CN108101069A - A kind of exhaust gas produces ammonium fluosilicate co-producing white carbon black raw material process after recycling - Google Patents
A kind of exhaust gas produces ammonium fluosilicate co-producing white carbon black raw material process after recycling Download PDFInfo
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- CN108101069A CN108101069A CN201711462717.8A CN201711462717A CN108101069A CN 108101069 A CN108101069 A CN 108101069A CN 201711462717 A CN201711462717 A CN 201711462717A CN 108101069 A CN108101069 A CN 108101069A
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- ammonium hydroxide
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- ammonium
- white carbon
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic 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
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The present invention relates to the exhaust gas generated in a kind of technique using phosphoric acid production, by itself and ammonium hydroxide hybrid reaction, the higher ammonium fluosilicate of purity, and by-product white carbon black raw material is made in the higher fluosilicic acid of impurity content that ocratation tail gas absorption obtains.The ammonium fluosilicate that content made from fluorine absorption is 7 19wt.%,Purity is low,Impurity content is high,After its simple filtration,The ammonium hydroxide of 20wt.% is added to,Control the addition speed and addition of ammonium hydroxide,Reaction system PH is controlled within 5 always,Gained reacting liquid filtering obtains filter cake as silicon dioxide gel,It can be used as white carbon black raw material,Gained filtrate, which is evaporated, is concentrated into saturation,Decrease temperature crystalline is carried out again,Through separation of solid and liquid,Obtain ammonium fluosilicate crystal,And crystalline mother solution,Crystalline mother solution is reacted back to the mixed rear continuation of fluosilicic acid raw material with ammonium hydroxide,Multiple mother liquor is recycled as by-product is avoided to be enriched with,After several Xun Huans can be spaced,It is used as fluorine absorbing liquid,The condensed water of evaporation and concentration can be used as liquefied ammonia ammonium hydroxide material process,It can also be used for fluorine and absorb process,It gives an actual example in explanation and is carried out explanation,This technique is green safe,It is generated almost without any discarded object,Raw material availability is high,Production cost is low.
Description
Technical field
The present invention relates to the exhaust gas generated in a kind of technique using phosphoric acid production, the impurity content that ocratation tail gas absorption obtains
By itself and ammonium hydroxide hybrid reaction, the higher ammonium fluosilicate of purity, and by-product white carbon black raw material is made in higher fluosilicic acid.
Technical background
Fluorine resource is internationally recognized strategic resource, produces and uses and is paid much attention to be subject to countries in the world.And fluorine provides
Source is mainly derived from fluorite, the strategy of fluorite resource is protected with the exhaustion and country of fluorite resource, being fluorinated the development of work needs
Seek new Fluorine source, recycle existing fluorine resource and save existing fluorite resource.Rock phosphate in powder more than China, 80%
Phosphoric acid is produced for phosphatic fertilizer company, during Wet-process Phosphoric Acid Production, the fluorine in phosphorus ore is with HF and SiF4Form effusion, this portion
Fluorine resource is divided to account for the 38%~45% of the total fluorinated volume of rock phosphate in powder, causes the fluorine wasting of resources and environmental pollution.
Domestic most enterprise constantly inhales fluorinated tail gas using recirculated water, and after enriched, production concentration is low, impurity content is higher
Fluosilicic acid.The low fluosilicic acid of these grades is difficult to sell away or even need processing of paying out of one's own pocket；Or the fluosilicic acid and sodium of recycling
Reactant salt generates prodan and is sold as product, but generates a large amount of sour waters simultaneously, often produces 1t prodan products, row
It puts 15-20t and contains silica gel, prodan and hydrogen ion, acid ion (Cl-Or SO4 2-、SiF6 2-、F-) etc. sour water,
Mating powerful sewage-treatment plant is needed, causes fluorine yield low, sewage disposal expense is big, and product cost is high, deficiency in economic performance.
Ammonium fluosilicate is as a kind of stabilization, and it is by-product fluosilicic acid to be easier to as the product of fluoride salt production intermediate
Good outlet, ammonium fluosilicate overcome the difficulty of transport and the corrosion of liquid fluosilicic acid as a kind of solid product；Due to tail gas
The fluosilicic acid product design for absorbing gained is only 5-15% or so, and the content and utilization rate of fluorine are very low, and ammonium fluosilicate can give birth to
Produce the solid product that purity is more than 98%.
For ammonium fluosilicate compared with prodan, dissolubility is good, as the intermediate of fluorine-containing salt production, has the excellent of bigger
Gesture, ammonium fluosilicate are mainly used as disinfectant in brewing industry, glass etching agent, fabric mothproofing agent, timber preservative, metal welding
Fluxing agent is also used for electroplating industry and prepares cryolith etc..Also, utilize the fluosilicic acid production fluosilicic acid of phosphatic fertilizer company
Ammonium further produces the fluorination work series of products such as solid fluorinated ammonium, solid ammonium hydrogen fluoride, anhydrous hydrogen fluoride, and ammonium fluosilicate is
As an important intermediate products of phosphorus ore association fluorine silicon resource comprehensive utilization.
The content of the invention
As shown in drawings, present invention process, first by the ammonium hydroxide of 5-20% and fluorinated tail gas through water absorb the fluosilicic acid of gained into
Ammonium hydroxide is added slowly in silicate fluoride solution and is stirred continuously, monitors reaction system in reaction process in real time by row hybrid reaction
PH value, in ammonium hydroxide adition process, the pH value of system gradually rises, control PH below 5, stop ammonium hydroxide add in, continue to stir
It mixes, reaction a period of time.
The precipitation of silica of partial white can be generated in reaction process, after filtration, washing and drying as production hard charcoal
Black raw material, filtrate enter evaporative concentration stage of saline.
To prevent the excessively high product for influencing reaction of evaporating temperature, concentration process can carry out evaporation under negative pressure, to reduce
Evaporating temperature reduces influence of the temperature to reaction and product.By the mistake that filtrate is evaporated to saturation state or has a small amount of crystal to be precipitated
Saturation state, evaporation gained filtrate go to be used as the absorbing liquid that fluorine absorbs process, it is also possible to which, as liquefied ammonia ammonium hydroxide, concentrate enters cold
But Crystallization Procedure.
Concentrate carries out decrease temperature crystalline in cooling process, and low temperature causes the solubility of ammonium fluosilicate to reduce, so as to which fluorine be precipitated
The fluosilicic acid that purity is more than 98wt.% can be made using filtering, washing, drying in ammonium silicate solid, the solid for the precipitation that cools down
Ammonium crystal.Filtering gained filtrate, is sufficiently mixed, recycled back to the stage of reaction and silicate fluoride solution.
With the increase for applying mechanically number, the accumulation of by-product will certainly be caused, present invention process design is certain secondary in Xun Huan
After number, filtrate will not recycle, and be used as absorbing liquid back to initial fluorine absorption section, so as to open next filtrate cycle set
Operation cycle.
The characteristics of this process is, is combined being concentrated by evaporation with crystallisation by cooling, using ammonium fluosilicate solubility compared with
Low, solubility is more sensitive to temperature, and other side reaction products or impurities exhibit are relatively high, and solubility is to temperature change
There is no that ammonium fluosilicate is apparent for comparing, control control by-product is precipitated during crystallisation by cooling, so as to improve product
Purity.
In addition, evaporation gained condensed water, can be used as fluorinated tail gas absorbing liquid, it can also be used to which liquefied ammonia ammonium hydroxide will not be formed
The waste of resource reduces production cost.The filtrate of decrease temperature crystalline process filtering gained, repetition are applied mechanically, and improve raw material availability, drop
Low production originally, reduces waste liquid and generates, eliminate environmental pollution.This technique is green safe, is generated almost without any discarded object.
Description of the drawings
Fig. 1 ammonium fluosilicate co-producing white carbon black raw material process FB(flow block)s
A kind of process flow chart hybrid reaction processes of the Fig. 2 as example
Fig. 3 is concentrated by evaporation process as a kind of process flow chart of example
A kind of process flow chart crystallisation by cooling processes of the Fig. 4 as example
1, reaction kettle 2, reaction liquid storage tank 3, reaction solution delivery pump 4, flame filter press 5, filtrate tank 6, filtrate conveying in Fig. 2
Pump
7, evaporation concentrator 8 in Fig. 3, concentrate delivery pump 9 concentrate liquid storage tank 10, knockout drum 11, vacuum pump 12,
Steam condenser 13, condensate tank 14, condensate liquid delivery pump
15, cooler crystallizer 16, centrifuge 17, mother liquor holding tank 18, mother liquor delivery pump in Fig. 4
Example explanation
With reference to example figure, the art inventions are introduced, raw material fluosilicic acid is added in reaction kettle 1 first into Fig. 2, while also has
The crystallization that 18 conveyings come in Fig. 4 centrifuges the mother liquor of gained, and the two is thoroughly mixed in reaction kettle, and reaction kettle 1 is by following
Ring water management jacket temperature, while ammonium hydroxide is slowly added in reaction kettle 1, and opening for ammonium hydroxide pipeline valve is controlled under the control of PH meters
It closes, after PH is increased to 5, ammonium hydroxide valve is closed, and stops adding in, and 1 bottom valve of reaction kettle opens the blowing into reaction liquid storage tank 2, then
Reaction solution is conveyed from reaction solution delivery pump 3 to flame filter press 4, for flame filter press after press filtration, filtrate enters filtrate tank 5, filter
Cake is white carbon black raw material, and filtrate is delivered to evaporation and concentration process through filtrate delivery pump 6.
Fig. 3 by filtrate delivery pump 6 convey Lai filtrate enter evaporation concentrator 7, heat source is provided by jacket steam, carry out
The evaporation and concentration of filtrate, concentrate enter concentration liquid storage tank 9, and the steam for evaporating generation enters steam condenser 12, cold by cycling
But water is condensed, and the condensed water of generation enters condensate tank 13, and the negative pressure for evaporating system is provided by vacuum pump 11, vacuum pump
It is preceding to be equipped with knockout drum 10.Condensed water in condensate tank 13 is delivered to fluorine by condensed water delivery pump 14 and absorbs process and liquid
Ammonia ammonium hydroxide process.Concentrate is delivered to crystallisation by cooling process by concentrate delivery pump 8.
Fig. 4 be crystallisation by cooling process, by concentrate delivery pump 8 convey come concentrate enter cooler crystallizer 15, folder
It is freeze cycle water in set, solid ammonium fluosilicate is precipitated after concentrate cooling, centrifuge 16 is entered by bottom discharge valve, consolidate
Liquid separates, and centrifuges the solid of gained as ammonium fluosilicate solid, and centrifugation is mother liquid obtained into mother liquor holding tank, finally by mother liquor delivery pump
18 are transported to mother liquor the reaction kettle 1 of hybrid reaction process.All of above process can operate continuously, valve instrument etc. it is chain and
It automatically controls.
Claims (5)
1. a kind of exhaust gas produces ammonium fluosilicate co-producing white carbon black raw material process after recycling, it is characterized in that：Using in phosphoric acid production
Fluosilicic acid obtained by the ocratation tail gas absorption of generation is raw material, but is not limited to the fluosilicic acid that simply phosphoric acid production generates, letter
With certain density ammonium hydroxide hybrid reaction after single-filtering, reaction end is controlled with pH value.After filtering, obtained solid washing drying,
Obtain white carbon；Acquired solution is evaporated concentration, the further crystallisation by cooling of concentrate, and the crystal for cooling down precipitation is filtered, washing
After dry, obtain ammonium fluosilicate solid；Filter mother liquid obtained back to fluosilicic acid and phosphoric acid hybrid reaction stage, recycling is more
Mother liquor after secondary recycled is more to ensure that product purity is unaffected after certain number is cycled due to the accumulation of by-product
Mother liquor after secondary utilization returns to fluorinated tail gas absorber portion, for absorbing fluorinated tail gas.
2. the fluorinated tail gas as claimed in claim 1 absorbs the fluosilicic acid of gained, it is characterised in that：Purity is 7-20%, fluorine
Silicic acid by silica can be also dissolved in hydrofluoric acid or mixed silica flour, fluorination except being made using ocratation tail gas absorption
It heats and is made after calcium and the concentrated sulfuric acid.
3. the certain density ammonium hydroxide as claimed in claim 1, it is characterised in that：Ammonia concn≤20wt.%, can be by liquefied ammonia
Dilution is absorbed with the condensation vaporizing described in claim 1 to be made.
4. the fluosilicic acid as claimed in claim 1 is reacted with ammonium hydroxide, it is characterised in that：Ammonium hydroxide should be slowly added into fluosilicic acid
Among solution, reaction end should be 5 or lower for the PH of reaction system.
5. the filtrated stock as claimed in claim 1 is repeatedly applied mechanically, which is characterized in that crystallisation by cooling filtrated stock and Fluoride for Raw Material
Silicic acid is mixed, and after being sufficiently mixed, ammonium hydroxide is slowly added among the solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711462717.8A CN108101069A (en) | 2017-12-28 | 2017-12-28 | A kind of exhaust gas produces ammonium fluosilicate co-producing white carbon black raw material process after recycling |
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| CN201711462717.8A CN108101069A (en) | 2017-12-28 | 2017-12-28 | A kind of exhaust gas produces ammonium fluosilicate co-producing white carbon black raw material process after recycling |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108928825A (en) * | 2018-07-24 | 2018-12-04 | 深圳市深投环保科技有限公司 | The method of silica and ammonium fluosilicate is separated and recovered from fluorine-containing dust |
| CN108996510A (en) * | 2018-06-25 | 2018-12-14 | 确成硅化学股份有限公司 | The preparation method of dustless easy dispersed silicon dioxide |
| CN109574017A (en) * | 2018-11-23 | 2019-04-05 | 贵州开磷氟硅化工有限责任公司 | A method of SiF4 and anhydrous hydrogen fluoride are prepared by raw material of fluosilicic acid |
| CN113023749A (en) * | 2021-03-15 | 2021-06-25 | 盛隆资源再生（无锡）有限公司 | Method for resource utilization of etching process waste |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU882926A1 (en) * | 1980-05-05 | 1981-11-23 | Ленинградский Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Технологический Институт Им. Ленсовета | Method of producing ammonium silicon fluoride |
| CN101269816A (en) * | 2008-05-16 | 2008-09-24 | 夏克立 | Method for producing fluorine series compounds and white carbon black |
| CN101850978A (en) * | 2010-06-06 | 2010-10-06 | 程建方 | Method for preparing ammonium fluosilicate by utilizing tail gas containing fluorine in phosphatic fertilizer production |
| CN102701214A (en) * | 2012-06-28 | 2012-10-03 | 贵州开磷（集团）有限责任公司 | Method for preparing high-purity ammonium fluosilicate |
| CN102976336A (en) * | 2012-12-24 | 2013-03-20 | 贵州省化工研究院 | Method for preparing ammonium fluosilicate solids from fluorosilicone compounds |
-
2017
- 2017-12-28 CN CN201711462717.8A patent/CN108101069A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU882926A1 (en) * | 1980-05-05 | 1981-11-23 | Ленинградский Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Технологический Институт Им. Ленсовета | Method of producing ammonium silicon fluoride |
| CN101269816A (en) * | 2008-05-16 | 2008-09-24 | 夏克立 | Method for producing fluorine series compounds and white carbon black |
| CN101850978A (en) * | 2010-06-06 | 2010-10-06 | 程建方 | Method for preparing ammonium fluosilicate by utilizing tail gas containing fluorine in phosphatic fertilizer production |
| CN102701214A (en) * | 2012-06-28 | 2012-10-03 | 贵州开磷（集团）有限责任公司 | Method for preparing high-purity ammonium fluosilicate |
| CN102976336A (en) * | 2012-12-24 | 2013-03-20 | 贵州省化工研究院 | Method for preparing ammonium fluosilicate solids from fluorosilicone compounds |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108996510A (en) * | 2018-06-25 | 2018-12-14 | 确成硅化学股份有限公司 | The preparation method of dustless easy dispersed silicon dioxide |
| CN108928825A (en) * | 2018-07-24 | 2018-12-04 | 深圳市深投环保科技有限公司 | The method of silica and ammonium fluosilicate is separated and recovered from fluorine-containing dust |
| CN109574017A (en) * | 2018-11-23 | 2019-04-05 | 贵州开磷氟硅化工有限责任公司 | A method of SiF4 and anhydrous hydrogen fluoride are prepared by raw material of fluosilicic acid |
| CN113023749A (en) * | 2021-03-15 | 2021-06-25 | 盛隆资源再生（无锡）有限公司 | Method for resource utilization of etching process waste |
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Application publication date: 20180601 |