waste residues
CN205222444U (en) * 2015-11-06 2016-05-11 中国十七冶集团有限公司 A collection dress self -discharging case that is used for short steel pipe of handling scaffold

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101654274A (en) * 2009-09-15 2010-02-24 赖成文 Barium chloride production technology
CN102628105A (en) * 2012-04-18 2012-08-08 青海省安全生产科学技术中心 Method for comprehensively recycling and using baric waste slag in refined aluminum production process
CN103374662A (en) * 2012-04-18 2013-10-30 青海省安全生产科学技术中心 Device for recycling waste residues containing barium comprehensively during refined aluminum production process
CN203889909U (en) * 2014-05-28 2014-10-22 广州港集团有限公司 Bottom-opening cargo hopper lifting appliance for bulk cargo loading operation
CN104085781A (en) * 2014-07-16 2014-10-08 中建三局第一建设工程有限责任公司 Earth loading and transporting device
CN105271347A (en) * 2015-10-16 2016-01-27 重庆市川渝矿业有限责任公司 Method for preparing high-purity barium salt by using witherite-barytocalcite industrial waste residues
CN205222444U (en) * 2015-11-06 2016-05-11 中国十七冶集团有限公司 A collection dress self -discharging case that is used for short steel pipe of handling scaffold

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106145174A (en) * 2016-07-04 2016-11-23 深州嘉信化工有限责任公司 A kind of barium sulfate barium slag produces the method for industrial chlorinating titanate
CN107177733A (en) * 2017-06-05 2017-09-19 中南大学 A kind of method of barite deposit refining and edulcoration synthetical recovery calcium and magnesium
CN107177733B (en) * 2017-06-05 2018-12-21 中南大学 A kind of method of barite deposit refining and edulcoration synthetical recovery calcium and magnesium
CN113754160A (en) * 2020-06-01 2021-12-07 中冶长天国际工程有限责任公司 Method and system for cleanly recovering calcium chloride from acidic flue gas washing wastewater

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Inventor after: Sun Zhongxin

Inventor after: Zhao Yong

Inventor after: Zhao Hui

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Inventor before: Ding Shunuan

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Address after: 053871 front grinding head industrial zone, Hengshui, Hebei, Shenzhou

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