CN100339303C - Manufacture of boron-containing compound using cotton balls hydrothermal method and its comprehensive utilization - Google Patents

Manufacture of boron-containing compound using cotton balls hydrothermal method and its comprehensive utilization Download PDF

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CN100339303C
CN100339303C CNB2006100466666A CN200610046666A CN100339303C CN 100339303 C CN100339303 C CN 100339303C CN B2006100466666 A CNB2006100466666 A CN B2006100466666A CN 200610046666 A CN200610046666 A CN 200610046666A CN 100339303 C CN100339303 C CN 100339303C
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borax
sodium
metaborate
many
solutions
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CN1850605A (en
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胡德生
仲剑初
王斐
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Dalian University of Technology
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Dalian University of Technology
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Abstract

The present invention provides a boron-containing compound prepared by an ulexite hydrothermal method and comprehensive utilization thereof. Raw materials which are used are ulexite mineral powder or probertite mineral powder of which the granularity is from 80 to 200 meshes, and no less than 37.5 wt% of B2O3 is contained in the ulexite mineral powder or the probertite mineral powder. Calcium borate products and sodium polyborate solution which meet the boron containing requirement of alkali-free glass, and no less than 40 wt% of B2O3 and no more than 0.5 wt% of Na2O are contained in the calcium borate products and the sodium polyborate solution. The sodium polyborate solution is comprehensively utilized to be treated by evaporating concentration and cooling crystallisation, and borax products can be fabricated without additionally adding sodic alkalis or salts. Boracic acid can be prepared by adding a small quantity of sulfuric acid in borax mother solution after crystal separation, and comparatively pure calcium metaborate can be prepared by adding CaO or Ca(OH)2 in the borax mother solution or the sodium-containing sodium polyborate solution of borax which is not separated; sodium metaborate can be additionally produced simultaneously.

Description

With manufacture of boron-containing compound using cotton balls hydrothermal method and comprehensive utilization thereof
Technical field
The present invention relates to chemical field comprehensive utilization cotton balls and make the hydrothermal method of lime borate, borax, boric acid and sodium metaborate.
Background technology
Cotton balls (Na 2O2CaO5B 2O3) can be used as the boracic raw material and be directly used in glass industry and the ceramic industry, but owing to contain Na 2O has limited its direct use range.
Cotton balls according to following reaction, can make boric acid with the sulfuric acid decomposition as the important source material of making boric acid and borax:
Na 2O·2CaO·5B 2O3·nH 2O+3H 2SO 4→10H 3BO 3+Na 2SO 4+2CaSO 4↓
(n=10 or 16)
Can make borax according to following reaction:
2〔Na 2O·2CaO·5B 2O 3·nH 2O〕+2Na 2CO 3+2NaHCO 3+H 2O→5Na 2B 4O 7·10H 2O
+4CaCO 3↓
By above-mentioned reaction formula as can be known, as the sodium in the raw material cotton balls of system borax, all be transformed into the saltcake (Na of low value 2SO 4); As the raw material of system borax, need to consume two kinds of extra sodium carbonate salt that valency is high.
Colorabbia Italia S. P. A. had proposed a kind of patented technology in 1991, and in alkaline medium, the depolymerization cotton balls is produced the method for borax, and its reaction formula is:
2〔Na 2O·2CaO·5B 2O 3·16H 2O〕+NaOH＝2.5Na 2B 4O 7·10H 2O+4CaO·5B 2O3·7H 2O
This method still will consume the higher sodium hydroxide of price and keep alkaline condition and additional sodium.In addition, the lime borate of generation still can not satisfy non-alkali glass to sodium oxide content (Na 2O≤0.5%) requirement can only be as the raw material of producing boric acid.
In China, there are two with the patented technology of ulexite preparing boric acid calcium, one " with the method for manufacturing calcium borate from ulexite " (CN1654327A) reaction of foundation is:
Na 2O·2CaO·5B 2O 3·16H 2O+2HCl+2Ca(OH) 2→2〔CaO·B 2O 3·6H 2O〕↓
+2CaO·3B 2O 3·9H 2O↓+2NaCl
Or Na 2O2CaO5B 2O 316H 2O+2HCl+3Ca (OH) 2→ 5 (CaOB 2O 36H 2O)+2NaCl
Adopt hydrochloric acid and lime to decompose ulexite, shortcoming is that the salt acid value is expensive.
Chinese patent " manufacturing method of calcium borate by dissociating ulexite in limebase prooess " (CN 1654326A) according to reaction formula be:
Na 2O·2CaO·5B 2O 3·16H 2O+CaO＝2NaBO 2+CaO·B 2O 3·6H 2O↓+2CaO·3B 2O 3·
9H 2O↓+H 2O
Or 2 (Na 2O2CaO5B 2O 316H 2O)+3CaO+7H 2O=4NaBO 2+ 5 (CaOB 2O 36H 2O)
↓+2CaO·3B 2O 3·9H 2O
It is to decompose ulexite with inexpensive lime to make lime borate the by-product sodium metaborate.
It is when being raw material with the ulexite breeze that there is the common shortcoming in above-mentioned two kinds of technology, because the existence of impurity is difficult to make pure boric acid calcium salt.
The objective of the invention is to decompose cotton balls with hydrothermal method, make the lime borate that conforms with non-alkali glass boracic raw material, many Sodium Tetraboratees salt brine solution that depolymerization is come out is made borax, boric acid, lime borate and sodium metaborate with cheap raw material as required.
Summary of the invention
The present invention decomposes the cotton balls breeze with hydrothermal method, and it is soluble in water to contain the sodium multi-borate, and residue is a water-fast impurity in the borate of calcium and the raw ore.After the washing of residue process, the drying, contain B for purity 86～95% 2O 3〉=37.5% cotton balls or oblique cotton balls (Na 2O2CaO5B 2O 310H 2O) breeze can be made and contains B 2O 3〉=40%, Na 2The lime borate product that conforms with production non-alkali glass boracic ingredient requirement of O≤0.5%; Contain the sodium multi-borate aqueous solution through evaporation concentration, crystallisation by cooling, do not need extra alkali or the salt that contains sodium that adds, can make the borax product; Borax mother liquor after the Crystallization Separation, wherein Na 2O/B 2O 3＜0.35, use than being the sulfuric acid of the method much less of raw material preparing boric acid with borax or cotton balls, can produce boric acid; Mother liquor behind the Crystallization Separation borax or contain sodium multi-borate solution without what separate borax adds CaO or Ca (OH) 2, can make purer calcium metaborate, simultaneously the by-product sodium metaborate.
Concrete scheme of the invention process is:
The hydrothermal method of making boron compound with the cotton balls breeze is to be that 80～200 order purity are 86～95% to contain B with granularity 2O 3The cotton balls breeze of 〉=37.5% (weight) or oblique cotton balls breeze are raw material, and it is 2～15: 1 that adding wash water, clear water or mother liquor make liquid-solid ratio, 120～200 ℃ of temperature, and pressure 0.1～1.5MPa, hydrothermal decomposition reaction 2～12 hours obtains Na 2O≤0 5% (weight), B 2O 3〉=40% (weight), calcareous solid borate and undissolved raw ore residue through press filtration, washing, drying, obtain lime borate; Obtain Na simultaneously 2O/B 2O 3Mol ratio is less than the 0.5 many dobell's solutions as the pure calcium metaborate of manufacturing, sodium metaborate, borax or boric acid.
One of many sodium borate solution comprehensive utilizations that hydrothermal method makes are to contain B 2O 320～100g/l, Na 2O/B 2O 3Mol ratio is many dobell's solutions of 0.3～0.45, under normal pressure, adds 0.95～1.3 times of (1-Na 2O/B 2O 3Mol ratio) CaO of quantity or Ca (OH) 2, down reaction 2～10 hours of normal temperature, control pH=10～12, after reaction finishes, with the slip press filtration, filter cake with the clear water washing after, 100～200 ℃ of dryings, time≤3 hour obtain containing B 2O 341.5～42.5% (weight), CaO33～35% (weight) and Na 2The calcium metaborate of O≤0.5% (weight); The filtrate that press filtration obtains is sodium metaborate solution, and after evaporation concentration, crystallisation by cooling, centrifugation, obtaining purity is NaBO 2〉=98% sodium metaborate.
Two of many sodium borate solution comprehensive utilizations that hydrothermal method makes are with many sodium borate solutions separated into two parts: wherein a part is according to above-mentioned method of comprehensive utilization, by adding CaO or Ca (OH) 2Produce calcium metaborate product and sodium metaborate solution; Another part is allocated sodium boron than making borax with the sodium metaborate solution that the former obtains.The amount that two portions distribute is finally to make Na 2O/B 2O 3Mol ratio be 0.48～0.52 to be as the criterion, allotment can make the borax Na of purity 〉=95% after evaporation concentration, crystallisation by cooling, centrifugation do not add the alkali or the salt that contain sodium 2B 4O 710H 2O.
Three of many sodium borate solution comprehensive utilizations that hydrothermal method makes, be earlier with many dobell's solutions evaporation concentration to B 2O 3Content reaches 100～180g/l, and proportion is 1.26～1.31, is cooled to 28 ℃, and borax is separated out in crystallization, filters, and uses the clear water washing leaching cake, obtains purity and be 95% Na 2B 4O 710H 2The O borax; Obtaining proportion simultaneously is 1.08～1.10, contains B 2O 370～90g/l, Na 2Borax mother liquor and the wash water of O15～20g/l, after the mixing, evaporation concentration is to B 2O 3Concentration is 150～200g/l, at 85～95 ℃, adds concentration 92.5%H 2SO 4Be neutralized to pH=2～3, reaction is cooled to room temperature after finishing, and separates out boric acid, and the clear water washing leaching cake is used in centrifugation, and drying obtains product boric acid.Mother liquid of boric acid is again through evaporation concentration, and saltcake Na is separated out in crystallization at high temperature 2SO 4, isolate Na 2SO 4After, mother liquor returns with the borax mother liquor and mixes evaporation.
The principle of invention
1, the principle of decomposition cotton balls is to have in the presence of the water, makes it to take place following decomposition reaction by high temperature action:
2 (Na 2O2CaO5B 2O 3NH 2O) → 2 Na 2O5 B 2O 3+ 4CaO5B 2O 3YH 2O ↓ sodium pentaborate (2Na 2O5B 2O 3) soluble in water, and priceite (4CaO5 B 2O 3YH 2O) water insoluble, thus realize that the sodium calcium in the ulexite separates;
2, the principle of Crystallization Separation borax is to utilize sodium pentaborate at high temperature degree of supersaturation is bigger, and about 40 ℃, sodium pentaborate and borax are full altogether, are lower than 40 ℃, i.e. crystallization goes out borax.The principle of borax mother liquor preparing boric acid with by identical 2 Na of borax with the sulfuric acid reaction preparing boric acid 2O5B 2O 3+ 2H 2SO 4+ 13H 2O → 2Na 2SO 4+ 10H 3BO 3The feed liquid crystallisation by cooling goes out boric acid, and mother liquid evaporation concentrates, at high temperature Na 2SO 4Solubleness reduces, thereby realizes Na 2SO 4With H 3BO 3Separate mother liquid recycling.
3, produce the principle of boric acid, lime borate and sodium metaborate by many dobell's solutions and be that raw material is identical, just processing condition difference to some extent with borax.
Production process is as follows:
(1) cotton balls decomposes, and in the reactor with the chuck heating, at first adds the wash water of washing boron calcium filter cake of 2～15 times of cotton balls amounts and filtrate or the clear water that part is filtered boron calcium, and to add 80～200 order purity then be 86～95% (weights), contain B 2O 3〉=37.5% cotton balls breeze.Closed reactor starts whipping appts, and chuck feeds steam heating, rises to 120～200 ℃, keeps the still internal pressure at 0.1～1.5MPa, constant temperature and pressure 2～12 hours.
(2) sodium calcium separates (press filtration and washing), reach predetermined resolving time after, slip in the still is pressed toward the pressure filter press filtration, the pressure of pressure filter is kept 0.3～0.6MPa; Filtrate is that many sodium borate solutions (contain B 2O 320～100g/1), collection is stored in many sodium borate solutions storage tank.With 60～95 ℃ of hot wash filter cakes, the clear water amount is 1.5～3 times of cotton balls breeze, is washed till in the effusive wash water to contain B 2O 3Till＜the 1g/l.Filter cake dries up with 0.3～0.5MPa again, filter cake can be drawn off, and this filter cake is the lime borate that contains impurity in the original ore powder.
(3) lime borate drying.The temperature of dried material is at 100～200 ℃, time of drying≤6 hour, and dried product contains B 2O 340～42%, CaO24～30%, Na 2O≤0.5%.
(4) cotton balls decomposes the utilization of many sodium borate solutions of gained, and looking market demand has multiple mode:
(4-1) make one of calcium metaborate and sodium metaborate comprehensive utilization, in the normal-pressure reaction kettle that band stirs, it contains B to add many sodium borate solutions 2O 320～100g/l, Na 2O/B 2O 3=0.3～0.45 (mol ratio), according to the sodium boron in the solution than (Na 2O/B 2O 3), add CaO or Ca (OH) 2Amount, its amount is 0.95～1.3 times (1-X).X is Na herein 2O/B 2O 3(mol/mo1), reacted at normal temperatures 2～10 hours, pH=10～12 after reaction finishes, send pressure filter to filter with shurry pump, and filtrate is sodium metaborate solution, and filter cake draws off and sends to drying, 100～200 ℃ of drying temperatures after washing with clear water.Time＜3 hour can make and contain B 2O 341.5～42.5%, CaO33～35%Na 2The calcium metaborate product of O＜0.5%.The sodium metaborate solution evaporation concentration is cooled to 20～30 ℃ to proportion 1.30～1.38, and sodium metaborate is separated out in crystallization, and is dry under 80～100 ℃, obtains product sodium metaborate Na BO 24H 2O, content 〉=98%.Sodium metaborate mother liquor and wash water loop back evaporation.
(4-2) make two of calcium metaborate and borax comprehensive utilization: with many dobell's solutions separated into two parts, a part at first spends the manufacturing calcium metaborate, adds CaO or Ca (OH) 2, produce calcium metaborate according to (4-1) described process.The many dobell's solutions of the sodium metaborate solution that produces in the production and another part mix, and are used for producing borax, both proportionings with the sodium boron after cooperating than (Na 2O/B 2O 3) be 0.5 calculating, the solution of working good can by evaporation, concentrate cooling by existing public technology, and crystallization goes out borax (Na 2B 4O 710H 2O), centrifugation, and, can obtain commodity borax (purity 〉=95%) with after a small amount of clear water washing leaching cake, borax mother liquor and wash water return evaporation.
(4-3) make three of borax and boric acid comprehensive utilization: with many sodium borate solution heating, evaporation is concentrated into B 2O 3100～180g/1 is cooled to 20～35 ℃ of crystallizations and goes out borax (Na 2B 4O 710H 2O), centrifugation, and, can make commodity borax (Na with clear water washing borax filter cake 2B 4O 710H 2O 〉=95%).Borax wash water and mother liquor as making boric acid, are pressed existing public technology together, and evaporation concentration is to B 2O 3Concentration is 150～200g/l, maintains the temperature at 85～90 ℃, adds the sulfuric acid neutralization, up to the acidity pH of reaction mass till 2～3.Subsequently feed liquid is cooled to 20～35 ℃ of crystallizations and goes out boric acid, mother liquor is removed in centrifugation, uses the clear water washing leaching cake, and wet boric acid is through super-dry, and 80～120 ℃ of drying temperatures can obtain commodity boric acid, and mother liquid of boric acid and wash water be heating evaporation together, concentrates, and makes Na 2SO 4At high temperature separate out, be deposited in the case of saltouing of vaporizer, feed liquid is concentrated into B 2O 380～100g/l stops evaporation concentration, neutralizes with the borax mother liquor of operation after concentrating during feed liquid is gone.The sodium sulfate of saltouing in the case draws off while hot, filters the sodium sulfate (Na that draws off with the whizzer centrifugation that insulation is arranged or with steam pressurized 2SO 4) contain H 3BO 3Amount is 0.5～1.5%, and filtrate is returned and mixed cake evaporation with the borax mother liquor.
Description of drawings Fig. 1 is with manufacture of boron-containing compound using cotton balls hydrothermal method and comprehensive utilization process schematic flow sheet thereof.
Characteristics of the present invention:
The present invention adopts hydro-thermal method to decompose ulexite (Na2O·2CaO·5 B 2O3·nH 2O), do not consume other reactant namely Sodium calcium line borate is resolved into boric acid calcium salt (solid) and many sodium borate solutions. This solid contains Na2O≤0.5% satisfies Alkali-free glass fibre boracic ingredient requirement. Na in these many sodium borate solutions2O/B 2O 3Mol ratio＜0.45, impure few, without the more expensive compounds containing sodium of price (be NaOH, Na2CO 3Or NaHCO3), only can make with cheap calcium oxide Go out calcium metaborate, borax or kodalk. The sulfuric acid that consumes when making boric acid is than being that raw material lacks 20% with borax.
Embodiment
Embodiment 1
In a useful volume is 6 meters 3The stress reaction jar that is provided with steam jacket in, add 2 meters in 2 meters of boron calcium washing lotions and clear water 3, start and stir, add and (contain B by 180 purpose ulexite breezes more than 95% 2O 33.8%CaO12.23%Na 2O6.77%) 1000kg closes the pipeline valve of turnover retort, and the hole cover of obturaging feeds steam heating and boosts. when the jar internal pressure reaches 0.4MPa, and 150 ℃ of temperature.Keep jar internal pressure and temperature-resistant, decomposed 6 hours, Gu feed the steam of 0.6MPa subsequently material force feed in the jar to pressure filter is carried out liquid～separation, the inlet pressure 0.4MPa that keeps pressure filter, filtrate (many sodium borate solutions) is collected in the multi-borate storage tank, till no filtrate is flowed out, obtain 4.03 meters of filtrates 3, proportion 1.06, composition are B 2O 345g/l Na 2O15.9g/l is with 2 meters of 85 ℃ of hot water 3Washing leaching cake, washing lotion are collected in the washing lotion storage tank, use for batching.Filter cake on the compressor draws off after drying up with the pressurized air of 0.6MPa, obtains wet cake 662kg, and it is sent to drying process, with hollow paddle stirring drier drying, keeps 150 ℃ of temperature of charge, stops 2 hours in the machine, promptly draws to contain B 2O 340.5%, CaO25.9%Na 2The lime borate product 470kg of O＜0.2%.
Embodiment 2
In a useful volume is 6M 3The stress reaction jar that is provided with the steam heating chuck in, add boron calcium washing lotion 2.2M 3, clear water 2.2M 3Start and stir, add and (contain B by the oblique cotton balls breeze of 180 purposes more than 95% 2O 344.13%CaO14.7%Na 2O7.86%) 1000kg closes the pipeline valve of turnover retort, and the hole cover of obturaging feeds steam heating and boosts.When the jar internal pressure reaches 0.9MPa, 180 ℃ of temperature.Keep jar internal pressure and temperature-resistant, decomposed 10 hours.Slowly open bleeder valve subsequently, Gu material force feed in the jar to pressure filter is carried out liquid-separation, keeping the inlet pressure of pressure filter is 0.4MPa, when the jar internal pressure is reduced to 0.4MPa, feed the steam of 0.6MPa, continuation is with the material force feed is to pressure filter in the jar, and material drains in jar, till the pressure filter ejection steam.Filtrate (many dobell's solutions) is collected in the multi-borate storage tank.Obtain 4.4 meters of filtrates 3, proportion 1.07 contains B 2O 352.5g/l Na 2O18.71g/l is with 85 ℃ of hot water 2.2M 3Washing leaching cake, washing lotion are collected in the washing lotion storage tank, use for batching.Filter cake on the compressor draws off after drying up with the pressurized air of 0.6MPa, obtains wet cake 764kg, and it is sent to drying process, with hollow paddle stirring drier drying, keeps 160 ℃ of temperature of charge, stops 2 hours, promptly obtains containing B 2O 340.68%, CaO27.07%Na 2The lime borate product 543kg of O＜0.1%.
Embodiment 3
At a volume 6M 3Have in the retort of stirring, pump into the many dobell's solutions 4.03m that obtains by example 1 3, open and stir, drop into the slaked lime powder 127.7kg that contains CaO72%, temperature of reaction normal temperature, reacted 5 hours, the pH=10.5 stopped reaction is delivered to pressure filter with shurry pump, pressure 0.4MPa before the maintenance machine, filtrate flow is to the light liquid storage tank of sodium metaborate, treat that filtrate is dripped to the greatest extent after, use 0.3m 3Clear water filter wash cake, washing lotion also flow in the light liquid bath.Use the air blow drying filter cake of 0.4MPa at last, till not having water droplet to flow out.Draw off filter cake, obtain 395kg and contain B 2O 3The wet cake of 28.95%CaO23.28%, wet cake is sent to drying process, with hollow paddle stirring drier drying, keeps 130 ℃ of materials, stops 2 hours, can obtain containing B 2O 342.46%CaO34.07%Na 2The calcium metaborate product of O0.18% (purity 98.5%) 270kg.
With the sodium metaborate solution 4M that collects in the light liquid bath 3(contain NaBO 235.6g/l) and meta-acid mother liquid of sodium 461kg be pumped to evaporization process, adopt existing disclosed technology, inspissation is to NaBO 2500g/l delivers to the crystallisation by cooling jar, is cooled to 30 ℃, Na BO 2.4H 2The O crystallization is separated out, centrifugation, and wet sodium metaborate is in the hot-air flow drying, and 100 ℃ of drying temperatures obtain 258kg sodium metaborate product, and purity 〉=98% contains NaBO 223.6% sodium metaborate mother liquor 460kg returns evaporation.
Embodiment 4
The many dobell's solutions 4.05m that obtains by example 1 3Separated into two parts: A and B.A measures 1.34m 3Be used for making calcium metaborate, press method and the step of embodiment 3, input contains the slaked lime 42.3kg of CaO72%, can make to contain B 2O 342.46%CaO34.07%Na 2The calcium metaborate product 88kg of O0.18% draws sodium metaborate mother liquor and wash water 1.33m 3(contain NaBO 235.6g/l) be sent to the manufacturing borax.
With above-mentioned sodium metaborate mother liquor and wash water all with many dobell's solutions B (2.71m 3) after the mixing, be sent to evaporization process, evaporate, concentrate by disclosed technology, be cooled to 30 ℃, crystallization goes out borax, and 0.1m is used in centrifugation 3After the clear water washing, draw off and draw the 432kg borax (borax contains Na 2B 4O 710H 2O95%)
Embodiment 5
By many dobell's solutions proportion 1.06 that example 1 obtains, volume 4.03m 3, use double-effect evaporation, be concentrated into proportion 1.28, B 2O 3Content 15% is sent to the crystallisation by cooling operation, is chilled to 28 ℃, and crystallization goes out borax filters, and uses clear water 0.15m 3Washing leaching cake draws off and obtains 318kg borax (purity Na 2B 4O 710H 2O95%).Filtrate proportion 1.09, volume 0.858m 3Contain B 2O 381.7g/l, Na 2O16.77g/l; Wash water 0.15m 3' contain B 2O 38g/l, Na 2O3.6g/l merges and is sent to boric acid operation manufacturing boric acid together.
Borax mother liquor and wash water are mixed back and Na 2SO 4Mother liquor evaporates together, is concentrated into to contain B 2O 313%, maintain the temperature at 90 ℃, add 92.5 H 2SO 425.52kg, be neutralized to pH=2～3, after reaction finishes, be sent to the cooling of crystallisation by cooling jar, the centrifugation of crystallization boric acid goes out boric acid, with the clear water washing, behind the centrifuge dripping, draw boric acid, after drying, obtain product boric acid 124kg, by existing public technology, mother liquor evaporates once more, concentrates at high temperature to isolate Na 2SO 434kg (contains H 2BO 3＜1%) Na, 2SO 4Mother liquor returns with the borax mother liquor and evaporates.Consume 92.5%H with this method boric acid per ton 2SO 4, only 206kg has only 80% of borax-sulfuric acid process.

Claims (4)

1, a kind ofly makes the hydrothermal method of boron compound, it is characterized in that this method is is that 80～200 order purity are 86～95% to contain B with granularity with the cotton balls breeze 2O 3The cotton balls breeze of 〉=37.5% (weight) or oblique cotton balls breeze are raw material, and it is 2～15: 1 that adding wash water, clear water or mother liquor make liquid-solid ratio, 120～200 ℃ of temperature, and pressure 0.1～1.5MPa, hydrothermal decomposition reaction 2～12 hours obtains Na 2O≤0.5% (weight), B 2O 3Calcareous solid borate of 〉=40% (weight) and undissolved raw ore residue are through press filtration, washing, drying, obtain the lime borate product; Obtain Na simultaneously 2O/B 2O 3Mol ratio is less than many dobell's solutions of the pure calcium metaborate of 0.5 manufacturing, sodium metaborate, borax or boric acid.
2, the integrated application of the many dobell's solutions that obtain according to the described hydrothermal method of claim 1 is characterized in that and will contain B 2O 320～100g/l, Na 2O/B 2O 3Many dobell's solutions of mol ratio 0.3～0.45 under normal pressure, add 0.95～1.3 times of (1-Na 2O/B 2O 3Mol ratio) CaO of quantity or Ca (OH) 2, down reaction 2～10 hours of normal temperature, control pH=10～12, after reaction finishes, with the slurry press filtration, filter cake with the clear water washing after, 100～200 ℃ of dryings, time≤3 hour obtain containing B 2O 341.5～42.5% (weight), CaO33～35% (weight) and Na 2The calcium metaborate of O＜0.5% (weight); The filtrate that press filtration obtains is sodium metaborate solution, and through evaporation concentration, crystallisation by cooling, after the centrifugation, obtaining purity is NaBO 2〉=98% sodium metaborate.
3, the integrated application of the many dobell's solutions that obtain according to the described hydrothermal method of claim 1 is characterized in that many sodium borate solutions separated into two parts: wherein a part is according to the application method of claim 2, by adding CaO or Ca (OH) 2Produce calcium metaborate product and sodium metaborate solution; Another part is allocated sodium boron than making borax with the sodium metaborate solution that the former obtains; The amount that two portions distribute is finally to make Na 2O/B 2O 3Mol ratio is 0.48～0.52 to be as the criterion, and allotment makes the borax Na of purity 〉=95% after evaporation concentration, crystallisation by cooling, centrifugation do not add the alkali that contains sodium 2B 4O 710H 2O.
4, the integrated application of the many dobell's solutions that obtain according to the described hydrothermal method of claim 1 is characterized in that earlier many dobell's solutions evaporation concentration to B 2O 3Content reaches 100～180g/l, and proportion is 1.26～1.31, is cooled to 28 ℃, and borax is separated out in crystallization, filters, and uses the clear water washing leaching cake, obtains purity and be 95% Na 2B 4O 710H 2The O borax; Obtain proportion simultaneously and be 1.08～1.10 and contain B 2O 370～90g/l, Na 2Borax mother liquor and the wash water of O15～20g/l, after the mixing, evaporation concentration is to B 2O 3Concentration is 150～200g/l, at 85～95 ℃, adds concentration 92.5%H 2SO 4Be neutralized to pH=2-3, reaction is cooled to room temperature after finishing, and through separating out boric acid, the clear water washing leaching cake is used in centrifugation, and drying obtains product boric acid; Mother liquid of boric acid is at high temperature separated out Na again through evaporation concentration 2SO 4Saltcake is isolated Na 2SO 4After, mother liquor returns with the borax mother liquor and mixes evaporation.
CNB2006100466666A 2006-05-22 2006-05-22 Manufacture of boron-containing compound using cotton balls hydrothermal method and its comprehensive utilization Expired - Fee Related CN100339303C (en)

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CN103011187B (en) * 2012-12-14 2014-12-03 陕西师范大学 Preparation method of nano-sized CaO.3 B2o3.4 H2O
CN107963913A (en) * 2017-11-10 2018-04-27 中国天辰工程有限公司 The wash mill and washing methods of a kind of ulexite
CN108301045B (en) 2018-03-15 2021-02-12 中国科学院新疆理化技术研究所 Calcium metaborate birefringent crystal, preparation method and application thereof
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