AU6794498A - Continuous non-polluting liquid phase titanium dioxide process - Google Patents
Continuous non-polluting liquid phase titanium dioxide process Download PDFInfo
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- AU6794498A AU6794498A AU67944/98A AU6794498A AU6794498A AU 6794498 A AU6794498 A AU 6794498A AU 67944/98 A AU67944/98 A AU 67944/98A AU 6794498 A AU6794498 A AU 6794498A AU 6794498 A AU6794498 A AU 6794498A
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- Australia
- Prior art keywords
- filtrate
- filter cake
- titanium dioxide
- water
- titanium
- Prior art date
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 37
- 239000004408 titanium dioxide Substances 0.000 title claims description 14
- 239000007791 liquid phase Substances 0.000 title claims description 5
- 239000002253 acid Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- 239000012065 filter cake Substances 0.000 claims description 42
- 239000000706 filtrate Substances 0.000 claims description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 31
- 239000002893 slag Substances 0.000 claims description 29
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 24
- 230000007062 hydrolysis Effects 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- 239000000049 pigment Substances 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 claims description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 11
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002198 insoluble material Substances 0.000 claims description 8
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical group O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 11
- 238000010924 continuous production Methods 0.000 claims 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical class [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- AKMXMQQXGXKHAN-UHFFFAOYSA-N titanium;hydrate Chemical compound O.[Ti] AKMXMQQXGXKHAN-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
WO 98/54095 PCT/US98/06499 1 CONTINUOUS NON-POLLUTING LIQUID PHASE TITANIUM DIOXIDE PROCESS Background 5 There are two types of titanium dioxide pigments; both have a tetragonal crystal form. One crystal form is anatase (a soft crystal), and the other is rutile (a hard crystal). Anatase, which comprises nearly half of the market, is used in the paper, textile fiber and plastic industries where a soft pigment will not wear away the cutting knives, extruders and injection equipment. The sulfate process is amenable to the manufacture 10 of anatase pigments. The vapor phase chloride process is limited to the production of rutile. The prior process employing sulfates produced a large amount of pollution. Development of this new process eliminates most of the pollution. For a better understanding of the invention, this sulfate process is described. 15 Drying and Grinding Ilmenite ore or titanium slag (containing 1 to 5% humidity as received in a plant) is first dried to 0.3% humidity. It is then ground to from an average of 80 to 98% minus 200 mesh. 20 Digestion A typical Ilmenite digestion reacted at 85% reaction acid is described as follows. 71,000 pounds of 660 Baum6 sulfuric acid are charged into a reactor, and air agitation is started. 45,000 pounds of Ilmenite ground ore are slowly added (over 30 minutes), and then 6700 pounds of acceleration water are added. A reaction starts at from 950 to 25 105 0 C, and the temperature in the reactor rises rapidly from 1200 to 200 0 C with the evolution of 10,000 to 12,000 pounds of steam (with entrained acids), which is vented to the atmosphere, causing so-called acid rain, the reaction is often violent, emptying to the atmosphere with explosive force. When the reaction is complete, the resulting porous mass is allowed to cool, and water is added to dissolve soluble iron and titanium sulfates. 30 Metallic iron is added to reduce any ferric sulfate formed, and the thus-obtained slurry (suspension) is pumped to settling tanks. This operation takes from about 12 to 24 hours.
WO 98/54095 PCT/US98/06499 2 Settling and Washing Due to the presence of rutile in the ground ore, gangue minerals and colloids (mostly silica gel formed when digesting ore or slag) the suspension cannot be filtered directly, and it is pumped to settling tanks where the clear supernatant liquor and settled 5 solids (mud) are obtained. The settled solids are again dispersed and washed counter currently in a series of settling tanks to recover a maximum amount of titanium sulfate. The number of required tanks and their size take considerable land and entail significant cost. 10 Filtration The combined clear settled liquors from the first settlers (together with leach liquor) are filtered and led to a vacuum evaporator (when using ilmenite ore) or directly to a hydrolysis process (when using slag, which contains less iron). Evaporation under vacuum at temperatures below 60 0 C is necessary to prevent 15 premature hydrolysis. Copperas from a vacuum evaporator crystallizer is filtered, washed and dumped to sewage or sold. A typical analysis of the concentrated filtered solution ready for hydrolysis is: Analyis Typical Value Sp. Gr. 1.620 at 60 0 C 20 % TiO 2 15.4 % FeSO 4 10.8 % H 2
SO
4 27.7 Hydrolysis 25 The solution is then heated to a temperature of 960 C, and hydrolysis is started by pumping part of the liquor into 96 0 C hot water (about of the liquor volume) over a period of 16 minutes. The mixture is then brought to a boil (102 0 C to 108 0 C). Boiling is continued until about 96% of the titanium is recovered. The resulting suspension is led to a series of counter-current filter arrangements 30 (e.g., Moore filters), in which the titanium hydrate is separated and washed. The resulting solution (containing weak sulfuric acid) is discharged to sewage.
WO 98/54095 PCT/US98/06499 3 The preceding process causes significant pollution, which is the reason why it is being abolished in all industrialized countries. Summary of the Invention 5 A prime purpose of the present invention is to use a series of novel steps which prevent pollution and establish a more economical sulfate process which can produce anatase (required in the paper, textile fiber, and plastic industries) and rutile (for paints, etc.). An object of the invention is to eliminate acid rain, overflow of effluent to water 10 ways and injection of effluents into the ground. Another object is conservation of water. A further object is efficient heat balance management. Still further objects are apparent from the following description. The process does not require drying or grinding ore or slag, thus eliminating costly equipment and labor. Unground wet ilmenite ore as delivered, containing from 1 15 to 5% H20, or titanium slag is continuously fed to a reactor with from 65 to 85% hot sulfuric acid (121'C to 200 0 C) in sufficient quantity to keep the resulting slurry liquid (3 to 8/1 sulfuric acid to ore ratio, depending on acid concentration, which can oscillate between 65% and 85%). The reaction is very rapid, breaking large particles into a fine suspension, and agitation is provided either mechanically or with air spargers. The 20 reactor is made of sufficient size so that retention time (which is in the order of from 2 to 8 hours) of the ore or slag and acid is sufficient to digest 90% of the TiO 2 . The reacted slurry is then continuously fed to a vacuum filter instead of the first spray dryer as depicted in antecedent patent application Serial No. 08/645,344. (Filtration produces about a 4 to 1 acid to TiO 2 ratio. As a result a spray drying 25 technique was previously developed to evaporate the excess acid back to a 2/1 acid to TiO 2 ratio). The use of a water wash to remove the excess acid was not generally considered because the titanyl cake is water soluble. However, it has been found that dissolution of titanyl sulfate is not rapid and a displacement wash of water (slightly acidified) does in 30 fact remove excess acid without removing much titanium dioxide. This has now become the preferred process, and one of the advantages is that the displacement wash yields strong acid which can be recycled back to the reactor.
WO 98/54095 PCT/US98/06499 4 Acid strength can be from 55 to 85%; 65% is preferred because it has a minimum solubility of salts. When iron is left in the oxidized state, it appears to be removed to some extent from the raw cake by the washing procedure. The ability to recycle acid directly back to the reactor makes it possible to 5 decouple the spray drier for the Moore acid recycle from the reactor loop, and it is only used to concentrate dilute 25% acid. The acid from the Moore filter and the above slurry wash contains all the iron sulfate coming from the system. Since ferrous sulfate is insoluble in concentrated sulfuric acid, it is removed by filtration after being concentrated by evaporation in the sole spray 10 drier, and the acid is re-circulated to the reactor. The gases from the reactor and from the sole spray drier (containing mostly water vapor and some acid) are condensed and used to wash the cake. In this manner more than 97% of the acid is recovered at this point. The cake (containing titanyl sulfate, ferrous sulfate, ferric sulfate and insolubilized 15 colloids) from the reactor filter is partially dissolved in acid water from condensers, taking care not to exceed a temperature of 60 0 C, preventing premature hydrolysis. Reducing agent is added to reduce the iron to the 2 valent state and to put 3 grams per liter of the titanium to the 3 valent state. The resulting suspension is then filtered in a rotary filter with pre-coat and filter aid. The obtained filter cake is washed and discarded 20 after proper neutralization. Obtained filtrate is then conducted to a hydrolysis department, where it is hydrolyzed, without first removing copperas (ferrous sulfate), to produce titanium oxide hydrate. The resulting suspension is filtered to obtain filter cake. The washed filter cake (titanium dioxide hydrate) is chemically treated with a precalcination addition of 25 chemicals and calcined in a fluidized calciner at a temperature around 925 0 C to 980 0 C to form anatase, which is cooled, ground and packed. Hot gases from the fluidizer, containing sulfuric acid and some titanium dioxide, are recycled to the sole spray dryer, which absorbs the acid and any SO 3 formed and evaporates the water. (Note that the sole spray dryer is really an evaporator). 30 There are a number of distinct aspects to the subject invention, each of which comprises process steps or equipment supporting such steps. Several of the aspects (in process terms) are as follows: WO 98/54095 PCT/US98/06499 5 a) reacting titanium ore or slag with hot sulfuric acid, separating out filter cake of titanyl sulfate from the resulting reaction product, combining the cake with acid water to form a partially dissolved product as a suspension, filtering the suspension, hydrolyzing the thus-obtained filtrate to convert titanium dioxide 5 hydrate, and calcining the titanium dioxide hydrate to obtain anatase pigment; b) using hot gases from the calcining means to evaporate the solutions obtained from the reaction of titanium ore or slag with hot sulfuric acid from hydrolysis; c) recycling hot gases (containing sulfuric acid) from the calcine and wash water from titanium dioxide hydrate filtering means to spray dryer means for producing 10 ferrous sulfate monohydrate and for producing acid water for partially dissolving free-flowing solids from the reaction product of titanium ore or slag with hot sulfuric acid; and d) recycling filtrate (hot concentrated sulfuric acid) from ferrous sulfate monohydrate filtering means to the reactor means for reacting titanium ore or 15 slag with hot sulfuric acid. Brief Description of the Drawing Figure 1 is a schematic presentation of the process and equipment suitable for the invention. 20 Details Raw material, e.g., pre-oxidized slag or Ilmenite, is fed through line (2) to reactor (1). Hot gas is fed through line (4) to provide agitation by means of a Pachuca tube (5). Acid is fed through line (3) with make up acid from line (6). Together with recovered 25 acid from the spray evaporator (34), reacted product (containing titanyl sulfate, iron sulfate and other sulfates) overflows from reactor (1) through line (7) to rotary filter (8). Obtained filter cake is given a displacement wash on rotary filter (8), whose water comes in through line (14). The washed filter cake is delivered through line (9) to dissolving tank (10). Concentrated acid from rotary filter (8), together with displacement wash, is 30 returned to reactor (1) through line (3), which also receives make-up concentrated acid through line (6). Steam, together with some acid formed during reaction in reactor (1), is led through line (11) to condenser (12), and from condenser (12) through line (13) to WO 98/54095 PCT/US98/06499 6 dissolving tank (10). Additional water containing acid from condenser (41) is led through line (15) to dissolving tank (10). Reducing material (iron, aluminum) is added to dissolving tank (10), together with insoluble materials, through line (16) to filter (17). Clear filtrate from filter (17) is led through line (18) to pre-heater (19), and from pre 5 heater (19) through line (20) to hydrolysis tank (21). Unreacted ore and insoluble material is delivered from filter (17) through line (22) to waste. Hot liquor from pre heater (19) is then introduced through line (20) to hydrolysis tank (21), in which it reacts with hot water from line (24), which has been previously introduced to seed and start hydrolysis. The resulting mixture is then brought to a boil, using live steam transmitted 10 through line (25). After hydrolysis, the obtained titanium dioxide hydrate flows through line (26) to Moore filters (27). Filter cake from Moore filters (27) is delivered through line (29) to fluid bed calciner (30), where it meets hot gases from line (31). Calcined titanium dioxide is delivered through line (39) to coolers, packing, and grinding, not shown. Gases flow from cyclone (32) through line (33) to spray drier (34) through line 15 (35) to filter (36). Insoluble ferrous sulfate monohydrate from filter (36) is delivered through line (37) to washing, drying and packing, not shown. Concentrated acid is led through line (42) to line (3) and thus delivered back to reactor (1). Steam [with some acid from spray drier (34)] is led through line (40) to condenser (41). Water [with some acid from condenser (41)] is led to dissolving tank (10) through line (15). 20 Example Beach sand and 65% sulfuric acid are added into a reactor with an acid to ore ratio of from 5:1 to 7:1. The resulting admixture is heated to 180 0 C and agitated for 8 hours. 25 The reacted ore slurry is discharged into a filter, and a vacuum of-28mm Hg is pulled to separate excess fluid. The filtrate is 57.3% acid, 7.8% Fe 2
(SO
4
)
3 , 0.4% TiO 2 . Thus-obtained filter cake is washed with 2% acidified water. The filtrate contains 40.65% acid, 1.79% TiO 2 and 9.1% Fe(SO4) 3 . The cake contains 16.2% TiO 2 , 12.7% Fe 2
(SO
4
)
3 and 33% acid, giving a 2.0 to 30 1.0 acid to TiO 2 ratio.
WO 98/54095 PCT/US98/06499 7 Acidified water (4% acid) is added to the cake to dissolve it. Aluminum powder is added to reduce the resulting solution and produce 2 grams per liter of reduced TiO 2 . The solution is heated to 50 0 C to promote the dissolving. Insoluble solids are separated from the thus-obtained product by means of a filter, 5 washed and dumped. The filtrate contains 14.3% TiO 2 , 4.4% FeSO 4 , and 26.5% sulfuric acid, giving a 1.9 acid to TiO 2 ratio. The solution (filtrate) and a weighed amount of water are preheated. The resulting hot solution is fed into hot water in the hydrolysis tank. The mixture is brought 10 to a boil. After hydrolysis the obtained TiO 2 hydrate is filtered and washed. The obtained filter cake is treated for calcination and calcined at from 925 0 C to 980 0 C to obtain the desired pigment quality. The invention and its advantages are readily understood from the foregoing description. It is apparent that various changes may be made in the process and 15 apparatus without departing from the spirit and scope of the invention or sacrificing its material advantages. The process and apparatus hereinbefore described are merely illustrative of preferred embodiments of the invention.
Claims (14)
1. A non-polluting liquid-phase process for producing titanium dioxide pigment from titanium ore or slag which comprises the following steps: a) reacting the ore or slag with sulfuric acid to obtain a solid-form reaction product, 5 b) wash-filtering the reaction product with wash water to obtain filter cake and filtrate comprising used wash water, c) recycling the filtrate to step (a), d) separating out and recovering, in aqueous solution, water-soluble components of the filter cake, 10 e) subjecting the water-soluble components, in solution, to hydrolysis to convert titanium values therein to titanium dioxide hydrate, and f) calcining the titanium dioxide hydrate to obtain titanium dioxide pigment.
2. A process of claim 1 which comprises the following steps: 15 g) dissolving in water water-soluble components of the filter cake obtained in step (b), h) filtering the product of step (g) to obtain a clear filtrate, i) hydrolyzing the clear filtrate to obtain titanium dioxide hydrate, j) filtering the product of step (i) to obtain a further filter cake, and 20 k) calcining the further filter cake to obtain calcined titanium dioxide.
3. A process of claim 1 for converting titanium ore or slag to anatase pigment, which process is a continuous process comprising the following steps: a) reacting the ore or slag with sulfuric acid to obtain, as a reaction product, titanyl 25 sulfate, iron sulfate and other sulfates, b) filtering and washing the reaction product to obtain a washed filter cake, filtrate and used wash water, c) recycling the filtrate and used wash water to step (a), d) dissolving in water water-soluble components, comprising titanyl sulfate, iron 30 sulfate and other water-soluble sulfates, of the washed filter cake, e) filtering the product of step (d) to obtain a clear filtrate, f) hydrolyzing the clear filtrate to obtain titanium dioxide hydrate, and WO 98/54095 PCT/US98/06499 9 g) calcining the titanium dioxide hydrate to obtain titanium dioxide pigment.
4. A process of claim 3 wherein titanium ore is reacted in step (a).
5 5. A process of claim 4 wherein the titanium ore is ilmenite.
6. A process of claim 3 wherein preoxidized titanium slag is reacted in step (a). 10
7. Apparatus for converting titanium ore or slag to anatase pigment, which apparatus comprises: a) reactor means to react the titanium ore or slag with sulfuric acid and to obtain a reaction product comprising titanyl sulfate, iron sulfate and other sulfates, b) means to introduce the ore or slag into the reactor means; 15 c) means to introduce the sulfuric acid into the reactor means, d) means to agitate reacting components within the reactor means, e) first filter means to obtain filter cake and filtrate from the reaction product, f) means to conduct the reaction product from the reactor means to the first filter means; 20 g) means to wash the filter cake with wash water and to obtain washed filter cake and used wash water, h) means to recycle filtrate from first filter means (e) and the used wash water to reactor means (a), i) dissolving tank means to place in aqueous solution water-soluble components, 25 including titanium values, of the washed filter cake, the aqueous solution further comprising, undissolved, insoluble material, j) means to conduct the washed filter cake to the dissolving tank means, k) means to conduct water to the dissolving tank means, 1) first separator means to separate the aqueous solution from the insoluble material 30 obtained from the dissolving tank means, m) hydrolysis tank means to hydrolyze dissolved titanium values in said last-noted aqueous solution to obtain titanium dioxide hydrate, WO 98/54095 PCT/US98/06499 10 n) means to conduct the aqueous solution, free from insoluble material, from the first separator means to the hydrolysis tank means, o) second filter means to separate obtained titanium dioxide hydrate from filtrate, p) means to conduct product from the hydrolysis tank means to the second filter 5 means, q) calciner means to convert the titanium dioxide hydrate to anatase pigment, and r) means to conduct titanium dioxide hydrate from the second filter means to the calciner means. 10
8. Apparatus of claim 7 further comprising: s) spray-drier means, t) means to conduct gas from the calciner means to the spray-drier means, u) means to conduct filtrate from the second filter means to the spray-drier means, v) second separator means, 15 w) means to conduct concentrated acid containing ferrous sulfate monohydrate to the second separator means, x) means to withdraw insoluble ferrous sulfate monohydrate from the second separator means, and y) means to conduct concentrated acid from the second separator means to reactor 20 means (a).
9. Apparatus according to claim 8 wherein means (k) comprises means to conduct steam together with some acid formed in reactor means (a) and means to conduct steam and some acid from spray-drier means (s) to the dissolving tank means. 25
10. A process of claim 1 for converting titanium ore or slag to anatase pigment which comprises the following steps: a) reacting the titanium ore or slag with sulfuric acid, under agitation, to obtain a reaction product comprising titanyl sulfate, iron sulfate and other sulfates, 30 b) filtering the reaction product to obtain filter cake and filtrate, c) washing the filter cake with wash water to obtain washed filter cake and used wash water, WO 98/54095 PCT/US98/06499 11 d) recycling the filtrate and the used wash water to step (a), e) dissolving in water water-soluble components, including titanium values of the washed filter cake, the resulting aqueous solution further comprising, undissolved, insoluble material, 5 f) separating the aqueous solution from the insoluble material, g) hydrolyzing dissolved titanium values in the aqueous solution to obtain titanium dioxide hydrate, h) filtering obtained titanium dioxide hydrate from filtrate, which contains acid and ferrous sulfate monohydrate, 10 i) calcining the titanium dioxide hydrate to convert it to anatase pigment, j) conducting heat and gas from step (i) to step (k), k) spray-drying the filtrate, which contains acid and ferrous sulfate monohydrate, to obtain concentrated acid, insoluble ferrous sulfate monohydrate and steam, 1) recycling the concentrated acid to step (a), 15 m) recycling the steam, containing some acid, to step (c), and n) conducting steam and some acid produced in step (a) to step (c).
11. A non-polluting liquid-phase process for producing titanium dioxide pigment from titanium ore or slag which comprises the following steps: 20 a) reacting titanium ore or slag with hot sulfuric acid to obtain a reaction product, b) filtering the reaction product to separate filter cake of titanyl sulfate from the reaction product, c) combining the filter cake with acid water to form a partially-dissolved product as a suspension, 25 d) filtering the suspension to obtain filtrate thereof, e) hydrolyzing the filtrate to convert titanium values therein to titanium dioxide hydrate, and f) calcining the titanium dioxide hydrate to obtain hot gases and anatase pigment. 30
12. A process of claim 11 which comprises filtering the product of step (e) to obtain a further filtrate and filter cake, and using the hot gases (containing sulfuric acid) from step (f) to evaporate liquid from the further filtrate. WO 98/54095 PCT/US98/06499 12
13. A process of claim 12 which comprises washing the further filter cake to obtain washed filter cake and used wash water, recycling the hot gases from step (f) and used wash water to spray dryer (evaporator) means for producing ferrous sulfate monohydrate and acid water, and using the acid water in step (c). 5
14. A process of claim 13 which comprises filtering the ferrous sulfate monohydrate from the acid water to obtain hot concentrated sulfuric acid filtrate, and recycling the hot concentrated sulfuric acid filtrate to step (a). WO 98/54095 PCT/US98/06499 13 AMENDED CLAIMS [received by the International Bureau on 5 August 1998 (05.08.98); original claims 1, 2 and 10 amended; remaining claims unchanged (2 pages)] WHAT IS CLAIMED IS: 1. A non-polluting liquid-phase process for producing titanium dioxide pigment from titanium ore or slag which comprises the following steps: a) reacting the ore or slag with sufficient sulfuric acid to obtain a liquid slurry reaction 5 product, b) filtering the reaction product to obtain a filter cake, c) wash-filtering the filter cake with wash water to obtain a further filter cake and filtrate comprising used wash water, d) recycling the filtrate to step (a), 10 e) separating out and recovering, in aqueous solution, water soluble components of the filter cake, f) subjecting the water-soluble components, in solution, to hydrolysis to convert titanium values therein to titanium dioxide hydrate, and g) calcining the titanium dioxide hydrate to obtain titanium 15 dioxide pigment. 2. A process of claim 1 wherein step (c) comprises g) dissolving in water water-soluble components of the filter cake obtained in step (b), and the process further comprises: 20 h) filtering the product of step (c) to obtain a clear filtrate, i) hydrolyzing the clear filtrate to obtain titanium dioxide hydrate, j) filtering the product of step (i) to obtain a further filter cake, and k) calcining the further filter cake to obtain calcined titanium dioxide. 25 3. A process of claim 1 for converting titanium ore or slag to anatase pigment, which process is a continuous process comprising the following steps: a) reacting the ore or slag with sulfuric acid to obtain, as a reaction product, titanyl sulfate, iron sulfate and other sulfates, b) filtering and washing the reaction product to obtain a washed filter cake, filtrate and 30 used wash water, c) recycling the filtrate and used wash water to step (a), d) dissolving in water water-soluble components, comprising titanyl sulfate, iron sulfate and other water-soluble sulfates, of the washed filter cake, e) filtering the product of step (d) to obtain a clear filtrate, 35 f) hydrolyzing the clear filtrate to obtain titanium dioxide hydrate, and AMENDED SHEET (ARTICLE 19) WO 98/54095 PCT/US98/06499 14 n) means to conduct the aqueous solution, free from insoluble material, from the first separator means to the hydrolysis tank means, o) second filter means to separate obtained titanium dioxide hydrate from filtrate, 5 p) means to conduct product from the hydrolysis tank means to the second filter means, q) calciner means to convert the titanium dioxide hydrate to anatase pigment, and r) means to conduct titanium dioxide hydrate from the second filter means to the calciner means. 10 8. Apparatus of claim 7 further comprising: s) spray-drier means, t) means to conduct gas from the calciner means to the spray-drier means, u) means to conduct filtrate from the second filter means to the spray-drier means, v) second separator means, 15 w) means to conduct concentrated acid containing ferrous sulfate monohydrate to the second separator means, x) means to withdraw insoluble ferrous sulfate monohydrate from the second separator means, and y) means to conduct concentrated acid from the second separator means to reactor 20 means (a). 9. Apparatus according to claim 8 wherein means (k) comprises means to conduct steam together with some acid formed in reactor means (a) and means to conduct steam and some acid from spray-drier means (s) to the dissolving tank means. 25 10. A process of claim 1 for converting titanium ore or slag to anatase pigment which comprises the following steps: a) reacting the titanium ore or slag with excess sulfuric acid, under agitation, to obtain a reaction product comprising titanyl sulfate, iron sulfate and other sulfates, 30 b) filtering the reaction product to obtain filter cake and filtrate, c) washing the filter cake with wash water to obtain washed filter cake and used wash water, AMENDED SHEET (ARTICLE 19)
Applications Claiming Priority (7)
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| US87623497A | 1997-06-16 | 1997-06-16 | |
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| US08/917941 | 1997-08-22 | ||
| US08/917,941 US6048505A (en) | 1997-06-16 | 1997-08-22 | Continuous non-polluting liquid phase titanium dioxide process and apparatus |
| PCT/US1998/006499 WO1998054095A1 (en) | 1997-05-30 | 1998-04-01 | Continuous non-polluting liquid phase titanium dioxide process |
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| AU67944/98A Ceased AU744330B2 (en) | 1997-05-30 | 1998-04-01 | Continuous non-polluting liquid phase titanium dioxide process |
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| CN (1) | CN1165488C (en) |
| AU (1) | AU744330B2 (en) |
| CA (1) | CA2323671A1 (en) |
| WO (1) | WO1998054095A1 (en) |
| YU (1) | YU72299A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321889A (en) * | 2020-11-04 | 2021-02-05 | 沪本新材料科技（上海）有限公司 | Manufacturing process of liquid titanium dioxide for PVC plastic production |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10332530A1 (en) * | 2003-07-17 | 2005-02-10 | Kerr-Mcgee Pigments Gmbh | Process for reducing the soluble chromate content in cement and a preparation of cement and water-soluble metal sulphates |
| CN101553585B (en) * | 2006-09-06 | 2012-05-30 | Bhp比利顿创新公司 | A sulfate process |
| WO2010034083A1 (en) * | 2008-09-29 | 2010-04-01 | Bhp Billiton Innovation Pty Ltd | A sulfate process |
| CN101723448B (en) * | 2009-12-29 | 2013-11-06 | 攀钢集团研究院有限公司 | Method for preparing titaniferous solution |
| CN101898791B (en) * | 2010-06-25 | 2012-10-03 | 四川龙蟒钛业股份有限公司 | Method for preparing rutile titanium dioxide from new process titanium slag |
| CN102560117A (en) * | 2011-11-23 | 2012-07-11 | 王景峰 | Method for recovering titanium dioxide and nickel sulfate from multilayer capacitance wastes |
| EP2623564A1 (en) * | 2012-02-03 | 2013-08-07 | Omya International AG | Installation for the purification of minerals, pigments and/or fillers and/or the preparation of precipitated earth alkali carbonate |
| CN103145181B (en) * | 2013-04-02 | 2014-12-03 | 宜宾天原集团股份有限公司 | Three-phase fluidized continuous reaction device for preparing rutile by hydrochloric acid leaching method |
| EP3257816A1 (en) * | 2016-06-14 | 2017-12-20 | Kronos International, Inc. | Production of nano-particulate titanium dioxide |
| EA037945B1 (en) * | 2017-03-02 | 2021-06-10 | Метсо Ототек Финланд Ой | Method for treating titanium-containing slag |
| CN107649089A (en) * | 2017-10-26 | 2018-02-02 | 攀钢集团攀枝花钢铁研究院有限公司 | The reactor of production sulfuric acid titaniferous compound is reacted for process intensification continuous acidolysis |
| CN112624189B (en) * | 2021-01-14 | 2023-03-28 | 上海安赐环保科技股份有限公司 | Method and system for recycling waste acid and white water of titanium dioxide produced by sulfuric acid process |
| CN115367795B (en) * | 2022-09-01 | 2024-02-20 | 山东东佳集团股份有限公司 | Novel process for preparing ammonium sulfate by recycling catalyst titanium dioxide washing liquid in acid-making tail gas system |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2774650A (en) * | 1953-05-01 | 1956-12-18 | Nat Lead Co | Method for decomposition of titaniferous ores |
| US4038363A (en) * | 1975-10-21 | 1977-07-26 | Quebec Iron & Titanium Corporation-Fer Et Titane Due Quebec, Inc. | Upgrading sorelslag for production of synthetic rutile |
| US4288418A (en) * | 1979-08-10 | 1981-09-08 | Nl Industries, Inc. | Process for manufacturing titanium dioxide |
| US4505886A (en) * | 1983-07-01 | 1985-03-19 | Nl Industries, Inc. | Process for preparing high quality titanium dioxide |
| DE3343256A1 (en) * | 1983-11-30 | 1985-06-05 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING TITANIUM DIOXIDE |
| US4552730A (en) * | 1984-08-27 | 1985-11-12 | The United States Of America As Represented By The Secretary Of The Interior | Recovery of titanium from perovskite using sulfuric acid leaching |
| DE3524053A1 (en) * | 1985-07-05 | 1987-01-08 | Bayer Antwerpen Nv | METHOD FOR PRODUCING HIGH QUALITY TITANIUM DIOXIDE BY THE SULFATE METHOD |
| US5591506A (en) * | 1995-05-10 | 1997-01-07 | Kemicraft Overseas Limited | Non-polluting alkali-metal bisulfate system for producing titanium dioxide pigment |
| US5618331A (en) * | 1995-12-04 | 1997-04-08 | Kemicraft Overseas Limited | Vapor phase fluidized bed sulfation of titaniferous materials |
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1998
- 1998-04-01 WO PCT/US1998/006499 patent/WO1998054095A1/en active IP Right Grant
- 1998-04-01 CN CNB988077345A patent/CN1165488C/en not_active Expired - Fee Related
- 1998-04-01 CA CA002323671A patent/CA2323671A1/en not_active Abandoned
- 1998-04-01 AU AU67944/98A patent/AU744330B2/en not_active Ceased
- 1998-04-01 YU YU72299A patent/YU72299A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321889A (en) * | 2020-11-04 | 2021-02-05 | 沪本新材料科技（上海）有限公司 | Manufacturing process of liquid titanium dioxide for PVC plastic production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1265635A (en) | 2000-09-06 |
| YU72299A (en) | 2001-09-28 |
| CA2323671A1 (en) | 1998-12-03 |
| CN1165488C (en) | 2004-09-08 |
| AU744330B2 (en) | 2002-02-21 |
| WO1998054095A1 (en) | 1998-12-03 |
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