CN105439163A - Method for preparing high-purity boric acid for boron carbide - Google Patents
Method for preparing high-purity boric acid for boron carbide Download PDFInfo
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- CN105439163A CN105439163A CN201510876827.3A CN201510876827A CN105439163A CN 105439163 A CN105439163 A CN 105439163A CN 201510876827 A CN201510876827 A CN 201510876827A CN 105439163 A CN105439163 A CN 105439163A
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- maleic anhydride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
- C01B35/109—Purification; Separation; Concentration
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention provides a method for preparing high-purity boric acid for boron carbide and relates to a preparation method of the chemical raw material boric acid. The method comprises the steps that step one, maleic anhydride and acrylic acid are used as polymeric monomers, and an initiator is added to perform polymerization reaction so as to prepare a maleic anhydride-acrylic acid copolymer; step two, a modifier is added to modify the prepared maleic anhydride-acrylic acid copolymer, wherein the calcium ion chelating capacity of the modified maleic anhydride-acrylic acid copolymer is 289.3 mg/ml, and the calcium carbonate dispersion capability is 202.5 mg/ml; step three, the high-purity boric acid is prepared by adopting a chelating adsorption method, a process is simple, and the purification effect is good; step four, a chelating agent can be recycled, and secondary environment pollution and resource waste are avoided. The prepared high-purity boric acid is mainly used for production of the boron carbide and is used for aircraft armor so as to improve its hardness, high-temperature resistance performance and the like.
Description
Technical field
The present invention relates to a kind of chemical industry boric acid preparation method, particularly relate to a kind of norbide high-purity boracic acid preparation method.
Background technology
At present, norbide is widely used in the aspects such as structured material, chemical feedstocks, electrical property, nuclearity energy, composite ceramics both at home and abroad, wherein, in structured material, can be used for the processing of various hard metal, corundum or glass, also can produce wear-resisting, corrosion resistant norbide device; In addition, external application boron carbide material also can be used as cutting blade, mortar, beater etc.; Also can be used as the lightweight armor of vertisplane, bullet-proof vest, bearing face, correction tool etc.The boronating agent that chemical feedstocks can be used as steel or other alloys at steel surface boronizing, to generate intensity and the wear resistance of FeB thin layer strongthener; Also can be used for the additive of some metal matrix friction materialss; When reduction-chemical combination legal system gets boride powder, norbide, as boron source, can produce the powder such as TiB2, ZrB2, CrB2, also can manufacture halogenation boron, borane etc., be called " the norbide method " of producing powder.Utilize norbide electrical property can make norbide-graphite thermal galvanic couple.The advantage that its neutron absorption capability is strong that utilizes in nuclearity energy is used as the functional element such as neutron absorber material control rod, regulating rod, emergency rod, safety rod, shielding rod.Boron carbide composite ceramic application aspect improves its sintering behavior by adding sintering aid, obtain cheap and good-quality boron carbide product, also can add a large amount of SiC and make matrix material, it is applied in the sealing of industrial muzzles, pump and hot extruding die field, is that a kind of high temperature with wide application prospect is anti-corrosion, high-abrasive material.
Inadequate owing to producing norbide boric acid purity used, containing a certain amount of calcium ion, cause boron carbide ceramics to have two fatal weakness: one is that the fracture toughness property of boron carbide ceramics is very low; Two is that covalent linkage content, up to 93.9%, thus, obtains highdensity sintered compact very difficult with firmly covalent linkage connection between atom.Therefore, remove the calcium ion in boric acid, the purity improving boric acid is most important.The method of domestic and international production high-purity boracic acid is a lot, as recrystallization method, ion exchange method, esterification-distillation method, electrochemistry and infiltration embrane method etc., but these methods have respective shortcoming, purification effect, the energy consumption that such as cannot obtain satisfaction introduce impurity, complex process etc. greatly, easily, and in many purification process, mostly have ignored the removal of calcium ion.
Adopt chelating absorption method to prepare high-purity boracic acid, technique is simple, and purification effect is good, and sorbent material recoverable, avoid environmental pollution and the wasting of resources.Obtained high-purity boracic acid mainly for the production of norbide, for aircraft armor, to strengthen its hardness and the performance such as high temperature resistant.
At present, domestic industrial boric acid purity is lower, general between 99%-99.5%, do not reach some special industries such as laser crystals, telecommunication optical fiber and nuclear industry to the requirement of boric acid purity, therefore, purify to existing industrial boric acid, prepare high-purity boracic acid extremely urgent, the method preparing high-purity boracic acid both at home and abroad mainly contains following several:
(1) recrystallization method is the main production process of the boric acid of purity more than 99.5%;
(2) ion exchange method is that a kind of spent ion exchange resin of answering is by the method for magazins' layout;
(3) esterification-hydrolysis method obtains high-purity boracic acid;
(4) electrochemistry and infiltration embrane method reach the object of purifying boric acid;
(5) complexometry, adds complexing agent and can shelter the metallic cation impurity be purified in material, thus reduces the concentration of metallic cation, and recrystallization, obtains high-purity boracic acid;
(6) additive method: chelating absorption method, extraction process, multiple method are also used.
More than prepare in the method for high-purity boracic acid, all have ignored the content problem of calcium ion in boric acid, mainly remove the calcium ion in industrial boric acid for this reason.The method of deliming has multiple, and method conventional is both at home and abroad roughly divided into the precipitator method, cation exchange resin processes, interpolation Scale inhibitors method, extraction process, flotation process, interpolation flocculation agent method, absorption method, membrane separation process and distillation method etc.Membrane separation process and distillation method are seldom used alone, often using ion exchange method or the precipitator method as pre-treatment.The maleic anhydride acrylic copolymer of synthesis is added properties-correcting agent and carries out modification, the ability of modified copolymer of maleic anhydride and acrylic acid chelating calcium ion is 289.3mg/ml, and calcium carbonate dispersive ability is 202.5mg/ml.Adopt chelating absorption method to prepare high-purity boracic acid, technique is simple, and purification effect is good.Intercalating agent recoverable, avoids secondary environmental pollution and the wasting of resources.
Summary of the invention
The object of the present invention is to provide a kind of norbide high-purity boracic acid preparation method, the method for polymerization single polymerization monomer, adds initiator, synthesis of maleic anhydride acrylic copolymer with maleic anhydride and vinylformic acid.Meanwhile, the maleic anhydride acrylic copolymer of synthesis is added properties-correcting agent and carries out modification, obtained high-purity boracic acid produces norbide, can strengthen its hardness and the performance such as high temperature resistant.
The object of the invention is to be achieved through the following technical solutions:
A kind of norbide high-purity boracic acid preparation method, described method comprises following process:
A. first, maleic anhydride and distilled water is added in the four-hole boiling flask that thermometer and condensation reflux unit be housed, after maleic anhydride dissolves completely, measure vinylformic acid, take simultaneously massfraction be 6.67% ammonium persulphate be dissolved in distilled water, its concentration is made to be 0.02mol/L, as initiator, in four-hole boiling flask, drip vinylformic acid and ammonium persulfate aqueous solution simultaneously, after isothermal reaction, solution is put into rotatory evaporator, carries out underpressure distillation, gained liquid is copolymer of maleic anhydride and acrylic acid;
B. in the four-hole boiling flask that thermometer and condensation reflux unit be housed, maleic anhydride, properties-correcting agent and distilled water is added, after maleic anhydride and sodium allyl sulfonate dissolve completely, measure vinylformic acid, take ammonium persulphate is dissolved in distilled water simultaneously, drips vinylformic acid and ammonium persulfate aqueous solution in four-hole boiling flask simultaneously; After dropwising, isothermal reaction, pours in rotatory evaporator by reacted solution, and gained liquid is sulfonic group copolymer of maleic anhydride and acrylic acid;
C. taking industrial boric acid adds in there-necked flask, remove ionized water stirring and dissolving, be mixed with boric acid saturated solution, after boric acid all dissolves, according to the calcium sequestration capacity size of sulfonic group copolymer of maleic anhydride and acrylic acid, the sulfonic group copolymer of maleic anhydride and acrylic acid of 2ml is accurately measured as sorbent material with transfer pipet, add in boric acid saturated solution, vacuum filtration is carried out while hot immediately after reaction terminates, impurity screening, puts into refrigerator cold-storage by filtrate, separates out boric acid crystal, again carry out suction filtration, the boric acid crystal of gained is put into baking oven dry;
D. gained filtrate is concentrated, use rotatory evaporator that unnecessary moisture is evaporated away, again filter, drying obtains a little boric acid crystal, and sulfuric acid is dripped in surplus solution, use high speed tabletop centrifuge to carry out centrifugal, solid-liquid separation, reclaim sorbent material, owing to adding a large amount of water in reaction process, therefore reclaim in sorbent material and contain a little water, therefore need to reuse rotatory evaporator and moisture is steamed, finally obtain purer sorbent material.
Described a kind of norbide high-purity boracic acid preparation method, in described step a, the solution after isothermal reaction puts into rotatory evaporator, and bath temperature is adjusted to 50 DEG C, and circulation hydraulic vacuum pump pressure rises to 0.09MPa and carries out underpressure distillation 1.5h.
Described a kind of norbide high-purity boracic acid preparation method, in described step b, the solution after isothermal reaction is poured in rotatory evaporator, bath temperature is adjusted to 50 DEG C, and circulation hydraulic vacuum pump pressure rises to 0.09MPa and carries out underpressure distillation 1.5h.
Described a kind of norbide high-purity boracic acid preparation method, in described step c, carries out vacuum filtration while hot immediately after isothermal reaction terminates, impurity screening, filtrate is put into refrigerator cold-storage, be cooled to about 5 DEG C, separates out boric acid crystal, again carries out suction filtration.
Advantage of the present invention and effect are:
1. the present invention is with modified copolymer of maleic anhydride and acrylic acid for intercalating agent, and the ability of chelating calcium ion is strong, and it is 289.3mg/ml that calcium ion huge legendary turtle closes ability, and calcium carbonate dispersive ability is 202.5mg/ml.
2. the present invention adopts chelating absorption method to prepare high-purity boracic acid, and technique is simple, and purification effect is good.
3. intercalating agent recoverable of the present invention, avoids secondary environmental pollution and the wasting of resources.Obtained high-purity boracic acid mainly for the production of norbide, for aircraft armor, to strengthen its hardness and the performance such as high temperature resistant.
Accompanying drawing explanation
Fig. 1 is the technology of the present invention route sketch;
Fig. 2 is that product performance of the present invention characterize multipolymer IR figure;
Fig. 3 is the IR figure that product performance of the present invention characterize modified copolymer;
Fig. 4 is the SEM figure that product performance of the present invention characterize product boric acid.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
The present invention with the maleic anhydride of modification and acrylic polymer for intercalating agent; To industrial boric acid refining removing calcium ion, with maleic anhydride and vinylformic acid for polymerization single polymerization monomer, add initiator, synthesis of maleic anhydride acrylic copolymer.Meanwhile, the maleic anhydride acrylic copolymer of synthesis is added properties-correcting agent and carries out modification, the ability of modified copolymer of maleic anhydride and acrylic acid chelating calcium ion is 289.3mg/ml, and calcium carbonate dispersive ability is 202.5mg/ml.Adopt chelating absorption method to prepare high-purity boracic acid, technique is simple, and purification effect is good.Intercalating agent recoverable, avoids secondary environmental pollution and the wasting of resources.Obtained high-purity boracic acid mainly for the production of norbide, for aircraft armor, to strengthen its hardness and the performance such as high temperature resistant.
Ultimate principle of the present invention:
Polyreaction is as follows:
General planning of the present invention:
The first step, with maleic anhydride and vinylformic acid for polymerization single polymerization monomer, adds initiator, carries out polyreaction, obtained copolymer of maleic anhydride and acrylic acid; Second step, adds properties-correcting agent, carries out modification to obtained copolymer of maleic anhydride and acrylic acid; 3rd step, adopts chelating absorption method to prepare high-purity boracic acid; 4th step, intercalating agent is recycled.
Technological method of the present invention:
This project for intercalating agent with the modified copolymer prepared, adopts huge legendary turtle to close the method for absorption, deviates from the calcium ion in industrial boric acid, and recrystallization obtains the high-purity boracic acid being applicable to norbide production, and meanwhile, intercalating agent is recycled.
Specific embodiment of the present invention:
(1) in the four-hole boiling flask that thermometer and condensation reflux unit be housed, maleic anhydride and 200ml distilled water is added, be warming up to 80 DEG C, start agitator to start to stir, rotating speed is 350r/min, after maleic anhydride dissolves completely, measure vinylformic acid, take simultaneously massfraction be 6.67% ammonium persulphate to be dissolved in distilled water (concentration is 0.02mol/L) as initiator, in four-hole boiling flask, drip vinylformic acid and ammonium persulfate aqueous solution simultaneously, control two kinds of solution and drip off at about 60min; After dropwising, isothermal reaction 3h.Finally, reacted solution is put into rotatory evaporator, bath temperature is adjusted to 50 DEG C, circulation hydraulic vacuum pump pressure rises to 0.09MPa and carries out underpressure distillation 1.5h, and gained liquid is copolymer of maleic anhydride and acrylic acid.
(2) in the four-hole boiling flask that thermometer and condensation reflux unit be housed, add maleic anhydride, properties-correcting agent and distilled water, be warming up to 80 DEG C, start agitator and start to stir, rotating speed is 350r/min.After maleic anhydride and sodium allyl sulfonate dissolve completely, measure vinylformic acid, take ammonium persulphate simultaneously and be dissolved in distilled water, in four-hole boiling flask, drip vinylformic acid and ammonium persulfate aqueous solution simultaneously, control two kinds of solution and drip off at about 60min; After dropwising, isothermal reaction 3h, pours in rotatory evaporator by reacted solution, bath temperature is adjusted to 50 DEG C, and circulation hydraulic vacuum pump pressure rises to 0.09MPa and carries out underpressure distillation 1.5h, and gained liquid is sulfonic group copolymer of maleic anhydride and acrylic acid.
(3) accurately taking 29.78g industrial boric acid adds in there-necked flask, measure 200ml deionized water and stirring again to dissolve, thermostat water bath Heating temperature to 60 DEG C, be mixed with boric acid saturated solution, after boric acid all dissolves, according to the calcium sequestration capacity size of sulfonic group copolymer of maleic anhydride and acrylic acid, accurately measure the sulfonic group copolymer of maleic anhydride and acrylic acid of 2ml as sorbent material with transfer pipet, add in boric acid saturated solution, isothermal reaction; Carry out vacuum filtration while hot immediately, impurity screening after reaction terminates, filtrate is put into refrigerator cold-storage, is cooled to about 5 DEG C, separate out boric acid crystal, again carry out suction filtration, the boric acid crystal of gained is put into baking oven dry.
(4) experiment gained filtrate is concentrated, use rotatory evaporator that unnecessary moisture is evaporated away, again filter, drying obtains a little boric acid crystal, and sulfuric acid is dripped in surplus solution, use high speed tabletop centrifuge to carry out centrifugal, solid-liquid separation, reclaim sorbent material, owing to adding a large amount of water in reaction process, therefore reclaim in sorbent material and contain a little water, therefore need to reuse rotatory evaporator and moisture is steamed, finally obtain purer sorbent material.
Claims (4)
1. a norbide high-purity boracic acid preparation method, is characterized in that, described method comprises following process:
A. first, maleic anhydride and distilled water is added in the four-hole boiling flask that thermometer and condensation reflux unit be housed, after maleic anhydride dissolves completely, measure vinylformic acid, take simultaneously massfraction be 6.67% ammonium persulphate be dissolved in distilled water, its concentration is made to be 0.02mol/L, as initiator, in four-hole boiling flask, drip vinylformic acid and ammonium persulfate aqueous solution simultaneously, after isothermal reaction, solution is put into rotatory evaporator, carries out underpressure distillation, gained liquid is copolymer of maleic anhydride and acrylic acid;
B. in the four-hole boiling flask that thermometer and condensation reflux unit be housed, maleic anhydride, properties-correcting agent and distilled water is added, after maleic anhydride and sodium allyl sulfonate dissolve completely, measure vinylformic acid, take ammonium persulphate is dissolved in distilled water simultaneously, drips vinylformic acid and ammonium persulfate aqueous solution in four-hole boiling flask simultaneously; After dropwising, isothermal reaction, pours in rotatory evaporator by reacted solution, and gained liquid is sulfonic group copolymer of maleic anhydride and acrylic acid;
C. taking industrial boric acid adds in there-necked flask, remove ionized water stirring and dissolving, be mixed with boric acid saturated solution, after boric acid all dissolves, according to the calcium sequestration capacity size of sulfonic group copolymer of maleic anhydride and acrylic acid, the sulfonic group copolymer of maleic anhydride and acrylic acid of 2ml is accurately measured as sorbent material with transfer pipet, add in boric acid saturated solution, vacuum filtration is carried out while hot immediately after reaction terminates, impurity screening, puts into refrigerator cold-storage by filtrate, separates out boric acid crystal, again carry out suction filtration, the boric acid crystal of gained is put into baking oven dry;
D. gained filtrate is concentrated, use rotatory evaporator that unnecessary moisture is evaporated away, again filter, drying obtains a little boric acid crystal, and sulfuric acid is dripped in surplus solution, use high speed tabletop centrifuge to carry out centrifugal, solid-liquid separation, reclaim sorbent material, owing to adding a large amount of water in reaction process, therefore reclaim in sorbent material and contain a little water, therefore need to reuse rotatory evaporator and moisture is steamed, finally obtain purer sorbent material.
2. a kind of norbide high-purity boracic acid preparation method according to claim 1, it is characterized in that, in described step a, the solution after isothermal reaction puts into rotatory evaporator, bath temperature is adjusted to 50 DEG C, and circulation hydraulic vacuum pump pressure rises to 0.09MPa and carries out underpressure distillation 1.5h.
3. a kind of norbide high-purity boracic acid preparation method according to claim 1, it is characterized in that, in described step b, the solution after isothermal reaction is poured in rotatory evaporator, bath temperature is adjusted to 50 DEG C, circulation hydraulic vacuum pump pressure rises to 0.09MPa and carries out underpressure distillation 1.5h.
4. a kind of norbide high-purity boracic acid preparation method according to claim 1, is characterized in that, in described step c, carry out vacuum filtration while hot immediately after isothermal reaction terminates, impurity screening, filtrate is put into refrigerator cold-storage, be cooled to about 5 DEG C, separate out boric acid crystal, again carry out suction filtration.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112850732A (en) * | 2021-01-25 | 2021-05-28 | 浙江爱科新材料有限公司 | Preparation method of high-purity boric acid for lithium battery cathode material |
| CN114014670A (en) * | 2021-11-08 | 2022-02-08 | 大连正兴磨料有限公司 | Preparation method of boron carbide sputtering target with characteristics of high purity and high density |
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| CN114014670A (en) * | 2021-11-08 | 2022-02-08 | 大连正兴磨料有限公司 | Preparation method of boron carbide sputtering target with characteristics of high purity and high density |
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