CN107298455A - A kind of method that spent acid of utilization hydrochloric acid and hydrofluoric acid prepares calcirm-fluoride - Google Patents

A kind of method that spent acid of utilization hydrochloric acid and hydrofluoric acid prepares calcirm-fluoride Download PDF

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Publication number
CN107298455A
CN107298455A CN201710600351.XA CN201710600351A CN107298455A CN 107298455 A CN107298455 A CN 107298455A CN 201710600351 A CN201710600351 A CN 201710600351A CN 107298455 A CN107298455 A CN 107298455A
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China
Prior art keywords
fluoride
calcirm
acid
solution
hydrochloric acid
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CN201710600351.XA
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李江
肖玉岭
李飞
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Zibo Fei Yuan Chemical Co Ltd
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Zibo Fei Yuan Chemical Co Ltd
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Priority to CN201710600351.XA priority Critical patent/CN107298455A/en
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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
    • C01F11/22Fluorides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

Abstract

The present invention relates to the method that the spent acid of a kind of production method of calcirm-fluoride, more particularly to a kind of utilization hydrochloric acid and hydrofluoric acid prepares calcirm-fluoride, step mainly has:Spent acid and calcium chloride solution is added dropwise, the mol ratio for controlling calcium chloride and hydrogen fluoride is 1:2.1 2.15, after completion of dropping, continue to react 1 1.5 hours;Insulation is to 40 50 DEG C, and stirring is reacted 2 hours;Staticly settle and obtain calcirm-fluoride solid, gained filtrate is the hydrochloric acid solution of enrichment to 12%~18.6%;Washing of precipitate, filtering obtains being fluorinated calcium product.The method of the present invention has calcium fluoride particles degree big, easily filtering, and technique is simple, and production cost is low, can reclaim calcirm-fluoride and hydrochloric acid, thoroughly solves the pollution problem of industrial fluorine-containing spent acid at present.

Description

A kind of method that spent acid of utilization hydrochloric acid and hydrofluoric acid prepares calcirm-fluoride
Technical field
Prepared the present invention relates to the spent acid of a kind of production method of calcirm-fluoride, more particularly to a kind of utilization hydrochloric acid and hydrofluoric acid The method of calcirm-fluoride.
Background technology
As fluorine chemical industry is developed rapidly, fluorite money reserves are gradually decreased, and this seriously threatens fluorine chemical industry Sustainable development, therefore, the artificial preparation of calcirm-fluoride increasingly attracts attention.The fluorine-containing spent acid of industry is production in industrial processes Raw Funing tablet substantially exceeds the waste water of limited value of discharge standard, and fluoride waste has to the health and the ecological balance of human and animal There is serious threat, therefore fluoride wastewater treatment and research are particularly important.2 points based on more than, research prepares one kind and adopted With the calcium precipitation fluorine removal of low cost, and coproduction has sales value hydrochloric acid, there is larger economic value and social value.
At present, the spent acid containing hydrogen fluoride is all fluorine chemical byproduct mostly, including produces the production such as Nitrogen trifluoride, lithium aluminium Raw.The characteristics of these spent acid one is that concentration is high, and after processing, HF concentration is that 33%, HCl concentration is 9.5%.Two be to contain HF, contains HCl again.Three be also containing a certain amount of organic matter and other impurity.
Therefore, when preparing calcirm-fluoride using above-mentioned spent acid, the calcirm-fluoride of generation, granularity is smaller, and organic in spent acid Thing or impurity form thick sediment, it is difficult to filter, and filtration time is long, it is necessary to carry out dewater treatment with centrifuge, Complex process, cost is high.
The content of the invention
The technical problem to be solved in the present invention is to provide the side that the spent acid of a kind of utilization hydrochloric acid and hydrofluoric acid prepares calcirm-fluoride Method, big with calcium fluoride particles degree, easily filtering, technique is simple, and production cost is low, can reclaim calcirm-fluoride and hydrochloric acid, thoroughly Solve the pollution problem of industrial fluorine-containing spent acid at present.
The present invention is realized by following measures.
A kind of method that spent acid of utilization hydrochloric acid and hydrofluoric acid prepares calcirm-fluoride, it is characterised in that comprise the following steps:
(1) acid pickle is taken, wherein HF concentration is that 33%, HCl concentration is 9.5%;
(2) calcium chloride solution of configuration concentration 18%~30%;
(3) suitable quantity of water is added in first order reaction kettle, is incubated to 80 DEG C~85 DEG C, stirring, while spent acid and calcium chloride solution is added dropwise, Rate of addition is controlled, the micro- excess of HF is remained, the mol ratio for controlling calcium chloride and hydrogen fluoride is 1:2.1-2.15, completion of dropping Afterwards, continue to react 1-1.5 hours, then regulation makes HF weight percentages in final solution be 1-1.5%;
(4) solution of step 3 is added in second order reaction kettle, be incubated to 40-50 DEG C, stirring is reacted 2 hours, then, regulation makes HF weight percentages are 0.2-0.5% in final solution;
(5) solution in step 4 is added in third-order reaction kettle and carries out staticly settling 60min -90min, natural filtration obtains fluorine Change calcium solid, gained filtrate is the hydrochloric acid solution of enrichment to 12%~18.6%;
(6) by 2~3 times pure water of the calcirm-fluoride solid with its quality, wash in five times, precipitate and filter, to neutrality;
(7) gained solid is dried to obtain fluorination calcium product in 106 DEG C of drying boxes.
The above-mentioned method for preparing calcirm-fluoride, it is preferred that time for adding is 1 hour in the step 3.
The above-mentioned method for preparing calcirm-fluoride, it is preferred that the speed of agitator 30-40r/min in step 3;Stirring in step 4 Mix speed 20-30r/min.
The method for preparing calcirm-fluoride of the present invention, first, in step 3, height of the reaction temperature control at 80 DEG C~85 DEG C Temperature, can make HF and CaCl2Fast reaction, and produce substantial amounts of CaF2Molecule, meanwhile, higher temperature can be so as to organic Thing and impurity denaturation, the CaF prevented2Molecule is bonded.
Second, in step 3, using dropwise addition spent acid and calcium chloride solution, and remain the micro- excess of HF simultaneously, control The mol ratio of calcium chloride and hydrogen fluoride is 1:2.1-2.15, calcirm-fluoride is quickly generated also for hydrogen fluoride and calcium chloride is made Grain, prevents the bonding of molecule.After completion of the reaction, calcirm-fluoride particle diameter is basic in 30-80um for step 1.
3rd, in step 4, control temperature keeps micro- excess of hydrogen fluoride to 40-50 DEG C, can make small fluorine Change calcium particle formation calcirm-fluoride microcrystal grain, particle diameter reaches 250-300um.
4th, in step 3-4, the content of hydrogen fluoride in the solution is gradually reduced, finally up to 0.2-0.5%.By above-mentioned Control, you can with ensure generate larger particles degree calcirm-fluoride, in turn ensure that in the hydrochloric acid being made, the content of hydrogen fluoride to the greatest extent may be used Lacking for energy, reaches the standard of commercial Application.
5th, preparation method of the invention, it is ensured that CaCl2Thoroughly reacted with HF, Ca in mother liquor+It is almost nil, without load CaF is separated out in being reacted after the heart2Precipitation, yield is more than 99.3%.The hydrochloric acid of by-product 12%~18.6%, value is very high.Not yet There are the other waste products of generation, reach environment protection emission requirement.
Embodiment
Embodiment 1
(1) acid pickle is taken, wherein HF concentration is that 33%, HCl concentration is 9.5%.(Percentage by weight);
(2) configuration concentration 25%(Percentage by weight)Calcium chloride solution;
(3) 100Kg water is added in first order reaction kettle, is incubated to 85 DEG C, it is 35r/min to control mixing speed, while spent acid is added dropwise And calcium chloride solution, rate of addition is controlled, the micro- excess of HF is remained, the mol ratio for controlling calcium chloride and hydrogen fluoride is 1:2.1. Time for adding is 1 hour.Finally, calcium chloride solution addition is 1000Kg, and acid pickle addition is 287Kg;
After completion of dropping, continue to react 1 hour, then add a small amount of calcium chloride solution, regulation makes HF weight in final solution Percentage composition is 1.5%;
(4) solution of step 3 is added in second order reaction kettle, insulation is to 45 DEG C, mixing speed 25r/min, reacts 2 hours, so Afterwards, adding a small amount of calcium chloride solution regulation makes HF weight percentages in final solution be 0.4%;
(5) solution in step 4 is added in third-order reaction kettle and carries out staticly settling 80min, natural filtration obtains calcirm-fluoride and consolidated Body, gained filtrate is the hydrochloric acid solution of enrichment to 15.8%;
(6) by 2 times pure water of the calcirm-fluoride solid with its quality, wash in five times, precipitate and filter, to neutrality;
(7) gained solid is dried to obtain fluorination calcium product in 106 DEG C of drying boxes, and weight is 178.3Kg, and purity is 99.24% 。
It should be noted last that:Above example is only used to illustrative and not limiting technical scheme, although ginseng The present invention is described in detail according to above-described embodiment, it will be understood by those within the art that;According to can to this Invention is modified or equivalent substitution, any modification or partial replacement without departing from the spirit and scope of the present invention, and its is equal It should cover among scope of the presently claimed invention.

Claims (3)

1. the method that the spent acid of a kind of utilization hydrochloric acid and hydrofluoric acid prepares calcirm-fluoride, it is characterised in that comprise the following steps:
(1) acid pickle is taken, wherein HF concentration is that 33%, HCl concentration is 9.5%;
(2) calcium chloride solution of configuration concentration 18%~30%;
(3) suitable quantity of water is added in first order reaction kettle, is incubated to 80 DEG C~85 DEG C, stirring, while spent acid and calcium chloride solution is added dropwise, Rate of addition is controlled, the micro- excess of HF is remained, the mol ratio for controlling calcium chloride and hydrogen fluoride is 1:2.1-2.15, completion of dropping Afterwards, continue to react 1-1.5 hours, then regulation makes HF weight percentages in final solution be 1-1.5%;
(4) solution of step 3 is added in second order reaction kettle, be incubated to 40-50 DEG C, stirring is reacted 2 hours, then, regulation makes HF weight percentages are 0.2-0.5% in final solution;
(5) solution in step 4 is added in third-order reaction kettle and carries out staticly settling 60min -90min, natural filtration obtains fluorine Change calcium solid, gained filtrate is the hydrochloric acid solution of enrichment to 12%~18.6%;
(6) by 2~3 times pure water of the calcirm-fluoride solid with its quality, wash in five times, precipitate and filter, to neutrality;
(7) gained solid is dried to obtain fluorination calcium product in 106 DEG C of drying boxes.
2. the method according to claim 1 for preparing calcirm-fluoride, it is characterised in that time for adding is 1 small in the step 3 When.
3. the method according to claim 1 for preparing calcirm-fluoride, it is characterised in that the speed of agitator 30-40r/ in step 3 min;Mixing speed 20-30r/min in step 4.
CN201710600351.XA 2017-07-21 2017-07-21 A kind of method that spent acid of utilization hydrochloric acid and hydrofluoric acid prepares calcirm-fluoride Pending CN107298455A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109734116A (en) * 2019-03-05 2019-05-10 浙江师范大学 A kind of CaF2The preparation method of nano material hollow sphere
CN111003869A (en) * 2019-12-26 2020-04-14 安徽工业大学 Hydrofluoric acid wastewater resource utilization method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102910664A (en) * 2012-11-06 2013-02-06 浙江大学 Method for recovering fluoride ions in freon by-product mixed acid
CN106865572A (en) * 2017-03-15 2017-06-20 湖北三雄科技发展有限公司 A kind of method of comprehensive utilization of lithium salts by-product nitration mixture

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102910664A (en) * 2012-11-06 2013-02-06 浙江大学 Method for recovering fluoride ions in freon by-product mixed acid
CN106865572A (en) * 2017-03-15 2017-06-20 湖北三雄科技发展有限公司 A kind of method of comprehensive utilization of lithium salts by-product nitration mixture

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109734116A (en) * 2019-03-05 2019-05-10 浙江师范大学 A kind of CaF2The preparation method of nano material hollow sphere
CN111003869A (en) * 2019-12-26 2020-04-14 安徽工业大学 Hydrofluoric acid wastewater resource utilization method

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