CN105439163B - A kind of boron carbide high-purity boracic acid preparation method - Google Patents
A kind of boron carbide high-purity boracic acid preparation method Download PDFInfo
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- CN105439163B CN105439163B CN201510876827.3A CN201510876827A CN105439163B CN 105439163 B CN105439163 B CN 105439163B CN 201510876827 A CN201510876827 A CN 201510876827A CN 105439163 B CN105439163 B CN 105439163B
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- acid
- maleic anhydride
- boron carbide
- boric acid
- acrylic acid
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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
A kind of boron carbide high-purity boracic acid preparation method, it is related to a kind of preparation method of industrial chemicals boric acid, this method first step, using maleic anhydride and acrylic acid as polymerized monomer, adds initiator, carry out polymerisation, maleic anhydride acrylic copolymer is made；Second step, modifying agent is added, obtained maleic anhydride acrylic copolymer is modified, the ability of modified maleic anhydride acrylic copolymer chelating calcium ion is 289.3mg/ml, and calcium carbonate dispersibility is 202.5mg/ml；3rd step, high-purity boracic acid is prepared using chelating absorption method, technique is simple, and purification effect is good.4th step, intercalating agent recoverable, avoids secondary environmental pollution and the wasting of resources.Obtained high-purity boracic acid is mainly for the production of boron carbide, for aircraft armor, to strengthen the performances such as its hardness and high temperature resistant.
Description
Technical field
The present invention relates to a kind of chemical industry boric acid preparation method, more particularly to a kind of boron carbide high-purity boracic acid preparation side
Method.
Background technology
At present, boron carbide has been widely used in structural material, chemical raw material, electrical property, nuclearity energy, composite ceramic both at home and abroad
Porcelain etc., wherein, in terms of structural material, available for the processing of various hard metal, corundum or glass, it can also produce resistance to
Mill, corrosion resistant boron carbide device；In addition, external application boron carbide material also acts as cutting blade, mortar, beater etc.；Also it can use
Make the lightweight armor of helicopter, bullet-proof vest, bearing face, correction tool etc..Can be used as on chemical raw material steel or its
The boronating agent of his alloy is in steel surface boronising, to generate the intensity and wearability of FeB thin layer reinforcing material；It can be additionally used in one
The additive of a little metal base frication materials；When reduction-chemical combination legal system takes boride powder, boron carbide can be produced as boron source
The powder such as TiB2, ZrB2, CrB2, halogenation boron, borane etc. can be also manufactured, be referred to as " the boron carbide method " for producing powder.Utilize
Boron carbide electrical property can make boron carbide-graphite thermocouple.The advantages of utilization its neutron absorption capability in nuclearity energy is strong is used as
The function element such as neutron absorber material control rod, regulating rod, emergency rod, safety rod, shielding rod.Boron carbide composite ceramic application side
Face can improve its sintering behavior by adding sintering aid, obtain cheap and good-quality boron carbide product, can also add substantial amounts of
Composite is made in SiC, and it is applied in industrial muzzles, the sealing of pump and hot extruding die field, is that one kind has
The high temperature of wide application prospect is anti-corrosion, high-abrasive material.
Because the boric acid purity used in production boron carbide is inadequate, containing a certain amount of calcium ion, boron carbide ceramics is caused to have
Two fatal weakness：First, the fracture toughness of boron carbide ceramics is very low；Second, with firm covalent key connection between atom, covalently
Linkage content is up to 93.9%, it is thus achieved that densely sintered body is extremely difficult.Therefore, the calcium ion in boric acid is removed, is improved
The purity of boric acid is most important.The method of production high-purity boracic acid is many both at home and abroad, such as recrystallization method, ion-exchange, esterification-steaming
Evaporate method, electrochemistry and infiltration embrane method etc., but these methods have the shortcomings that respective, for example, can not obtain satisfied purification effect,
Energy consumption is big, is easily introduced impurity, complex process etc., and in many purification process, have ignored the removal of calcium ion mostly.
High-purity boracic acid is prepared using chelating absorption method, technique is simple, and purification effect is good, and adsorbent recoverable, keeps away
Exempt from environmental pollution and the wasting of resources.Obtained high-purity boracic acid is hard to strengthen its for aircraft armor mainly for the production of boron carbide
The performance such as degree and high temperature resistant.
At present, domestic industrial boric acid purity is relatively low, typically between 99%-99.5%, does not reach laser crystal, Communication ray
The requirements of some special industries to boric acid purity such as fine and nuclear industry, therefore, are purified to existing industrial boric acid, are prepared high
Pure boric acid is extremely urgent, prepare both at home and abroad the method for high-purity boracic acid mainly have it is following several：
（1）Recrystallization method is main production process of the purity in 99.5 more than % boric acid；
（2）Ion-exchange is a kind of method for separating impurity using ion exchange resin；
（3）Esterification-Hydrolyze method obtains high-purity boracic acid；
(4) electrochemistry reaches the purpose of purifying boric acid with infiltration embrane method；
(5) complexometry, the metal cation impurity being purified in material can be sheltered by adding complexing agent, so as to reduce metal
The concentration of cation, recrystallization, obtains high-purity boracic acid；
（6）Other method：Chelate absorption method, extraction, a variety of methods and with etc..
In the method for high-purity boracic acid made above, the content problem of calcium ion in boric acid is all have ignored, is mainly removed for this
The calcium ion gone in industrial boric acid.The method of deliming has a variety of, and conventional method is roughly divided into the precipitation method both at home and abroad, cation is handed over
Change resin method, addition antisludging agent method, extraction, floatation, addition flocculant method, absorption method, membrane separation process and way of distillation etc..Film
Partition method and the way of distillation are seldom used alone, and are often used as pretreatment using ion-exchange or the precipitation method.By the maleic anhydride of synthesis
Acrylic copolymer adds modifying agent and is modified, and modified copolymer of maleic anhydride and acrylic acid chelates the ability of calcium ion
For 289.3mg/ml, calcium carbonate dispersibility is 202.5mg/ml.High-purity boracic acid is prepared using chelating absorption method, technique is simple,
Purification effect is good.Intercalating agent recoverable, avoids secondary environmental pollution and the wasting of resources.
The content of the invention
It is an object of the invention to provide a kind of boron carbide high-purity boracic acid preparation method, this method is with maleic anhydride and third
Olefin(e) acid is polymerized monomer, adds initiator, synthesis of maleic anhydride acrylic copolymer.Meanwhile by the maleic anhydride propylene of synthesis
Acid copolymer adds modifying agent and is modified, and obtained high-purity boracic acid produces boron carbide, can strengthen the property such as its hardness and high temperature resistant
Energy.
The purpose of the present invention is achieved through the following technical solutions：
A kind of boron carbide high-purity boracic acid preparation method, methods described include procedure below：
A. first, maleic anhydride and distilled water are added into the four-hole boiling flask equipped with thermometer and condensation reflux unit, is treated
After maleic anhydride is completely dissolved, acrylic acid is measured, while weighs the ammonium persulfate that mass fraction is 6.67% and is dissolved in distilled water
In, it is 0.02mol/L to make its concentration, as initiator, while acrylic acid and ammonium persulfate aqueous solution is added dropwise into four-hole boiling flask,
After isothermal reaction, solution is put into rotary evaporator, is evaporated under reduced pressure, gained liquid is that maleic acid anhydride-propenoic acid is total to
Polymers；
B. maleic anhydride, modifying agent and distilled water are added into the four-hole boiling flask equipped with thermometer and condensation reflux unit,
After maleic anhydride and ALS are completely dissolved, acrylic acid is measured, while weighs ammonium persulfate and is dissolved in distilled water,
Acrylic acid and ammonium persulfate aqueous solution is added dropwise into four-hole boiling flask simultaneously；After being added dropwise, isothermal reaction, by reacted solution
Pour into rotary evaporator, gained liquid is sulfonic group copolymer of maleic anhydride and acrylic acid；
C. weigh industrial boric acid to add in three-necked flask, remove ionized water stirring and dissolving, be configured to boric acid saturated solution, treat
After boric acid all dissolves, according to the calcium sequestration capacity size of sulfonic group copolymer of maleic anhydride and acrylic acid, with pipette correct amount
2ml sulfonic group copolymer of maleic anhydride and acrylic acid is taken to be added as adsorbent in boric acid saturated solution, reaction is stood after terminating
It is filtered by vacuum while hot, impurity screening, filtrate is put into refrigerator cold-storage, boric acid crystal is separated out, is filtered again, by institute
The boric acid crystal obtained is put into baking oven and dried；
D. gained filtrate is concentrated, unnecessary moisture evaporation is gone out using rotary evaporator, filters, is dried to obtain again
A little boric acid crystal, and sulfuric acid is added dropwise into surplus solution, centrifuged, separation of solid and liquid, reclaimed using high speed tabletop centrifuge
Adsorbent, due to adding substantial amounts of water in course of reaction, therefore reclaim in adsorbent and contain a little water, it is therefore desirable to make again
Moisture is steamed with rotary evaporator, finally gives purer adsorbent.
A kind of described boron carbide high-purity boracic acid preparation method, in the step a, the solution after isothermal reaction is put into rotation
Turn in evaporator, bath temperature is adjusted to 50 DEG C, and circulation hydraulic vacuum pump pressure rises to 0.09MPa and carries out vacuum distillation 1.5h.
A kind of described boron carbide high-purity boracic acid preparation method, in the step b, the solution after isothermal reaction pours into rotation
Turn in evaporator, bath temperature is adjusted to 50 DEG C, circulation hydraulic vacuum pump pressure rises to 0.09MPa and carries out vacuum distillation 1.5h.
A kind of described boron carbide high-purity boracic acid preparation method, in the step c, isothermal reaction terminate after immediately while hot
It is filtered by vacuum, impurity screening, filtrate is put into refrigerator cold-storage, be cooled to 5 DEG C or so, is separated out boric acid crystal, carry out again
Filter.
Advantages of the present invention is with effect：
1. the present invention, using modified copolymer of maleic anhydride and acrylic acid as intercalating agent, it is strong to chelate the ability of calcium ion, calcium
Ion chelating ability is 289.3mg/ml, and calcium carbonate dispersibility is 202.5mg/ml.
2. the present invention prepares high-purity boracic acid using chelating absorption method, 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 boron carbide, for aircraft armor, to strengthen the performances such as its hardness and high temperature resistant.
Brief description of the drawings
Fig. 1 is the technology of the present invention route sketch；
Fig. 2 is that properties of product of the present invention characterize copolymer IR figures；
Fig. 3 is the IR figures that properties of product of the present invention characterize modified copolymer；
Fig. 4 is the SEM figures that properties of product of the present invention characterize product boric acid.
Embodiment
With reference to embodiment, the present invention is described in detail.
The present invention is using modified maleic anhydride and acrylic polymer as intercalating agent；It is refined to industrial boric acid remove calcium from
Son, using maleic anhydride and acrylic acid as polymerized monomer, add initiator, synthesis of maleic anhydride acrylic copolymer.Meanwhile it will close
Into maleic anhydride acrylic copolymer add modifying agent be modified, modified copolymer of maleic anhydride and acrylic acid chelating
The ability of calcium ion is 289.3mg/ml, and calcium carbonate dispersibility is 202.5mg/ml.High purity boron is prepared using chelating absorption method
Acid, technique is simple, and purification effect is good.Intercalating agent recoverable, avoids secondary environmental pollution and the wasting of resources.Obtained height
Pure boric acid is mainly for the production of boron carbide, for aircraft armor, to strengthen the performances such as its hardness and high temperature resistant.
The general principle of the present invention：
Polymerisation is as follows：
The basic scheme of the present invention：
The first step, using maleic anhydride and acrylic acid as polymerized monomer, initiator is added, carries out polymerisation, Malaysia is made
Anhydride-acrylic acid copolymer；Second step, modifying agent is added, obtained copolymer of maleic anhydride and acrylic acid is modified；The
Three steps, high-purity boracic acid is prepared using chelating absorption method；4th step, intercalating agent recycle.
The technical method of the present invention：
This project, using the method for chelant absorption, deviates from industrial boric acid using the modified copolymer being prepared as intercalating agent
In calcium ion, be recrystallized to give suitable for boron carbide production high-purity boracic acid, meanwhile, intercalating agent recycle.
Specific embodiment of the present invention：
（1）Maleic anhydride and 200ml distilled water are added into the four-hole boiling flask equipped with thermometer and condensation reflux unit, is risen
Temperature starts agitator and starts to stir, rotating speed 350r/min, after maleic anhydride is completely dissolved, measure acrylic acid, together to 80 DEG C
When weigh mass fraction be 6.67% ammonium persulfate be dissolved in distilled water（Concentration is 0.02mol/L）As initiator, simultaneously
Acrylic acid and ammonium persulfate aqueous solution are added dropwise into four-hole boiling flask, two kinds of solution of control drip off in 60min or so；It is added dropwise
Afterwards, isothermal reaction 3h.Finally, reacted solution is put into rotary evaporator, bath temperature is adjusted to 50 DEG C, circulation hydraulic
Vacuum pump pressure rises to 0.09MPa and carries out vacuum distillation 1.5h, and gained liquid is copolymer of maleic anhydride and acrylic acid.
（2）Maleic anhydride, modifying agent and distilled water are added into the four-hole boiling flask equipped with thermometer and condensation reflux unit,
80 DEG C are warming up to, starts agitator and starts to stir, rotating speed 350r/min.Treat that maleic anhydride and ALS are completely dissolved
Afterwards, acrylic acid is measured, while weighs ammonium persulfate and is dissolved in distilled water, while acrylic acid and over cure are added dropwise into four-hole boiling flask
Sour aqueous ammonium, two kinds of solution of control drip off in 60min or so；After being added dropwise, isothermal reaction 3h, by reacted solution
Pour into rotary evaporator, bath temperature is adjusted to 50 DEG C, circulation hydraulic vacuum pump pressure rises to 0.09MPa and is evaporated under reduced pressure
1.5h, gained liquid are sulfonic group copolymer of maleic anhydride and acrylic acid.
（3）The accurate 29.78g industrial boric acids that weigh are added in three-necked flask, then measure 200ml deionized water stirring and dissolvings,
Thermostat water bath heating-up temperature is configured to boric acid saturated solution to 60 DEG C, after boric acid all dissolving, according to sulfonic group maleic acid
The calcium sequestration capacity size of acid anhydride-acrylic copolymer, the sulfonic group maleic acid anhydride-propenoic acid that 2ml is accurately measured with pipette are total to
Polymers is added in boric acid saturated solution, isothermal reaction as adsorbent；Reaction is filtered by vacuum while hot immediately after terminating, mistake
Impurity is filtered, filtrate is put into refrigerator cold-storage, is cooled to 5 DEG C or so, boric acid crystal is separated out, is filtered again, by the boron of gained
Acid crystal is put into baking oven and dried.
（4）Experiment gained filtrate is concentrated, unnecessary moisture evaporation is gone out using rotary evaporator, filtered again, is done
It is dry to obtain a little boric acid crystal, and sulfuric acid is added dropwise into surplus solution, centrifuged using high speed tabletop centrifuge, solid-liquid point
From, adsorbent is reclaimed, contains a little water in adsorbent due to adding substantial amounts of water in course of reaction, therefore reclaiming, therefore need to
Reuse rotary evaporator to steam moisture, finally give purer adsorbent.
Claims (4)
1. a kind of boron carbide high-purity boracic acid preparation method, it is characterised in that methods described includes procedure below：
A. first, maleic anhydride and distilled water are added into the four-hole boiling flask equipped with thermometer and condensation reflux unit, treats Malaysia
After acid anhydrides is completely dissolved, acrylic acid is measured, while weighs the ammonium persulfate that mass fraction is 6.67% and is dissolved in distilled water, is made
Its concentration is 0.02mol/L, as initiator, while acrylic acid and ammonium persulfate aqueous solution, constant temperature is added dropwise into four-hole boiling flask
After reaction, solution is put into rotary evaporator, is evaporated under reduced pressure, gained liquid is copolymer of maleic anhydride and acrylic acid；
B. maleic anhydride, modifying agent and distilled water are added into the four-hole boiling flask equipped with thermometer and condensation reflux unit, treats horse
Carry out acid anhydrides and after ALS is completely dissolved, measure acrylic acid, while weigh ammonium persulfate and be dissolved in distilled water, simultaneously
Acrylic acid and ammonium persulfate aqueous solution are added dropwise into four-hole boiling flask；After being added dropwise, isothermal reaction, reacted solution is poured into
In rotary evaporator, gained liquid is sulfonic group copolymer of maleic anhydride and acrylic acid；
C. weigh industrial boric acid to add in three-necked flask, remove ionized water stirring and dissolving, be configured to boric acid saturated solution, treat boric acid
All after dissolving, according to the calcium sequestration capacity size of sulfonic group copolymer of maleic anhydride and acrylic acid, accurately measured with pipette
2ml sulfonic group copolymer of maleic anhydride and acrylic acid is added in boric acid saturated solution, reacted after terminating immediately as adsorbent
It is filtered by vacuum while hot, impurity screening, filtrate is put into refrigerator cold-storage, boric acid crystal is separated out, is filtered again, by gained
Boric acid crystal be put into baking oven dry；
D. gained filtrate is concentrated, unnecessary moisture evaporation is gone out using rotary evaporator, filtered again, be dried to obtain a little
Boric acid crystal, and sulfuric acid is added dropwise into surplus solution, centrifuged using high speed tabletop centrifuge, separation of solid and liquid, recovery absorption
Agent, due to adding substantial amounts of water in course of reaction, therefore reclaim in adsorbent and contain a little water, it is therefore desirable to reuse rotation
Turn evaporator to steam moisture, finally give purer adsorbent.
A kind of 2. boron carbide high-purity boracic acid preparation method according to claim 1, it is characterised in that in the step a,
Solution after isothermal reaction is put into rotary evaporator, and bath temperature is adjusted to 50 DEG C, and circulation hydraulic vacuum pump pressure rises to
0.09MPa carries out vacuum distillation 1.5h.
A kind of 3. boron carbide high-purity boracic acid preparation method according to claim 1, it is characterised in that in the step b,
Solution after isothermal reaction is poured into rotary evaporator, bath temperature is adjusted into 50 DEG C, circulation hydraulic vacuum pump pressure rises to
0.09MPa carries out vacuum distillation 1.5h.
A kind of 4. boron carbide high-purity boracic acid preparation method according to claim 1, it is characterised in that in the step c,
Isothermal reaction is filtered by vacuum while hot immediately after terminating, and impurity screening, filtrate is put into refrigerator cold-storage, is cooled to 5 DEG C, is separated out
Boric acid crystal, is filtered again.
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| CN112850732B (en) * | 2021-01-25 | 2022-07-01 | 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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| CN102020287A (en) * | 2010-12-15 | 2011-04-20 | 沈阳化工大学 | Process for refining high-purity boric acid for borosilicate glass |
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| CN102001675A (en) * | 2010-12-10 | 2011-04-06 | 大连理工大学 | Method for preparing nuclear power-grade high-purity boracic acid |
| CN102020287A (en) * | 2010-12-15 | 2011-04-20 | 沈阳化工大学 | Process for refining high-purity boric acid for borosilicate glass |
| CN103554362A (en) * | 2013-10-18 | 2014-02-05 | 中国科学院广州化学研究所 | Maleic anhydride copolymer dispersing agent as well as preparation method and application thereof |
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