CN102795701A - Method for treating acidic waste water from titanium dioxide preparation by sulfuric acid method - Google Patents

Method for treating acidic waste water from titanium dioxide preparation by sulfuric acid method Download PDF

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CN102795701A
CN102795701A CN2012102956241A CN201210295624A CN102795701A CN 102795701 A CN102795701 A CN 102795701A CN 2012102956241 A CN2012102956241 A CN 2012102956241A CN 201210295624 A CN201210295624 A CN 201210295624A CN 102795701 A CN102795701 A CN 102795701A
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barium
waste water
acid
barium carbonate
sulfuric acid
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胡治邠
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胡治邠
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Abstract

A method for treating acidic waste water from titanium dioxide preparation by a sulfuric acid method is characterized in that barium carbonate is used as a treating agent, and the circulation flow of the treating agent is barium carbonate, barium sulfate, barium sulfide, and barium carbonate; the method comprises the following steps: adding barium carbonate into acidic waste water to generate barium sulfate precipitates, separating the barium sulfate from water so as to adjust the acid of the acidic waste water and to remove sulfate radicals to reach environmental protection requirements; reducing the barium sulfate into barium sulfide, injecting carbon dioxide into the barium sulfide aqueous solution to generate barium carbonate. The invention is provided aiming at the treatment of a lot of waste water generated in titanium dioxide production by a sulfuric acid method; the waste water is treated by acid adjustment by barium carbonate and sulfate radical removal so as to be reduced into clean water; the generated 'wastes' can be converted into the treating agent of barium carbonate for next acid adjustment and sulfate radical removal; therefore, cleaning production can be performed round and round, and almost no solid slag or waste water is produced.

Description

Sulfuric acid process is produced the method for the acid waste water improvement of white titanium pigment
Technical field
The sulfuric acid process that the present invention relates in the field of environment protection is produced the method for the acid-bearing wastewater improvement of white titanium pigment, makes the sector walk out the predicament of environment.Bittern in the chlor-alkali industry is removed nitre also can use, to arid and semiarid water-deficient area, the safety at water source is removed nitre and also can be used.
Background technology
At present, about 11,000,000,000 dollars of the global white titanium pigment output value is to be only second to synthetic ammonia, three big inorganic chemical products of phosphoric acid.[See, author Liu Fangbin, "sulfate process titanium dioxide environmental predicament can break?" China Chemical Industry News, Update time :2012 -05-29] titanium dioxide as many countries will be affected by the National Economic Development, a key chemical , the per capita consumption of titanium dioxide Di was also seen by the Economic Development of a country an important indicator of the level.Since 2000, China's annual output of titanium dioxide Fen industry from 34 tons to the current 1.8 million tons, second only to the United States has become the second largest titanium dioxide producer.
With economic development, China's growing demand for coatings, however, the production of titanium dioxide to sulfuric acid, Di plagued by environmental governance, it is difficult out of the woods.
Which does the environmental protection predicament that sulfuric acid process is produced white titanium pigment have?
1, factory's point is many, and small scale is polluted heavy; The whole world 100 families, China 63 families, enterprise's number is 60%, and output has only 20% of global output;
2,? Excessive emissions per ton of product, preclude the use of sulfuric acid to produce 1 ton of titanium dioxide water 100-150 tons, 1.6 tons of standard coal consumption, resulting in nearly 20% of the concentration of sulfuric acid containing wastewater eight tons, low concentrations 100 tons of acidic waste water, waste 8 tons, as well as containing SO 2 mist and dust exhaust 25,000 m 3 .. ......;
3, disposal of waste gas, water and industrial residue difficulty is little, but amount is big, and total control expense is too high.Sulfuric acid process waste water and dregs treatment cost is up to 1900 yuan of ton finished products.
The staple of Titanium White Production By Sulfuric Acid Process lower concentration acid waste water is: the water sample analysis result by the Zhuzhou is following:
Sulfuric acid=2---3% Ca 2+=650---750mg/l
Fe 2+=4--5g/l Cl -? =150--250mg/l
Mg 2+=70--150mg/l pH=1 TDS=32g/l
Can find out that from last data 1 ton of total TDS of waste water is 32kg/t, the sulfuric acid 20-30kg/t that contains per ton is as pressing 100 tons of calculating of 1 ton of white titanium pigment exhausting low-concentration of every production acid waste water; 3000 kg sulfuric acid (100 tons * 30kg/t=3000 kg sulfuric acid) are arranged; 10,000 tons of white titanium pigments just have 30,000 tons of sulfur waste acid, and are high like this " refuse " with the lime neutralization, lose soda ash again; Removing calcium, is again to produce a large amount of real obsolete gypsum and caustic soda (being waste residue).
The TDS that our acid waste water is issued in the strain state can find out that it is that sulfuric acid and vitriol are main waste water, Key is acid adjustment and removes vitriol.
The following document that has that proposes to be correlated with and improve one's methods:
Document one: one Chinese patent application " method that a kind of titanium dioxide acid waste water is handled; application number: 200610039259.2 applyings date: 2006-04-03 " has disclosed a kind of modification method that processes agent with unslaked lime; Improved the unslaked lime utilization ratio; Reduce the processing cost of waste water, and eliminated the useless admittedly secondary pollution of digestion slag.
Document two: Chinese patent: " method of method for producing gtitanium dioxide with sulphuric acid (having the right), application number: 200710202160.4 applyings date: 2007-10-19 ".The acid waste water that produces in the preparation process adds sodium hydroxide or Pottasium Hydroxide neutralization, and the vitriol electrolysis that neutralization produces generates the vitriol oil.This processing mode has been avoided the generation of a large amount of gypsum, and the vitriol after the neutralization both can be used as by-product sale simultaneously, also can the vitriol oil that the vitriol electrolysis generates be applied in the method for producing gtitanium dioxide with sulphuric acid once again.Sorry this patent is not mentioned the problem of energy consumption.
Document three: Chinese patent " method of decomposing ammonia sulfate reaches the method (having the right) of reclaim(ed) sulfuric acid from spent acid and acid waste water, application number: the 200910300912.X applying date: 2009-03-17 ".Used raw material CACO 3, ammonia (or ammoniacal liquor) and catalyzer FE 2O 3No consumption in theory can recycle, only need replenish The addition of C ACO when in fact using 3, NH 3And FE 2O 3Get final product, the spent acid and the waste water that produce during for the Processing of Preparation white titanium pigment provide a kind of new method.Because treatment capacity is big, the not fundamentally predicament of elimination environment protection treating.Do not see improved report to May 29 this year yet.
Foreign preclude the use of chlorinated waste discharge less technology, advanced technology, but China Why not engage in titanium oxide powder? Liu Fangbin industry experts Hon-Kit Lau told reporters: "engage in, and too difficult.Import of technique.Blockade on new techniques is done by offshore company, and is not for sale anyway; The exploitation of controlling oneself, domestic strong company developed 20 years, had only done a cover and had produced 1.5 ten thousand tons dingus per year and go into operation, technology can't be equal to external device ".
Liu Fang is refined, and the reporter also reveals, the chloridising device structure is complicated, requires high temperature resistantly, anticorrosive, and oxidation resistant extraordinary village material needs to drop into the equipment that a huge sum of money just can develop commercial value and comes.The problem of titanium resource also influences the introduction of chlorination in addition.Domestic titanium resource exists calcium-magnesium content high, can not remove again in the production, and the titanium dioxide quality does not increase.If imports from abroad, thanks to calcium and magnesium content below 1% Di high titanium slag as raw material, in the Economic Mutual Aid is not competitive.Chlorination process itself has some technical wind premiums, coupled with raw material did not meet the requirements of chlorination of titanium resources, so the large-scale introduction of sulfuric acid chloride instead of immature, not reality.Because homemade titanium resource also is not suitable for introducing chlorination plant, can only use Titanium White Production By Sulfuric Acid Process, but will solve the technical problem of environmental protection.Promptly reduce the high problem of expenses of environmental protection.
Domestic promotion sulfur, iron, titanium dioxide production and cogeneration technology is the development of the recycling industry chain, the "three wastes" is a practical, by Economic feasible solution.But still exist a large amount of waste residue problems not solve.
1 pair of gas and dust, etc., preclude the use of spray washing process and gravity settling equipment and measures to be effective in treatment:
2 titanium dioxide industry generated more than preclude the use of solid slag landfill past, the solid residue and other processing gypsum, although effective, but the volume is difficult to have effective, or even slightly, the solid residue mainly from low concentrations caused by wastewater treatment, so, our principle is to treat waste waste into products, ad infinitum.It is feasible how to let circulation become? Want the treatment of wastes with processes of wastes against one another to become product exactly, product is gone to control again useless, move in circles, fundamentally eliminate harm environment.This is main contents of the present invention places.
Summary of the invention
The purpose of this invention is to provide a kind of sulfuric acid process and produce the method that the acid waste water of white titanium pigment is administered, the treatment of wastes with processes of wastes against one another becomes product, product is gone to control again useless, moves in circles, and does not almost have waste water and waste residue and produces, and significantly useless cost is controlled in reduction.
Technical scheme of the present invention is: sulfuric acid process is produced the method for the acid waste water improvement of white titanium pigment, and it is characterized in that: the employing barium carbonate is a treatment agent, and the circulation process of treatment agent is: barium carbonate → permanent white → barium sulphide → barium carbonate; Barium carbonate is added acid waste water generate the barium sulfate precipitate thing, separate permanent white and water, acid waste water is neutralized with barium carbonate, and water quality reaches environmental requirement after removing vitriol; Again permanent white is reduced to barium sulphide, in barium sulfide solution, feeds carbonic acid gas and generate barium carbonate.
Aforesaid sulfuric acid process is produced the method for the acid waste water improvement of white titanium pigment, and it is characterized in that: barium carbonate is molecule or Powdered or ultrafine powder powder, to increase contact area.Can fast reaction speed, shorten acid adjustment and sulfate radical reaction times.
Aforesaid sulfuric acid process is produced the method for the acid waste water improvement of white titanium pigment, it is characterized in that: add sodium-chlor in acid adjustment and the sulfate radical process and make catalyzer.Can significantly shorten the time of acid adjustment and sulfate radical.Can accelerate the amount that acid adjustment neutralization and the speed of removing the vitriol process just can not add or still less add catalyzer like treatment agent refinement and treatment agent and sour water thorough mixing, purpose is to reduce expenses.
Aforesaid sulfuric acid process is produced the method for the acid waste water improvement of white titanium pigment, and it is characterized in that: the method that permanent white is reduced to barium sulphide is permanent white to be mixed high-temperature roasting with coke.Can accomplish that whole input of all resultants recycles.
Preparation of titanium sulfate as described above, the acidic waste water treatment method characterized in that: preclude the use of a venturi jet pump and fractional precipitation tank, solid-liquid mixture constituting the reaction apparatus.The reaction system for the heterogeneous reaction, for which preclude the use of a venturi jet pump barium carbonate powder was suction pump and the liquid to be treated into the hole in the pump and the pipe full contact, and the barium sulfate in the pipeline and the resultant separation tank (or settling tank) in a timely manner and System detachment.
With the carbon dioxide gas that produces in the reaction process, the stink damp compression is collected, and utilizes during in order to relevant preparation.
Described reduction (permanent white is reduced to barium sulphide) can be a several different methods of the prior art, such as: tiff coal dust reduction method, gas reduction method etc.
Tiff coal dust reduction method:
Tiff and hard coal are pressed tiff: hard coal=100: (25~27); Proportioning is pulverized (below the 5mm) after mixing; At 1000~1200 ℃ of following reducing roasting 1~2h; The thick barium sulphide melt of gained (contain BaS>65%) is through the hot water leaching, and barium sulfide solution concentration reaches about 220 g/L, leaves standstill clarification, filtration, evaporation, crystallization again and makes barium sulfide solution.Its chemical equation:
  BaSO 4+4C→BaS+4CO↑
Cinder after the leaching is discharged after washing, recyclable barium wherein, and its slag can be made non-burning brick, or makes material of construction and use.
The gas reduction method:
Tiff is fed hydrogen (or Sweet natural gas) at 850~900 ℃ carry out reduction reaction, can obtain purified, as not contain coal and ash content barium sulphide melt.
Its chemical equation: BaSO 4+ 4H 2→ BaS+4H 2O
Collect hydrogen sulfide gas, solution is filtered, oven dry detects purity, and the packing warehouse-in is in order to use again.
Whole process does not have useless solid slag and waste liquid, has only consumed reductive agent coke or Sweet natural gas.
Advantage of the present invention is following
1, the treatment agent barium carbonate can recycle repeatedly, and no waste residue does not have waste gypsum to produce, and does not have useless solid slag, has exempted from but freight charges.
2, acidic waste water after treatment at pH 7, total salt TDS <1000mg /> l?, The water did not fish out the soluble Ba 2 + ? Can be directly discharged, Ge reuse, conserve water.
3, the processing costs of 100 tons of acid waste waters will be lower than 800 yuan.
4, this method can preclude the use of a venturi jet pump and fractional precipitation tank, quick response, equipment investment, small footprint.
Embodiment
Sulfuric acid process is produced the method for the acid waste water improvement of white titanium pigment, and it is characterized in that: the employing barium carbonate is a treatment agent, and the circulation process of treatment agent is: barium carbonate → permanent white → barium sulphide → barium carbonate; Barium carbonate is added acid waste water generate the barium sulfate precipitate thing, separate permanent white and water, make acid waste water acid adjustment and sulfate radical reach environmental requirement; Again permanent white is reduced to barium sulphide, in barium sulfide solution, feeds carbonic acid gas and generate barium carbonate.Said barium carbonate can be a synthetic, or mineral composition, can be pure, also can be non-purifying substance.It not only can remove saltcake, the pH value that can also improve or regulate waste liquid.It can also reduce the total salt content in the waste liquid, i.e. TDS.
Aforesaid barium carbonate is molecule or Powdered or ultrafine powder powder.Because barium carbonate slightly soluble and water, thus its surface-area will be strengthened as much as possible, like this can fast reaction speed, shorten acid adjustment and sulfate radical reaction times.
Add sodium-chlor in aforesaid acid adjustment and the sulfate radical process and make catalyzer.Because the surface of barium carbonate possibly have thin permanent white layer originally; Or the surface has generated thin permanent white layer after still not joining the lower concentration sour water originally; The permanent white layer that should approach can hinder inner barium carbonate and participate in reaction, with the permanent white layer that sodium-chlor can be decorporated thin, added catalyzer and can see obviously that gas occurring satisfies; Be swift in response, thereby can significantly shorten time of acid adjustment and sulfate radical.
The method that aforesaid permanent white is reduced to barium sulphide is permanent white to be mixed high-temperature roasting with coke.Though prior art has multiple reductive method, be to use present method can accomplish that whole input of all resultants recycles, make factory need not produce and manage numerous products, reduce and produce and handling cost.
Preclude the use of a venturi jet pump and fractional precipitation tank, solid-liquid mixture constituting the reaction apparatus.The reaction system for the heterogeneous reaction, for which preclude the use of a venturi jet pump barium carbonate powder was suction pump and the liquid to be treated into the hole in the pump and the pipe full contact, and the barium sulfate in the pipeline and the resultant separation tank (or settling tank) in a timely manner and System detachment.
Concrete step is following:
A utilizes pulverous brium carbonate to be inorganic agent and little amount of catalyst sodium chloride; Both mix the back and are composite treating agent; The amount of catalyst sodium chloride depends on the circumstances, and the amount of catalyst sodium chloride is 1,/00 to 1/0,000 of a brium carbonate amount; Use the Venturi tube hybrid mode, use amount is ten thousand/several, if not then consumption is just bigger.
B. acid adjustment and sulfate radical: about 2 times of amounts of composite treating agent by the sulfuric acid quality are added in the waste liquid that is processed gradually, add in the waste liquid that is processed; Continuous observation pH value when near 7 the time, slows down the speed and the amount that add composite treating agent, fully stirs, and deposition leaves standstill, and shifts out clear liquid, and detection has sulfate radical-free; Catalyzer can mix earlier then with treatment agent and add, and also can both separately add, and can also add catalyzer after a while;
C. separate: filter with strainer, and the dilute acid wash throw out is dried promptly to get and precipitated product permanent white to there not being cl ions;
D. circulation: permanent white is made the treatment agent barium carbonate---permanent white and coke are mixed, reduction at a certain temperature, the product barium sulphide after the reduction is water-soluble, in barium sulfide solution, feeds dioxide gas, promptly gets the treatment agent barium carbonate.
Whole process has only consumed coke.
Being processed waste water contains: H 2SO 4, micro ion: Fe, Mg, Ca etc.
Its main chemical reactions principle is following:
Acid adjustment and sulfate radical: BaCO 3+ H 2SO 4→ BaSO 4 + H 2O+CO 2↑ (1)
BaCO 3+2H + →Ba +++?H 2O+CO 2↑ ?(1.1)
Ba +++SO 4 2- →BaSO 4? ↓ ?(1.2)
Circulation BaSO4+C → BaS+CO2 ↑ (3 )
BaS+CO 2+H 2O?→?BaCO 3? +H 2S↑ (4)
In the process of acid adjustment and sulfate radical, carbonate CO 3 2-Simultaneously also with Fe + 2, Mg + 2, Ca + 2Deng reacting, with its removal.
Embodiment
One, gets 1 kg treatment agent barium carbonate, 1g catalyzer sodium-chlor; Both mix the back and are composite treating agent;
Two, get the acid white titanium pigment waste water of lower concentration 1kg, record wherein that sulfuric acid content is 2% (sulfur acid 20g),, mix with the Venturi squirt pump to wherein progressively adding about 40g composite treating agent; The pH value rises to 7 gradually from 1, continues to stir, and gets clear liquid 2ml in centrifuge tube, with the analytical pure bariumchloride liquid that contains 1% hydrochloric acid; Drip 1-2 and drip, observation has or not white precipitate, then continues to add composite treating agent if having, and stirs; Otherwise, then stop to stir, clear liquid is emitted.
Three, the clear liquid testing result is following
PH=7 TDS=1.1 * 10 3Mg/l TDS clearance reaches 95%
Sulfate radical does not detect.Calcium, the magnesium amount also reduces many, and this water can directly discharge, or reuse.
Four, throw out (being permanent white) is cleaned oven dry.
Spent acid [1% concentration] in producing is soaked throw out (permanent white), fully stir, filter, wash till the white oven dry.
Till detecting no chlorine and leave with the 1% nitre silver solution that contains nitric acid, dry.
Five, circulation (preparation barium carbonate)
Coke is mixed with permanent white 1 to 1 quality, place 900--1000 degree centigrade of stove calcination reduction, the cooling back is soluble in water, removes by filter insolubles, in clear liquid, feeds CO 2Gas, promptly adularescent deposition generates, and this thing is barium carbonate, adds a small amount of (barium carbonate 1,/00 to 1/0,000) catalyzer in the barium carbonate, is composite treating agent.The H that is produced 2The oxidable vitriolic raw material of doing of S gas is used for production process of titanium pigment, and all products are recycled all.H 2S gas also can be done other purposes, as producing coating zinc sulfide white.
Titanium dioxide industry pollution is serious, the key is to deal with a large amount of sulfuric acid present invention patents for the production of titanium dioxide produced by a large number of wastewater treatment and proposed, particularly preclude the use of the waste water treatment agent (also known as saltpeter agent addition) Barium Carbonate it Ji can neutralize acid, adjusting the pH value; they can in addition to nitrate [ie sulfate sulfate] to remove one of the sulfate or sulfate (or known except NOx), the resulting "waste" turn it into for the next addition to sulfate or sulfate (or known except nitrate) treatment agent barium carbonate, cycle, cycle to clean production, virtually no solid residue.The chemistry subject and the chemical engineering science of the mystery that research material composition and structure and material transform are administered the efficient and low consumption of white titanium pigment waste water, are about to let white titanium pigment enterprise walk out the predicament of environment refractory reason!
The present invention also can be used for bittern and remove nitre and chlor-alkali industry except that nitre.
The present invention also can be used for the nitre that removes of drinking water modestly in the arid and semi-arid lands.

Claims (6)

1. sulfuric acid process is produced the method for the acid waste water improvement of white titanium pigment, and it is characterized in that: the employing barium carbonate is a treatment agent, and the circulation process of treatment agent is: barium carbonate → permanent white → barium sulphide → barium carbonate; Barium carbonate is added acid waste water generate the barium sulfate precipitate thing, separate permanent white and water, make acid waste water acid adjustment and sulfate radical reach environmental requirement; Again permanent white is reduced to barium sulphide, in barium sulfide solution, feeds carbonic acid gas and generate barium carbonate.
2. sulfuric acid process as claimed in claim 1 is produced the method for the acid waste water improvement of white titanium pigment, and it is characterized in that: barium carbonate is molecule or Powdered or ultrafine powder powder.
3. according to claim 1 or claim 2 sulfuric acid process is produced the method that the acid waste water of white titanium pigment is administered, and it is characterized in that: adding sodium-chlor is made catalyzer in acid adjustment and the sulfate radical process.
4. according to claim 1 or claim 2 sulfuric acid process is produced the method that the acid waste water of white titanium pigment is administered, and it is characterized in that: the method that permanent white is reduced to barium sulphide is permanent white to be mixed high-temperature roasting with coke.
5. sulfuric acid process as claimed in claim 3 is produced the method for the acid waste water improvement of white titanium pigment, and it is characterized in that: the method that permanent white is reduced to barium sulphide is permanent white to be mixed high-temperature roasting with coke.
As claimed in claim 3, wherein said titanium dioxide Preparation of sulfuric acid waste treatment method, characterized in that: preclude the use of a venturi jet pump and fractional precipitation tank, solid-liquid mixture constituting the reaction apparatus.
CN2012102956241A 2012-08-16 2012-08-16 Method for treating acidic waste water from titanium dioxide preparation by sulfuric acid method Pending CN102795701A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103663536A (en) * 2013-09-28 2014-03-26 赵同甫 Process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide
CN109012566A (en) * 2018-09-18 2018-12-18 渤海大学 The preparation method of secondary chlorine white clay foundation stone oil Organic Pollutants in Wastewater removal material
CN109264744A (en) * 2018-10-19 2019-01-25 湖南雅城新材料有限公司 A kind of recovery method as resource of low cost ferric phosphate nitrogen-containing wastewater

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1381406A (en) * 2001-04-18 2002-11-27 宋康尧 Process for using barium carbonate to treat high-content slfuric acid radicals in saline
CN1473760A (en) * 2003-07-01 2004-02-11 沈阳化工股份有限公司 Method for removing sulfuric radical from brine with barium carbonate
CN1752010A (en) * 2005-07-15 2006-03-29 陆巧芳 Method of producing barium sulfide and flue gas by calcining coal and barite to synthesize barium carbonate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1381406A (en) * 2001-04-18 2002-11-27 宋康尧 Process for using barium carbonate to treat high-content slfuric acid radicals in saline
CN1473760A (en) * 2003-07-01 2004-02-11 沈阳化工股份有限公司 Method for removing sulfuric radical from brine with barium carbonate
CN1752010A (en) * 2005-07-15 2006-03-29 陆巧芳 Method of producing barium sulfide and flue gas by calcining coal and barite to synthesize barium carbonate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103663536A (en) * 2013-09-28 2014-03-26 赵同甫 Process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide
CN109012566A (en) * 2018-09-18 2018-12-18 渤海大学 The preparation method of secondary chlorine white clay foundation stone oil Organic Pollutants in Wastewater removal material
CN109012566B (en) * 2018-09-18 2021-08-06 渤海大学 Preparation method of material for removing organic pollutants in hypochlorous white mud based petroleum wastewater
CN109264744A (en) * 2018-10-19 2019-01-25 湖南雅城新材料有限公司 A kind of recovery method as resource of low cost ferric phosphate nitrogen-containing wastewater

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Application publication date: 20121128