CN104843712A - Industrial fluosilicic acid purification and white carbon black co-production method - Google Patents
Industrial fluosilicic acid purification and white carbon black co-production method Download PDFInfo
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Abstract
An industrial fluosilicic acid purification and white carbon black co-production method belongs to the technical field of inorganic acid chemical production and purification. The method comprises the following steps: contacting an industrial fluosilicic acid solution with silica powders and carrying out heating, and collecting silicon tetrafluoride gas obtained after heating; absorbing the obtained silicon tetrafluoride gas directly by absorption liquid, and carrying out hydrolysis reaction to obtain a mixture of a fluosilicic acid solution and hydrated silicon dioxide solid; and separating the mixture to obtain the fluosilicic acid solution and the hydrated silicon dioxide solid. The method does not waste fluorine atoms in the purification process, and thus application range and additional value of the industrial fluosilicic acid are improved.
Description
Technical field
The invention belongs to Chemical Manufacture and the purification techniques field of mineral acid, specifically, the present invention relates to the treatment process that a kind of industrial silicofluoric acid and ground silica association response obtain more pure fluosilicic acid and white carbon black.
Background technology
Silicofluoric acid also known as silicofluoric acid, the molecular formula of silicofluoric acid: H
2siF
6, molecular weight 144.09, the most high-content of its aqueous solution is 60.92%, and being rendered as a kind of water white fuming liquid, relative density about 1.32, boiling point 108.5 DEG C, is that one has irritating smell, and holds strong acid in volatile one.Rare silicate fluoride solution has certain disinfectant properties, is usually used in the sterilization in the fields such as beer.Silicofluoric acid can be hydrolyzed at storage process and produce certain density hydrofluoric acid, thus can the silicate such as etching glass, pottery material.Because the silicofluoride of the metals such as plumbous and copper is solubility salt, thus industrial silicofluoric acid can wait metal with plumbous by dissolved copper, and silicofluoric acid and plumbous silicofluoride solution thereof are the electrolytic solution compositions of the most classical industrial Betts performing electrolytic refining on lead bullion at present.In addition, silicofluoric acid is important basic raw material producing in Sodium Silicofluoride, potassium, ammonia, magnesium, copper, barium, lead and other silicofluorides etc.The Metal plating especially of highly purified silicofluoric acid, wood preservation, beer sterilization, brewery industry equipment disinfection (1% ~ 2%H
2siF
6) and the plumbous indispensable important mineral acid of electrolytic refining.
Current industrial silicofluoric acid mainly comes from the by product in phosphate fertilizer industry by product and anhydrous hydrogen fluoride production process.Due in Rock Phosphate (72Min BPL) nearly 2% ~ 4% fluorine element exist, produce these fluorine elements in phosphate fertilizer process and become the form of hydrofluoric acid and silicon tetrafluoride gas to overflow by sulfuric acid acidation, be only absorbed by the water formation silicofluoric acid.Usually these silicofluoric acid contain a small amount of sulfate ion, calcium ion and phosphate anion, because sulfate ion and lead ion generate lead sulfate precipitation, thus these silicofluoric acid usually can not directly accept by lead electrolytic solution producer.Some silicofluoric acid producer adopts and in silicofluoric acid, adds a small amount of yellow lead powder (plumbous oxide) in advance remove the sulfate radical be wherein mingled with and reach the object tentatively provided.Comparatively speaking, industrial silicofluoric acid price is at 2600-3500 yuan/ton, and yellow lead powder price is near 14000 yuan/ton, and therefore this impurity-removing method brings the removal of impurities cost up to 600 yuan per ton to producer.In addition, utilizing fluorite and the vitriol oil of being fuming to prepare same also by-product fluosilicic acid in the process of anhydrous hydrogen fluoride, a lot of enterprise after simple process, as Industrial Wastewater Treatment, this not only will spend a certain amount of processing costs, also can cause the wasting of resources of silicofluoric acid.
Usually compared with the industrial silicofluoric acid of low-purity as the raw material of the fluorochemical such as Sodium Silicofluoride and aluminum fluoride, and its added value is not high.Also report is had, utilize ammonia or carbon ammonium and silicofluoric acid to react and generate ammonium silicofluoride, Neutral ammonium fluoride and white carbon black is generated with ammonia alkali solution ammonium silicofluoride, concentrated also thermolysis Neutral ammonium fluoride prepares ammonium bifluoride, ammonium bifluoride and sulfuric acid reaction generate ammonium sulfate, reclaim highly purified hydrogen fluoride for the preparation of high-purity fluorine silicic acid, the shortcoming of this kind of technique is exactly that intermediate conversion steps is various, and generation intermediate product and a large amount of byproduct cause the fluorine wasting of resources.
Chinese patent CN101134580 and CN101134583 all discloses the method for producing Potassium monofluoride with silicofluoric acid, react with Repone K, potassium hydroxide and silicofluoric acid respectively, obtain potassium silicofluoride, potassium silicofluoride is heated to 300-800 DEG C to decompose, generate Potassium monofluoride solid phase prod and silicon tetrafluoride gas, silicon tetrafluoride gas is after absorbing, then return to can silicofluoric acid processed or potassium silicofluoride.Because reaction process needs to consume the more expensive potassium hydroxide of a large amount of price, add that potassium silicofluoride decomposition reaction needs high-temperature roasting to cause energy consumption comparatively large, and rate of decomposition is low, industrial application value is low.
Summary of the invention
The object of the present invention is to provide a kind of clean method meeting the purification co-production white carbon black of the industrial silicofluoric acid of atom economy method, do not produce the waste of fluorine atom at purification process, thus improve range of application and the added value of industrial silicofluoric acid.
The method of the purification co-production white carbon black of a kind of industrial silicofluoric acid of the present invention, mainly comprises following process:
(1) industrial silicate fluoride solution is contacted with ground silica then heat, the silicon tetrafluoride gas obtained after collecting heating;
(2) silicon tetrafluoride gas obtained in step (1) directly absorbed with absorption liquid and occur to be hydrolyzed the mixture being obtained by reacting silicate fluoride solution and hydrated SiO 2 solid;
(3) mixture that obtains of separating step (2), obtains silicate fluoride solution and hydrated SiO 2 solid respectively.
Wherein further in order to accelerate the contact reacts of the described silicate fluoride solution of step (1) and ground silica, need in industrial silicate fluoride solution, to add catalyzer to promote the volatiling reaction of silicofluoric acid and ground silica contact process, catalyzer mainly contain in following material one or several: in phosphoric acid, perchloric acid, methylsulphonic acid, methyl acid phosphate and aminomethyl phosphonic acid, the consumption of its arbitrary catalyzer is the 0.01%-15% of silicofluoric acid weight percentage in industrial silicate fluoride solution.
In order to ensure that stable the continuing reacted carries out, and the SiF promoting reaction process to produce
4gas can be continual and steady from this reaction system volatilization, great many of experiments shows, in the present invention's industry silicofluoric acid+ground silica+above-mentioned catalyzer this specific environment, temperature of reaction controlled to be advisable at 30 DEG C ~ 110 DEG C, wherein preferable temperature is 55-105 DEG C.Too low temperature is not used in be obtained by reacting to produce and continues to obtain SiF
4gas, the HF of the too high temperature certain content of by-product simultaneously, makes the selectivity of catalyst reaction reduce.The feed ratio of general silicate fluoride solution and ground silica is amount to pure fluosilicic acid amount of substance in silicate fluoride solution: amount=(1.5 ~ 10) of amounting to silicon-dioxide pure substance in ground silica: 1.Above-mentioned reaction can be simplified to:
2H
2SiF
6+SiO
2＝3SiF
4+2H
2O。(1-1)
SiF
4gas absorbs through the silicofluoric acid of water or lower concentration, is again hydrolyzed into H
2siF
6, obtain H simultaneously
2siO
3(or some document representation is silicic acid), also can be expressed as SiO
2h
2o (hydrated SiO 2), the reaction of this process can be simplified to:
3SiF
4+3H
2O＝2H
2SiF
6+H
2SiO
3(1-2)
Or
3SiF
4+3H
2O＝2H
2SiF
6+SiO
2·H
2O (1-3)
Experiment shows, the absorption liquid of absorption silicon tetrafluoride gas is rare silicate fluoride solution by step (2), and rare silicofluoric acid concentration controls at 0-6mol/L, and absorption temperature is controlled at-10 DEG C to 60 DEG C, preferably-5 DEG C to 50 DEG C, the abundant hydrolysis of silicon tetrafluoride gas can be ensured.
The present invention's hydrated SiO 2 comprised step (3) obtains that further works obtains white carbon black after super-dry and roasting.
The present invention has low raw-material cost, easily control, operational path advantages of simple, advantage that resource utilization is high, has market and using value widely.
In one embodiment, described industrial silicate fluoride solution comprises the fluorine silicon acid waste products in by-product in phosphate fertilizer industry by-product and anhydrous hydrogen fluoride production process or other production processes.
In one embodiment, the pure amount of silicofluoric acid described in step (1) and the amount of substance of the pure amount of silicon-dioxide in ground silica are than 1.5 ~ 10:1, and preferred silica powder is excessive, further preferred 2-3:1.In one embodiment, described in step (1), heating evaporation temperature is 30 ~ 110 DEG C, preferred 55-105 DEG C.In one embodiment, with water or also can absorb silicon tetrafluoride gas with rare silicofluoric acid described in step (3), the mixture of silicofluoric acid and hydrated SiO 2 is obtained by reacting.
In one embodiment, step carries out suction filtration to mixture described in (3), makes solid-liquid separation, and filtrate is pure silicofluoric acid, and filter residue is white carbon black.
Utilize aforesaid method cheap industrial silicofluoric acid and ground silica can be fully utilized, the pure silicofluoric acid obtaining two kinds of high added values of preparation and high quality white carbon black products, turn waste into wealth.
According to method of the present invention, the source of industrial silicofluoric acid comprises the fluorine silicon acid waste products in by-product in phosphate fertilizer industry by-product and anhydrous hydrogen fluoride production process or other production processes, and concentration is unrestricted.
Utilize aforesaid method can effectively utilize cheap ground silica and industrial silicofluoric acid to prepare pure silicofluoric acid and the white carbon black product of the high added value of two kinds of different purposes, and the method energy consumption is low, environmental protection, can not produce anyly be difficult to process, the byproduct of contaminate environment.
Embodiment
Because industrial silicofluoric acid is placed through long-term, cause part SiF
4volatilize, make HF acid residual more in solution, simultaneously containing some other insoluble impuritiess.For above-mentioned containing the industrial silicofluoric acid of hydrofluoric acid or the useless silicofluoric acid of recovery, on the superincumbent basis of the present invention, contain the pre-treatment step of below industrial silicofluoric acid two, the method is specific as follows:
(1) pre-treatment of industrial silicofluoric acid
Industrial silicofluoric acid is carried out pre-filtering, to remove floating impurity etc.;
(2) the pre-dehydrogenation fluoric acid process of industrial silicofluoric acid
By the settled solution after step (1) pre-filtering process, mix at room temperature 20-25 DEG C with the excessive material containing active silica.
The 1.0-1.5:1 adopting the white carbon black of gained of the present invention or ground silica etc. to measure ratio according to chemical equation containing the material of active silica and the hydrofluoric acid in solution mixes at room temperature 20-25 DEG C, now in solution, original residual hydrofluoric acid and the new active silica dropped into react, obtaining silicofluoric acid, mainly there is following chemical reaction in this step:
6HF+SiO
2＝H
2SiF
6+2H
2O
Silicofluoric acid subsequently through pre-filtering and pre-de-hydrofluoric acid treatment enters silicofluoric acid purification process as elucidated before.For the ease of understanding method of purification of the present invention, obtain pure silicofluoric acid below to the purification of fluorine silicon acid waste liquid, the method for co-production white carbon black is further described in detail, and unrestricted application of the present invention.1, the pyrolytic gasification process of silicofluoric acid:
According to one embodiment of present invention, join in reactor after waste liquid containing silicofluoric acid is mixed with excessive ground silica at room temperature 20-25 DEG C and heat, when temperature reaches 30 DEG C ~ 110 DEG C, now silicofluoric acid and silicon-dioxide are under acidic medium, start to generate silicon tetrafluoride gas, the main generation of this step is reacted as follows:
2H
2SiF
6+SiO
2＝3SiF
4+2H
2O
In step 1, the silicofluoric acid in above-mentioned reaction formula in a heated condition, starts and silicon dioxde reaction generation silicon tetrafluoride gas, and evaporates from reaction system.
According to the embodiment of the present invention, the temperature of reaction in above-mentioned thermal degradation process is 30 ~ 110 DEG C, is preferably 55-105 DEG C.According to the embodiment of the present invention, if described temperature is lower than 30 DEG C, will the effect of distillation not be reached, cannot product be obtained; If described temperature is higher than 110 DEG C, part silicofluoric acid will be had directly to evaporate and with a large amount of foreign ion and water vapour, affect product silicofluoric acid purity, and cause output of white carbon black to reduce.
According to the embodiment of the present invention, the concentration of the waste liquid containing silicofluoric acid is unrestricted, as long as silicofluoric acid (pure amount) is 1.5 ~ 10:1 with the ratio of the amount of substance of silicon-dioxide (pure amount) in guarantee solution, if described ratio >10, ground silica will be caused to be deposited on base of evaporator, impact heat transfer and stirring, cause reaction not exclusively, throughput declines; If ratio <1.5, containing a large amount of hydrogen fluoride gas in the gas evaporated, affect purification silicofluoric acid effect and silicofluoric acid output.The difference of acid concentration and hydrofluoric acid concentration in the industrial silicofluoric acid that the present invention provides according to different sources and different manufacturers, suitably adjustment adds the amount of ground silica, ensures the quality of production and the production efficiency of silicofluoric acid.
2, the hydrolytic process of silicon tetrafluoride gas
According to one embodiment of present invention, the silicon tetrafluoride gas water of above-mentioned generation or rare silicofluoric acid are absorbed, make it at low temperatures hydrolysis reaction occur, generate the mixture of silicofluoric acid and hydrated SiO 2, wherein chemical equation is as follows:
3SiF4+3H
2O＝2H
2SiF
6+SiO
2·H
2O (1-4)
Although hydrated SiO 2 has multiple crystal water form, what its unification after roasting drying and dehydrating was single is silica form.The present invention in order to express easily, adopts single hydrated SiO 2 to represent.This hydrolysis reaction is a thermopositive reaction.Experiment shows, the temperature of reaction of this process should control at-5 ~ 25 DEG C, and optimum temps is 0-20 DEG C.
3, solid-liquid separation process
According to one embodiment of present invention, silicofluoric acid is separated with the solidliquid mixture of hydrated SiO 2, to obtain silicofluoric acid liquid and hydrated SiO 2 solid.4, the washing-roasting process of hydrated SiO 2
According to the embodiment of the present invention, washing, purifying process is carried out further to being separated the hydrated SiO 2 obtained, so that the silicofluoric acid removed in white carbon black and sour gas, wherein washings can be incorporated to silicofluoric acid stoste to be clean or as the one-level of low concentration in multistage washings.
Finally drying and calcination process are carried out to above-mentioned hydrated SiO 2, finally obtain pure high-quality white carbon black.
The purification of the present invention to fluorine silicon acid waste liquid obtain pure silicofluoric acid and the method and apparatus producing white carbon black comparatively prior art compare, only use chemical raw material industry silicofluoric acid and the ground silica of single cheapness, produce pure silicofluoric acid and white carbon black two kinds of high value added products.
This production equipment independence is strong, easily manipulates.
Pollution-free, environmental protection, environmental friendliness, does not produce any hostile environment, reluctant by product.
Embodiment 1
Get certain A and produce phosphate fertilizer factory fluorine silicon acid waste liquid 500L (silicofluoric acid concentration is 3.2M, and hydrofluoric acid concentration is 0.2M), ground silica: 65Kg (silica purity is 98%).Specific implementation process is as follows:
1) fluorine silicon acid waste liquid is filtered, remove floating impurity etc.;
2) mixed with ground silica 6.5Kg by fluorine silicon acid waste liquid 50.0L, mixing speed is 60r/min, fully reacts, and makes the hydrogen fluoride contained in silicofluoric acid be converted into silicofluoric acid.
3) mixture of reaction in step 2 is joined reacting by heating in reactor to decompose, temperature of reaction 75 DEG C, keeps constant temperature and Keep agitation, stirring velocity 120 revs/min, controls 8 hours reaction times, now obtains silicon tetrafluoride gas.
4) silicon tetrafluoride gas water (temperature is 15 DEG C) absorption reaction step 3 generated, generates the solidliquid mixture of silicofluoric acid and hydrated SiO 2.
5) mixture of the silicofluoric acid generated in step 4 and hydrated SiO 2 is carried out solid-liquid separation, wherein filtrate is silicofluoric acid, and filter cake is the hydrated SiO 2 solid of white.This white product carries out washing, dry and 400 DEG C of calcinings obtained white carbon black after 3 hours.
Test and titration results calculate by analysis, and obtain about 44 liters, concentration is 3.5M, and purity is 99.9% silicofluoric acid, simultaneously by-product white carbon black 6.1 kilograms.
Embodiment 2
Get certain hydrofluoric acid factory fluorine silicon acid waste liquid 100L (silicofluoric acid concentration is 2.7M, and hydrofluoric acid concentration is 1.1M), ground silica: 13Kg (silica purity is 98%).Specific implementation process is as follows:
1) fluorine silicon acid waste liquid is filtered, remove floating impurity etc.;
2) mixed with ground silica 13Kg by fluorine silicon acid waste liquid 100L, mixing speed is 50r/min, fully reacts 60min, is converted into corresponding silicofluoric acid fully to make the hydrogen fluoride in silicofluoric acid solution.
3) solidliquid mixture of reaction in step 2 is joined reacting by heating in reactor to decompose, temperature of reaction 70 DEG C, stirring velocity 150 revs/min, controls 9 hours reaction times, to obtain silicon tetrafluoride gas.
4) silicon tetrafluoride gas step 3 generated rare silicofluoric acid (concentration is 2M, and temperature is 25 DEG C) absorption reaction, generates the solidliquid mixture of silicofluoric acid and hydrated SiO 2.
5) whizzer is utilized to carry out solid-liquid separation the silicofluoric acid generated in step 4 and hydrated SiO 2 mixture, wherein filtrate is silicofluoric acid, filter cake is the hydrated SiO 2 of white, and washs white product, after drying, within 2 hours, obtains white carbon black 500 DEG C of calcinings.
6) through measuring and calculation, obtaining 95 liters of purity is 99.9%, and concentration is the silicofluoric acid of 3M, and corresponding white carbon black is 11 kilograms.
Embodiment 3
(silicofluoric acid concentration is 2.7M to get certain phosphate fertilizer plant fluorine silicon acid waste liquid 100L, hydrofluoric acid concentration is 1.1M), ground silica: 10Kg (silica purity is 98%), adds that embodiment 2 gained white carbon black (amounting to silica purity is 99.2%) 2 kilograms is raw material.Specific implementation process is as follows:
1) fluorine silicon acid waste liquid is filtered, remove floating impurity etc.
2) mix after dropping into 10 kilograms of ground silicas and 2 kilograms of white carbon blacks in fluorine silicon acid waste liquid 100L, mixing speed is 60r/min, fully reacts 50min, to remove the hydrogen fluoride in siliceous fluorspar acid solution, and it is made to be regenerated as corresponding silicofluoric acid.
3) mixture reacted in step 2 is joined reacting by heating in reactor to decompose, temperature of reaction 80 DEG C, keep stirring and heating, stirring velocity 150 revs/min, successive reaction 8 hours, to make reactant fully react, obtains silicon tetrafluoride gas.
4) enough rare silicofluoric acid (concentration is 1M, and temperature the is 25 DEG C) absorption reactions of silicon tetrafluoride gas step 3 generated, generate the liquid-solid mixture of silicofluoric acid and hydrated SiO 2.
5) utilize pressure filter to carry out repeatedly solid-liquid separation the silicofluoric acid generated in step 4 and white carbon black liquid-solid mixture, wherein filtrate is silicofluoric acid, and filter cake is hydrated SiO 2, and this filter cake obtains white carbon black in 1 hour through washing, drying and 500 degree of roastings.
6) through measuring and calculation, this experiment acquisition 130 liters of purity are 99.9%, and concentration is 2.8M silicofluoric acid, and by-product white carbon black 11 kilograms.
Embodiment 4
(silicofluoric acid concentration is 2.7M to get the fluorine silicon acid waste liquid 100L of same embodiment 3, hydrofluoric acid concentration is 1.1M), ground silica: 10Kg (silica purity is 98%), adds that embodiment 2 gained white carbon black (amounting to silica purity is 99.2%) 2 kilograms is raw material.Specific implementation process is as follows:
1) fluorine silicon acid waste liquid is filtered, remove floating impurity etc.;
2) mix after dropping into 10 kilograms of ground silicas and 2 kilograms of white carbon blacks in fluorine silicon acid waste liquid 100L, mixing speed is 60r/min, fully reacts 50min, to remove the hydrogen fluoride in siliceous fluorspar acid solution, and it is made to be regenerated as corresponding silicofluoric acid.
3) mixture reacted in step 2 to be joined in reactor reacting by heating to decompose, add 100 grams of phosphoric acid and the 50 grams of methylsulphonic acids catalyzer as reaction process simultaneously.Control temperature of reaction 85 DEG C, stirring velocity 120 revs/min, after 4 hours, reaction terminates, and collects the silicon tetrafluoride gas that reaction process volatilization produces.
4) enough rare silicofluoric acid (concentration is 1M, and temperature the is 25 DEG C) absorption reactions of silicon tetrafluoride gas step 3 generated, generate the liquid-solid mixture of silicofluoric acid and hydrated SiO 2.
5) utilize pressure filter to carry out repeatedly solid-liquid separation the silicofluoric acid generated in step 4 and white carbon black liquid-solid mixture, wherein filtrate is silicofluoric acid, and filter cake is hydrated SiO 2, and this filter cake obtains white carbon black in 1 hour through washing, drying and 500 degree of roastings.
6) through measuring and calculation, this experiment acquisition 130 liters of purity are 99.9%, and concentration is 2.8M silicofluoric acid, and by-product white carbon black 11 kilograms.
Embodiment 5
Get the silicofluoric acid waste liquid 500L (silicofluoric acid concentration is 3.2M, and hydrofluoric acid concentration is 0.2M) that certain sky reaches chemical plant production, ground silica: 65Kg (silica purity is 98%).Specific implementation process is as follows:
1) fluorine silicon acid waste liquid is filtered, remove floating impurity etc.;
2) mixed with ground silica 6.5Kg by fluorine silicon acid waste liquid 50.0L, mixing speed is 60r/min, fully reacts, and makes the hydrogen fluoride contained in silicofluoric acid be converted into silicofluoric acid.
3) mixture of reaction in step 2 is added 200 grams of phosphoric acid and the 100 grams of perchloric acid catalyzer as reaction process, then be passed in reactor and carry out carrying out decomposition reaction at 75 DEG C, keep constant temperature and Keep agitation, stirring velocity 150 revs/min, now obtain silicon tetrafluoride gas, until reaction terminates after 4 hours.
4) silicon tetrafluoride gas water (temperature is 15 DEG C) absorption reaction step 3 generated, generates the solidliquid mixture of silicofluoric acid and hydrated SiO 2.
5) mixture of the silicofluoric acid generated in step 4 and hydrated SiO 2 is carried out solid-liquid separation, wherein filtrate is silicofluoric acid, and filter cake is the hydrated SiO 2 solid of white.This white product carries out washing, dry and 400 DEG C of calcinings obtained white carbon black after 3 hours.
Test and titration results calculate by analysis, and obtaining about 44 liters of concentration is 3.5M, and purity is 99.9% silicofluoric acid, simultaneously by-product white carbon black 6.1 kilograms.
Claims (10)
1. a method for the purification co-production white carbon black of industrial silicofluoric acid, is characterized in that, mainly comprise following process:
(1) industrial silicate fluoride solution is contacted with ground silica then heat, the silicon tetrafluoride gas obtained after collecting heating;
(2) silicon tetrafluoride gas obtained in step (1) directly absorbed with absorption liquid and hydrolysis occur to be obtained by reacting silicofluoric acid molten
The mixture of liquid and hydrated SiO 2 solid;
(3) mixture that obtains of separating step (2), obtains silicate fluoride solution and hydrated SiO 2 solid respectively.
2. according to the method for claim 1, it is characterized in that, in order to accelerate the contact reacts of the described silicate fluoride solution of step (1) and ground silica, need in industrial silicate fluoride solution, to add catalyzer to promote the volatiling reaction of silicofluoric acid and ground silica contact process, catalyzer mainly contain in following material one or several: in phosphoric acid, perchloric acid, methylsulphonic acid, methyl acid phosphate and aminomethyl phosphonic acid, the consumption of its arbitrary catalyzer is the 0.01%-15% of silicofluoric acid weight percentage in industrial silicate fluoride solution.
3. according to the method for claim 2, it is characterized in that, temperature of reaction, in industrial this specific environment of silicofluoric acid+ground silica+catalyzer, controls at 30 DEG C ~ 110 DEG C by step (1).
4. according to the method for claim 3, it is characterized in that, temperature of reaction is 55-105 DEG C.
5. according to the method for claim 1, it is characterized in that, the feed ratio of silicate fluoride solution and ground silica is amount to pure fluosilicic acid amount of substance in silicate fluoride solution: amount to the amount of silicon-dioxide pure substance in ground silica for (1.5-10): 1.
6. according to the method for claim 5, it is characterized in that, the feed ratio of silicate fluoride solution and ground silica is amount to pure fluosilicic acid amount of substance in silicate fluoride solution: amount to the amount of silicon-dioxide pure substance in ground silica for (2-3): 1.
7. according to the method for claim 1, it is characterized in that, the absorption liquid of absorption silicon tetrafluoride gas is rare silicate fluoride solution by step (2), and rare silicofluoric acid concentration controls at 0-6mol/L, and absorption temperature is controlled at-10 DEG C to 60 DEG C.
8. according to the method for claim 7, it is characterized in that, absorption temperature-5 DEG C is to 50.
9. according to the method for claim 1, it is characterized in that, the hydrated SiO 2 that step (3) obtains obtains white carbon black after super-dry and roasting.
10. according to the method for claim 1, it is characterized in that, before carrying out step (1), process removing HF carried out to industrial silicate fluoride solution, comprise the following steps:
The pre-treatment of industry silicofluoric acid, filters industrial silicofluoric acid, removes floating impurity; Settled solution is mixed at room temperature 20-25 DEG C with the excessive material containing active silica; The 1.0-1.5:1 that the material of active silica measures ratio with the hydrofluoric acid in solution according to chemical equation adds.
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| CN106365189A (en) * | 2016-08-29 | 2017-02-01 | 昆明理工大学 | Comprehensive utilization method of silicon residue soil |
| CN110092523A (en) * | 2019-06-06 | 2019-08-06 | 盛隆资源再生（无锡）有限公司 | A kind of processing method of the fluorine-containing phosphorus-containing wastewater containing ammonia nitrogen |
| CN114436236A (en) * | 2020-11-06 | 2022-05-06 | 中国化学工业桂林工程有限公司 | Method for purifying cracking carbon black and by-producing fluosilicic acid |
| CN116443884A (en) * | 2023-06-07 | 2023-07-18 | 内蒙古星汉新材料有限公司 | Byproduct fluosilicic acid impurity removal process and potassium fluoride preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3971845A (en) * | 1972-09-30 | 1976-07-27 | Bayer Aktiengesellschaft | Recovery of hydrofluoric acid from aqueous fluosilicic acid |
| CN1267634A (en) * | 2000-03-23 | 2000-09-27 | 李远志 | One-step hydrolysis process of producing active white carbon from silicon tetrafluoride by product of phosophate fertilizer plant |
| CN103058202A (en) * | 2013-01-11 | 2013-04-24 | 瓮福（集团）有限责任公司 | Method for recycling silicon-producing white carbon black in wet-process phosphoric acid tail gas |
| CN103601195A (en) * | 2013-10-14 | 2014-02-26 | 班仁义 | Gas phase hydrolysis and fluoride-silicon separation method of silicon tetrafluoride |
| CN103864078A (en) * | 2012-12-17 | 2014-06-18 | 沁阳市昊达实业有限公司 | A method of removing residue hydrogen fluoride in fluosilicic acid |
-
2015
- 2015-04-24 CN CN201510201239.XA patent/CN104843712B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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