WO2021120280A1 - Dynamic and static-combined stirring system and process for preparing chromium salt by chromite liquid phase oxidation - Google Patents
Dynamic and static-combined stirring system and process for preparing chromium salt by chromite liquid phase oxidation Download PDFInfo
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- WO2021120280A1 WO2021120280A1 PCT/CN2019/128893 CN2019128893W WO2021120280A1 WO 2021120280 A1 WO2021120280 A1 WO 2021120280A1 CN 2019128893 W CN2019128893 W CN 2019128893W WO 2021120280 A1 WO2021120280 A1 WO 2021120280A1
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- Prior art keywords
- reaction
- stirring
- static
- barium
- chromium
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- 238000003756 stirring Methods 0.000 title claims abstract description 178
- 239000007791 liquid phase Substances 0.000 title claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 47
- 150000001844 chromium Chemical class 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 177
- 230000003068 static effect Effects 0.000 claims abstract description 98
- 239000007788 liquid Substances 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 79
- 238000000926 separation method Methods 0.000 claims abstract description 51
- 239000003513 alkali Substances 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 174
- 229910052782 aluminium Inorganic materials 0.000 claims description 79
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 64
- 239000011651 chromium Substances 0.000 claims description 59
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 57
- 229910052804 chromium Inorganic materials 0.000 claims description 57
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 claims description 52
- 229940083898 barium chromate Drugs 0.000 claims description 52
- 238000002156 mixing Methods 0.000 claims description 47
- 238000001556 precipitation Methods 0.000 claims description 46
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 40
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 239000002893 slag Substances 0.000 claims description 36
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 claims description 35
- 239000006228 supernatant Substances 0.000 claims description 35
- 230000035484 reaction time Effects 0.000 claims description 34
- 238000004062 sedimentation Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 27
- 238000004321 preservation Methods 0.000 claims description 23
- 238000004064 recycling Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- 238000006722 reduction reaction Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 12
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 10
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 10
- 229910001626 barium chloride Inorganic materials 0.000 claims description 10
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000000429 sodium aluminium silicate Substances 0.000 claims description 8
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- ALMAEWAETUQTEP-UHFFFAOYSA-N sodium;chromium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Cr+3] ALMAEWAETUQTEP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 39
- 238000002386 leaching Methods 0.000 abstract description 38
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 description 32
- 239000012071 phase Substances 0.000 description 26
- 239000007787 solid Substances 0.000 description 18
- 238000012546 transfer Methods 0.000 description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 238000010586 diagram Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- 238000007655 standard test method Methods 0.000 description 4
- FUIZKNBTOOKONL-DPSBJRLESA-K trisodium;5-[(e)-(3-carboxy-5-methyl-4-oxocyclohexa-2,5-dien-1-ylidene)-(2,6-dichloro-3-sulfonatophenyl)methyl]-3-methyl-2-oxidobenzoate Chemical compound [Na+].[Na+].[Na+].C1=C(C([O-])=O)C(=O)C(C)=C\C1=C(C=1C(=C(C=CC=1Cl)S([O-])(=O)=O)Cl)\C1=CC(C)=C(O)C(C([O-])=O)=C1 FUIZKNBTOOKONL-DPSBJRLESA-K 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003384 small molecules Chemical group 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/05—Stirrers
- B01F27/09—Stirrers characterised by the mounting of the stirrers with respect to the receptacle
- B01F27/091—Stirrers characterised by the mounting of the stirrers with respect to the receptacle with elements co-operating with receptacle wall or bottom, e.g. for scraping the receptacle wall
-
- 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
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/462—Sulfates of Sr or Ba
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention belongs to the technical field of hydrometallurgy and multiphase stirring reaction, and specifically relates to a dynamic and static combined stirring system and a process for preparing chromium salt by liquid-phase oxidation of chromite.
- Chromium salt is an important inorganic chemical product. my country is the largest country in the production of chromium salt, with an annual output of 400,000 tons. Traditional chromium salt production technology, especially calcium roasting technology, has been completely eliminated due to low resource utilization and a large amount of toxic chromium slag containing Cr(VI). At present, the calcium-free roasting process is commonly used in the chromium salt industry. Although the amount of chromium slag produced is greatly reduced, it still fails to completely solve the pollution problem of chromium slag. For this reason, the research and development of chromium salt cleaner production technology has attracted great attention from all walks of life. Among them, chromite liquid phase oxidation method, also known as chromite alkaline leaching method, is considered to be a clean process with great industrial application prospects.
- CN201010146648 proposes a method for producing sodium chromate by alkaline leaching of chromite, which is a relatively complete clean production process of chromite at present, but the disadvantage of this process is that the reaction temperature in the alkaline leaching process is relatively high (180°C ⁇ 320 °C); After leaching, it is diluted with a large amount of water and then solid-liquid separation, which greatly dilutes the concentration of unreacted alkali, and seriously affects the recycling of alkali in leaching; the use of calcium oxide to remove aluminum causes calcium-containing waste residue Accumulation, serious environmental pollution problems; the crude sodium chromate product separated from chromium/alkali is not easy to obtain pure product by evaporation crystallization process, and it consumes energy and time.
- the quality process is strengthened; (2) In order to achieve high efficiency chromium conversion rate, the amount of alkali is extremely large, the later recovery is difficult and the process is complicated; (3) The alkali concentration of the alkaline leaching solution is large, and the particle size of the reaction residue is small, which makes solid-liquid separation difficult; (4) It is difficult to separate the chromium salt and alkali in the leachate, and the obtained chromium salt contains a large amount of alkali, and the later purification process is complicated.
- the technical problem to be solved by the present invention is to provide a dynamic and static combined mixing system in view of the above-mentioned shortcomings of the prior art.
- the system is simple in structure and reasonable in design.
- Under the stirring action of the stirrer the reaction fluid in the stirring tank rotates and flows and mixes, and a rotating body centered on the stirring shaft is formed during stable operation.
- the formation of the rotating body is not conducive to the mixing of the components in the fluid.
- the present invention By installing multiple static stirring paddles, the original stable fluid rotating body is hindered and the symmetry of the original stable flow field is destroyed, so that the fluid rotates and splits, causing the fluid interface to be unstable, thereby realizing the fluid mixing in the flow field.
- the adjustment of the process achieves the purpose of enhancing the mass transfer of fluid mixing.
- a dynamic and static mixing system including a stirrer, characterized in that it also includes a plurality of static stirring paddles arranged in parallel with the stirring shaft of the agitator, and a plurality of The static stirring blade is arranged around the stirring shaft, and a stirring blade is installed at the bottom of the stirring shaft.
- the above-mentioned combined dynamic and static stirring system is characterized in that the distances between the plurality of static stirring paddles and the stirring shaft are all unequal.
- the above-mentioned combined dynamic and static stirring system is characterized in that the static stirring paddle is a slat-shaped stirring paddle, a cylindrical stirring paddle or a prismatic stirring paddle.
- the above-mentioned combined dynamic and static stirring system is characterized in that, with the stirring shaft of the stirrer as the center, the ratio of the installation radius of the static stirring paddle to the radius of the container used for stirring is 1:7.5 to 1:16.
- the present invention also provides a process for preparing chromium salt by liquid-phase oxidation of chromite by using the above-mentioned dynamic and static mixing system, which is characterized in that it includes:
- barium hydroxide to the supernatant to perform a precipitation reaction, after the reaction is completed, barium chromate precipitate A and aluminum-containing lye B are obtained separately;
- barium hydroxide to the washing slag solution for precipitation reaction, after the reaction is finished, barium chromate precipitation C and aluminum-containing lye D are obtained separately;
- the barium chromate precipitate A and the barium chromate precipitate C are dissolved in hydrochloric acid, and then a reducing agent is added to reduce the reaction to obtain a mixed solution of chromium chloride and barium chloride.
- the pH value of the mixed solution is adjusted so that the chromium is replaced with hydrogen.
- the form of chromium oxide is completely precipitated, and solid-liquid separation is used to obtain chromium hydroxide product.
- the above method is characterized in that the reaction temperature of the liquid phase oxidation reaction is 180° C. to 270° C., the oxygen partial pressure is 1.2 MPa to 2.6 MPa, the stirring speed is 500 rpm to 900 rpm, and the reaction time is 1 h to 5 h.
- the above method is characterized in that the mass ratio of sodium hydroxide and chromite is (2-5):1, and the mass of sodium hydroxide is 30% to 60% of the total mass of sodium hydroxide and water.
- the above method is characterized in that the temperature of the heat preservation and sedimentation is 70°C to 150°C, and the time is 120min to 210min.
- the above method is characterized in that when barium hydroxide is added to the supernatant liquid for precipitation reaction, the molar ratio of barium hydroxide to sodium chromate in the supernatant liquid is (1 ⁇ 1.2):1, and the reaction time is 1h ⁇ 2h, reaction temperature 60 ⁇ 80°C;
- the molar ratio of barium hydroxide to sodium chromate in the washing residue is (1 ⁇ 1.2):1
- the reaction time is 1h ⁇ 2h
- the reaction temperature is 60 ⁇ 80°C.
- the above method is characterized in that it further comprises adding sodium silicate slurry to the aluminum-containing lye D to perform a precipitation reaction, and after the reaction is completed, a low-aluminum lye and sodium aluminosilicate precipitation are obtained separately.
- the above method is characterized in that the molar ratio of the sodium silicate to the sodium aluminate in the aluminum-containing lye D is (1 to 1.2):1.
- the above-mentioned method is characterized in that it further comprises the step of returning the separated low-aluminum lye to the high-pressure reactor for recycling after supplementing alkali.
- the above method is characterized in that it also includes returning the aluminum-containing lye B to the autoclave for recycling.
- the above method is characterized in that the ratio of the sum of the amount of the barium chromate precipitate A and the amount of the barium chromate precipitate C to the amount of HCl in the hydrochloric acid is 1: (2-5), and the volume of the hydrochloric acid is The mass of barium chromate precipitate A and barium chromate precipitate C is 4 to 8 times the mass, where the unit of volume is mL and the unit of mass is g.
- the reducing agent is a small molecular alcohol organic substance, and the molar amount of the reducing agent is The theoretical reaction with barium chromate is 1 to 5 times the molar amount.
- the above method is characterized in that the stirring speed of the reduction reaction is 200 rpm to 400 rpm, the reaction temperature is 50°C to 80°C, and the reaction time is 1 h to 2 h.
- the above method is characterized in that barium hydroxide is used to adjust the pH value of the mixed solution to 8-9 after the reduction reaction.
- the above method is characterized in that it also includes adding sulfuric acid to the liquid phase obtained by solid-liquid separation after the chromium is completely precipitated in the form of chromium hydroxide until the barium precipitation is complete, to obtain a barium sulfate product.
- the present invention has the following advantages:
- the mixing system of the present invention has a simple structure and a reasonable design. Under the stirring action of the stirrer, the reaction fluid in the stirring tank rotates and flows and mixes, and a rotating body centered on the stirring shaft is formed during stable operation. The formation of the rotating body is not conducive to the mixing of the components in the fluid.
- the present invention By installing multiple static stirring paddles, the original stable fluid rotating body is hindered and the symmetry of the original stable flow field is destroyed, so that the fluid rotates and splits, causing the fluid interface to be unstable, thereby realizing the fluid mixing in the flow field. The adjustment of the process achieves the purpose of enhancing the mass transfer of fluid mixing.
- Adopting the dynamic and static mixing system of the present invention can significantly increase the chromium conversion rate in the liquid phase oxidation of chromite, greatly reduce the reaction time, and realize a fast and efficient chromium salt clean production method.
- the present invention proposes a new process route for preparing chromium salt by liquid phase oxidation of chromite, which innovatively solves the solid-liquid separation of chromite leaching process, the separation of chromium salt in high alkali medium, and the conversion of intermediate products. It is a key process problem of the series of chromium salts and has great industrial application prospects.
- the present invention proposes to adopt a high-pressure reactor equipped with a dynamic and static mixing paddle, so that the air phase in the upper part of the reactor is changed from the original single-region entrained mixing mode to multi-regional,
- the multiple mixing mode of multi-site entrainment greatly strengthens the gas-liquid-solid three-phase mass transfer process in the reaction system and improves the efficiency of the leaching reaction process.
- the present invention innovatively proposes the insulation and sedimentation separation process of the oxidation leaching system of chromite in a high-alkali medium, which solves the problem of solid-liquid separation. Compared with traditional methods such as dilution filtration and centrifugation, it significantly reduces the solid-liquid separation time and equipment investment cost, and can always keep the aluminum content in the supernatant liquid low, the alkali content is high, the aluminum content in the slag washing liquid is high, and the alkali content is low. It is conducive to the subsequent circulation and aluminum removal process, while retaining the original lye concentration to the greatest extent, greatly improving the efficiency of the direct recycling of the medium.
- the present invention proposes a new process for separating chromium salt directly from the chromite leaching solution by using the barium salt method, and a new process for converting barium chromate into chromium salt.
- a dissolution-reduction method of barium chromate with hydrochloric acid-organic matter as the system was proposed, which achieved the goal of preparing a series of chromium salts from barium chromate.
- the recycling of hydrochloric acid medium is realized, and pure barium sulfate products can be obtained.
- the reaction conditions of the process are mild, green and efficient.
- the present invention innovatively proposes a new process for removing aluminum from the chromite leaching solution in the lye after chromium-alkali separation. That is, sodium silicate is used as a precipitant and added to the lye to directly convert the sodium aluminate precipitation into sodium aluminosilicate. Further processing can obtain the by-product of sodium aluminosilicate molecular sieve with higher economic value, and the lye can be directly recycled In the leaching reaction step, it can improve economy and reduce energy consumption.
- Figure 1 is a schematic diagram of the structure of the dynamic and static combined stirring system of the present invention.
- Fig. 6 is a diagram showing the relationship between the chromium leaching rate and the leaching time of chromite liquid phase oxidation method for preparing chromium salt using a single dynamic stirring blade and the combined dynamic and static stirring system of the present invention.
- Fig. 7 is a schematic diagram of the structure of a high pressure reactor equipped with a dynamic and static mixing system according to the present invention.
- Fig. 8 is a schematic diagram of the process flow of the present invention.
- the dynamic and static mixing system of the present invention includes a stirrer 1, and also includes a plurality of static stirring paddles 12 arranged in parallel with the stirring shaft 2 of the stirrer 1, and the plurality of static stirring paddles 12 surround
- the stirring shaft 2 is provided, and a stirring blade 4 is installed at the bottom of the stirring shaft 2.
- the distances between the plurality of static stirring paddles 12 and the stirring shaft 2 are all unequal.
- the number of the static stirring blades 12 can be 2, 3, 4, 5, 6, and so on.
- the static stirring paddle 12 is a slat-shaped stirring paddle, a cylindrical stirring paddle or a prismatic stirring paddle.
- the ratio of the installation radius of the static stirring paddle 12 to the radius of the container used for stirring is 1:7.5 to 1:16.
- the specific working principle of the dynamic and static combined stirring system of the present invention is: the reaction system (such as solid-liquid, gas-liquid, liquid-liquid, gas-liquid-solid, etc.) under the stirring action of a stirrer, the reaction fluid rotates and mixes, During stable operation, a rotating body with the stirring shaft as the center is formed (as shown in Figures 2 and 3).
- the reaction system such as solid-liquid, gas-liquid, liquid-liquid, gas-liquid-solid, etc.
- the formation of the rotating body is not conducive to the mixing of the components in the fluid, but due to the static stirring paddle located in the flow field
- the existence of, the original stable fluid rotating body is hindered, destroying the symmetry of the original stable flow field, so that the fluid revolves and splits (as shown in Figure 4 and Figure 5), causing the fluid interface to be unstable, thus achieving
- the control of the fluid mixing process in the flow field achieves the purpose of enhancing the mass transfer of fluid mixing.
- the dynamic and static combined stirring system of the present invention is applied to a gas-liquid-solid three-phase mixed mass transfer reaction system.
- the gas above the stirring tank enters the solid-liquid two-phase in the container through the entrainment effect of stirring. Participate in the reaction in the system, and the gas phase has changed from the original mixing mode of entrainment in the flow field around the single dynamic agitator to the multiple mixing mode of the flow field around the dynamic agitator and the small flow field area near the multiple static stirring paddles, greatly increasing
- the gas-liquid-solid three-phase mass transfer area of the reaction system enhances the mass transfer between the phases.
- the acceleration of gas-liquid-solid three-phase mass transfer helps reduce the reaction time of the system.
- the combined dynamic and static stirring system helps to strengthen the mixing of the fluid in the stirred tank, enhance the entrainment of the gas phase in the gas-liquid-solid three-phase reaction, and increase the mass transfer rate between the phases in the reaction system. It can be used for various based
- the fluid mixing system of the stirred tank is especially suitable for the multiphase reaction system involving the solid structure that is stable and difficult to decompose.
- the system also has the characteristics of simple structure, low energy and high rate, low cost, and easy repair.
- the high-pressure reaction vessel equipped with a dynamic and static mixing system used in the present invention includes a high-pressure reaction vessel 8 with an opening at the top, and a sealing cover 3 arranged at the opening of the high-pressure reaction vessel 8.
- a stirrer 1 is installed, the stirring shaft 2 of the stirrer 1 is located in the high-pressure reactor 8, the bottom of the stirring shaft 2 is equipped with a stirring blade 4, and the sealing cover 3 is fixedly installed with a plurality of static stirring blades 12,
- the static stirring blade 12 is arranged around the stirring shaft 2, and one end of the plurality of static stirring blades 12 away from the sealing cover 3 penetrates into the high pressure reactor 8.
- the distances between the plurality of static stirring paddles 12 and the stirring shaft 2 are all unequal.
- the number of the static stirring blades 12 can be 2, 3, 4, 5, 6, and so on.
- the static stirring paddle 12 is a slat-shaped stirring paddle, a cylindrical stirring paddle, or a prismatic stirring paddle.
- thermocouple 7 is installed on the sealing cover 3.
- the lower end of the static stirring blade 12 is located above the stirring blade 4.
- the blades of the stirring blade 4 are ellipsoidal.
- the sealing cover 3 is provided with an air inlet and an air outlet, and an air inlet pipe 9 is installed on the air inlet.
- the air inlet pipe 9 penetrates into the high pressure reactor 8 and the bottom of the air inlet pipe 9 is close to the high pressure reactor 8
- An air inlet valve 5 is installed on the top of the air inlet pipe; an air outlet pipe is installed on the air outlet, and an air outlet valve 11 is installed on the top of the air outlet pipe.
- a pressure gauge 10 for detecting the pressure in the high-pressure reactor 8 is installed on the sealing cover 3.
- a heating jacket 6 is provided on the outside of the high-pressure reactor 8, and a groove for placing the high-pressure reactor 8 is opened in the middle of the heating jacket 6.
- a base 13 is provided at the bottom of the heating jacket 6.
- the high-pressure reactor equipped with a single dynamic stirring blade and the high-pressure reactor equipped with the dynamic and static combined stirring system of the present invention are used to prepare chromite by the liquid phase oxidation method of chromite ore respectively.
- the South African chromite powder is taken and ground to 300 mesh ( 48 ⁇ m), the content of Cr 2 O 3 is about 42.92% as measured by X-ray fluorescence spectrometer (XRF).
- the maximum chromium leaching rate in the leaching solution is only 90%, and it takes 300 minutes. It takes a long time; and after the reaction in the high-pressure reactor of the dynamic and static combined stirring system, the chromium leaching rate has reached 99% in only 240 minutes. And in a short time of 60min ⁇ 120min, the chromium leaching rate in the dynamic and static combined stirring system is about 2 times higher than the former.
- the dynamic and static combined stirring system of the present invention realizes the high-efficiency leaching of the chromite liquid phase oxidation method in a short time, and at the same time greatly improves the chromium leaching rate, avoids secondary recovery and resource waste, and the strengthening method of dynamic and static combination effectively improves the transmission in the system. It is suitable for all kinds of multi-phase reaction systems, and belongs to a new type of device that enhances multi-phase mass transfer with high efficiency.
- the process for preparing chromium salt by liquid-phase oxidation of chromite using the high-pressure reactor equipped with a dynamic and static mixing system includes:
- 125g of chromite (300 mesh), 250g of sodium hydroxide and 583g of water were added to the high pressure reactor equipped with a dynamic and static mixing system; under stirring conditions, oxygen was introduced into the high pressure reactor for liquid phase oxidation reaction.
- the reaction temperature of the oxidation reaction is 180°C
- the oxygen partial pressure is 1.2MPa (total pressure is about 2.4MPa)
- the stirring speed is 500rpm
- the reaction time is 1h
- the temperature of the heat preservation and sedimentation in the box is 70°C, and the time is 120min; the solid-liquid separation of the materials after the heat preservation and sedimentation is carried out to obtain the supernatant liquid and the reaction slag;
- reaction slag is washed countercurrently with water and then separated to obtain washing slag liquid and iron slag;
- the reducing agent is a small molecule alcoholic organic substance ethanol, and the molar amount of the reducing agent is 1 times the theoretical reaction molar amount with barium chromate to obtain a mixed solution of chromium chloride and barium chloride.
- the reduction rate of chromium is 72%; barium hydroxide is used to adjust the pH value of the mixed solution of chromium chloride and barium chloride to 8, so that chromium is completely precipitated in the form of chromium hydroxide, and the solid-liquid separation obtains the chromium hydroxide product.
- Dilute sulfuric acid is added to the liquid phase until the barium precipitation is complete, and a pure barium sulfate product is obtained.
- the dynamic and static mixing system of the present invention includes a stirrer 1, and also includes a plurality of static stirring paddles 12 arranged in parallel with the stirring shaft 2 of the stirrer 1, and the plurality of static stirring paddles 12 surround
- the stirring shaft 2 is provided, and a stirring blade 4 is installed at the bottom of the stirring shaft 2.
- the distances between the plurality of static stirring paddles 12 and the stirring shaft 2 are all unequal.
- the number of the static stirring blades 12 can be 2, 3, 4, 5, 6, and so on.
- the static stirring paddle 12 is a slat-shaped stirring paddle, a cylindrical stirring paddle or a prismatic stirring paddle.
- the ratio of the installation radius of the static stirring paddle 12 to the radius of the container used for stirring is 1:7.5 to 1:16.
- the specific working principle of the dynamic and static combined stirring system of the present invention is: the reaction system (such as solid-liquid, gas-liquid, liquid-liquid, gas-liquid-solid, etc.) under the stirring action of a stirrer, the reaction fluid rotates and mixes, During stable operation, a rotating body with the stirring shaft as the center is formed (as shown in Figures 2 and 3).
- the reaction system such as solid-liquid, gas-liquid, liquid-liquid, gas-liquid-solid, etc.
- the formation of the rotating body is not conducive to the mixing of the components in the fluid, but due to the static stirring paddle located in the flow field
- the existence of, the original stable fluid rotating body is hindered, destroying the symmetry of the original stable flow field, so that the fluid revolves and splits (as shown in Figure 4 and Figure 5), causing the fluid interface to be unstable, thus achieving
- the control of the fluid mixing process in the flow field achieves the purpose of enhancing the mass transfer of fluid mixing.
- the dynamic and static combined stirring system of the present invention is applied to a gas-liquid-solid three-phase mixed mass transfer reaction system.
- the gas above the stirring tank enters the solid-liquid two-phase in the container through the entrainment effect of stirring. Participate in the reaction in the system, and the gas phase has changed from the original mixing mode of entrainment in the flow field around the single dynamic agitator to the multiple mixing mode of the flow field around the dynamic agitator and the small flow field area near the multiple static stirring paddles, greatly increasing
- the gas-liquid-solid three-phase mass transfer area of the reaction system enhances the mass transfer between the phases.
- the acceleration of gas-liquid-solid three-phase mass transfer helps reduce the reaction time of the system.
- the combined dynamic and static stirring system helps to strengthen the mixing of the fluid in the stirred tank, enhance the entrainment of the gas phase in the gas-liquid-solid three-phase reaction, and increase the mass transfer rate between the phases in the reaction system. It can be used for various based
- the fluid mixing system of the stirred tank is especially suitable for the multiphase reaction system involving the solid structure that is stable and difficult to decompose.
- the system also has the characteristics of simple structure, low energy and high rate, low cost, and easy repair.
- the high-pressure reaction vessel equipped with a dynamic and static mixing system used in the present invention includes a high-pressure reaction vessel 8 with an opening at the top, and a sealing cover 3 arranged at the opening of the high-pressure reaction vessel 8.
- a stirrer 1 is installed, the stirring shaft 2 of the stirrer 1 is located in the high-pressure reactor 8, the bottom of the stirring shaft 2 is equipped with a stirring blade 4, and the sealing cover 3 is fixedly installed with a plurality of static stirring blades 12,
- the static stirring blade 12 is arranged around the stirring shaft 2, and one end of the plurality of static stirring blades 12 away from the sealing cover 3 penetrates into the high pressure reactor 8.
- the distances between the plurality of static stirring paddles 12 and the stirring shaft 2 are all unequal.
- the number of the static stirring paddles 12 can be 2, 3, 4, 5, 6, and so on.
- the static stirring paddle 12 is a slat-shaped stirring paddle, a cylindrical stirring paddle, or a prismatic stirring paddle.
- thermocouple 7 is installed on the sealing cover 3.
- the lower end of the static stirring blade 12 is located above the stirring blade 4.
- the blades of the stirring blade 4 are ellipsoidal.
- the sealing cover 3 is provided with an air inlet and an air outlet, and an air inlet pipe 9 is installed on the air inlet.
- the air inlet pipe 9 penetrates into the high pressure reactor 8 and the bottom of the air inlet pipe 9 is close to the high pressure reactor 8
- An air inlet valve 5 is installed on the top of the air inlet pipe; an air outlet pipe is installed on the air outlet, and an air outlet valve 11 is installed on the top of the air outlet pipe.
- a pressure gauge 10 for detecting the pressure in the high-pressure reactor 8 is installed on the sealing cover 3.
- a heating jacket 6 is provided on the outside of the high-pressure reactor 8, and a groove for placing the high-pressure reactor 8 is opened in the middle of the heating jacket 6.
- a base 13 is provided at the bottom of the heating jacket 6.
- the high-pressure reactor equipped with a single dynamic stirring blade and the high-pressure reactor equipped with the dynamic and static combined stirring system of the present invention are used to prepare chromite by the liquid phase oxidation method of chromite ore respectively.
- the South African chromite powder is taken and ground to 300 mesh ( 48 ⁇ m), the content of Cr 2 O 3 is about 42.92% as measured by X-ray fluorescence spectrometer (XRF).
- the maximum chromium leaching rate in the leaching solution is only 90%, and it takes 300 minutes. It takes a long time; and after the reaction in the high-pressure reactor of the dynamic and static combined stirring system, the chromium leaching rate has reached 99% in only 240 minutes. And in a short time of 60min ⁇ 120min, the chromium leaching rate in the dynamic and static combined stirring system is about 2 times higher than the former.
- the dynamic and static combined stirring system of the present invention realizes the high-efficiency leaching of the chromite liquid phase oxidation method in a short time, and at the same time greatly improves the chromium leaching rate, avoids secondary recovery and resource waste, and the strengthening method of dynamic and static combination effectively improves the transmission in the system. It is suitable for all kinds of multi-phase reaction systems, and belongs to a new type of device that enhances multi-phase mass transfer with high efficiency.
- the process for preparing chromium salt by liquid-phase oxidation of chromite using the high-pressure reactor equipped with a dynamic and static mixing system described in Example 2 includes:
- 125g of chromite (300 mesh), 250g of sodium hydroxide and 583g of water were added to the high pressure reactor equipped with a dynamic and static mixing system; under stirring conditions, oxygen was introduced into the high pressure reactor for liquid phase oxidation reaction.
- the reaction temperature of the oxidation reaction is 180°C
- the oxygen partial pressure is 1.2MPa (total pressure is about 2.4MPa)
- the stirring speed is 500rpm
- the reaction time is 1h
- the pressure is released and cooled, and then the materials in the autoclave are transferred to a constant temperature Heat preservation and sedimentation in the box, the temperature of heat preservation and sedimentation is 70°C, and the time is 120min; the solid-liquid separation of the materials after the heat preservation and sedimentation is carried out to obtain the supernatant liquid and the reaction slag;
- reaction slag is washed countercurrently with water and then separated to obtain washing slag liquid and iron slag;
- the reducing agent is a small molecule alcoholic organic substance ethanol, and the molar amount of the reducing agent is 1 times the theoretical reaction molar amount with barium chromate to obtain a mixed solution of chromium chloride and barium chloride.
- the reduction rate of chromium is 72%; barium hydroxide is used to adjust the pH value of the mixed solution of chromium chloride and barium chloride to 8, so that chromium is completely precipitated in the form of chromium hydroxide, and the solid-liquid separation obtains the chromium hydroxide product.
- Dilute sulfuric acid is added to the liquid phase until the barium precipitation is complete, and a pure barium sulfate product is obtained.
- the process for preparing chromium salt by liquid-phase oxidation of chromite using the high-pressure reactor equipped with a dynamic and static mixing system described in Example 2 includes:
- reaction slag is washed countercurrently with water and then separated to obtain washing slag liquid and iron slag;
- the reducing agent is a small-molecule alcoholic organic substance ethanol, and the molar amount of the reducing agent is 1 times the theoretical reaction molar amount with barium chromate to obtain a mixed solution of chromium chloride and barium chloride.
- the reduction rate of chromium is It is 96%; the pH value of the mixed solution of chromium chloride and barium chloride is adjusted to 8.5 with barium hydroxide, so that chromium is completely precipitated in the form of chromium hydroxide, and the solid-liquid separation obtains the chromium hydroxide product, which is separated by centrifugation Dilute sulfuric acid is added to the latter liquid phase until the barium precipitation is complete, and a pure barium sulfate product is obtained.
- the process for preparing chromium salt by liquid-phase oxidation of chromite using the high-pressure reactor equipped with a dynamic and static mixing system described in Example 2 includes:
- reaction slag is washed countercurrently with water and then separated to obtain washing slag liquid and iron slag;
- the reducing agent is a small molecular alcohol organic substance methanol, and the molar amount of the reducing agent is 5 times the theoretical reaction molar amount with barium chromate to obtain a mixed solution of chromium chloride and barium chloride.
- the reduction rate of chromium is 99%;
- Barium hydroxide is used to adjust the pH value of the mixed solution of chromium chloride and barium chloride to 9, so that chromium is completely precipitated in the form of chromium hydroxide, and the solid-liquid separation obtains the chromium hydroxide product.
- Dilute sulfuric acid is added to the liquid phase until the barium precipitation is complete, and a pure barium sulfate product is obtained.
- Example 5 According to the process of Example 5, the liquid phase oxidation reaction and the insulation sedimentation were carried out. After the solid-liquid separation, the chromium conversion rate was measured to be 99%. According to the molar ratio of barium hydroxide to sodium chromate in the supernatant liquid, the molar ratio of sodium chromate was 1.2:1. Barium hydroxide was added to the solution, and the reaction was stirred for 2 hours at a temperature of 80°C. After the reaction, barium chromate precipitate A and aluminum-containing lye B were separated.
- the measured chromium conversion rate was 97%; Liquid B is returned to the high-pressure reactor for recycling, supplemented with a small amount of sodium hydroxide and water, and carried out the liquid phase oxidation reaction under the same conditions. After the reaction, the pressure is released and cooled, and then the materials in the high-pressure reactor are transferred to the thermostat for heat preservation and sedimentation.
- the sedimentation temperature was 150°C
- the time was 210 minutes
- the measured chromium conversion rate was 99%, indicating that the recycling of aluminum-containing lye B has no effect on the chromium leaching.
- Example 5 According to the process of Example 5, the liquid phase oxidation reaction and insulation sedimentation were carried out. After the solid-liquid separation, the chromium conversion rate was measured to be 99%. The supernatant after the solid-liquid separation was directly recycled to the autoclave and supplemented with sodium hydroxide. With water, carry out the liquid phase oxidation reaction under the same conditions. After the reaction, the pressure is released and cooled, and then the materials in the autoclave are transferred to the thermostat for heat preservation and sedimentation. The temperature for heat preservation and sedimentation is 150°C and the time is 210min. After solid-liquid separation The measured conversion rate of chromium was 82%, indicating that excessive sodium chromate content in the supernatant would inhibit the leaching of chromium from chromite.
- Example 5 According to the process of Example 5, the liquid phase oxidation reaction and insulation sedimentation were carried out. After solid-liquid separation, the supernatant liquid and the reaction residue were obtained. The chromium conversion rate was measured to be 99%; the reaction residue was separated by countercurrent washing with water to obtain Slag washing liquid and iron slag; according to the molar ratio of barium hydroxide to sodium chromate in the washing slag solution of 1.2:1, barium hydroxide is added to the washing slag solution for precipitation reaction, the reaction time is 2h, and the reaction temperature is 80 °C; after the reaction, the barium chromate precipitate C and the aluminum-containing lye D are separated and the chromium conversion rate is 97%; according to the sodium silicate and aluminum-containing lye D, the molar ratio of sodium aluminate in the lye D is 1.2: 1.
- Example 5 According to the process of Example 5, the liquid phase oxidation reaction and insulation sedimentation were carried out. After solid-liquid separation, the supernatant liquid and the reaction residue were obtained. The chromium conversion rate was measured to be 99%; the reaction residue was separated by countercurrent washing with water to obtain Slag washing liquid and iron slag; according to the molar ratio of barium hydroxide to sodium chromate in the washing slag solution of 1.2:1, barium hydroxide is added to the washing slag solution for precipitation reaction, the reaction time is 2h, and the reaction temperature is 80 °C; After the reaction, the barium chromate precipitate C and the aluminum-containing lye D are separated and the chromium conversion rate is 97%; the aluminum-containing lye D is returned to the high-pressure reactor for recycling after making up the alkali; according to the same conditions The liquid phase oxidation reaction is carried out.
- the pressure is released and cooled, and then the materials in the autoclave are transferred to the thermostat for heat preservation and sedimentation.
- the temperature of heat preservation and sedimentation is 150°C and the time is 210min.
- the conversion of chromium is measured. The rate is 88%, indicating that the untreated aluminum-containing lye D can inhibit the leaching of chromium.
- the present invention proposes a new process route for preparing chromium salt by liquid phase oxidation of chromite, which innovatively solves the solid-liquid separation of chromite leaching process, the separation of chromium salt in high alkali medium, and the conversion of intermediate products into series
- the key process problem of chromium salt has great prospects for industrial application.
- the chromite liquid-phase oxidation leaching process it is proposed to use a high-pressure reactor equipped with a dynamic and static mixing paddle, so that the air phase in the upper part of the reactor is changed from the original single-region entrainment to the multi-region, multi-site volume.
- the multi-element mixing method of suction greatly strengthens the gas-liquid-solid three-phase mass transfer process in the reaction system and improves the efficiency of the leaching reaction process.
- the insulation sedimentation separation process of the oxidation leaching system of chromite in a high-alkali medium is proposed, which solves the problem of solid-liquid separation. Compared with traditional methods such as dilution filtration and centrifugation, it significantly reduces the solid-liquid separation time and equipment investment cost, and can always keep the aluminum content in the supernatant liquid low, the alkali content is high, the aluminum content in the slag washing liquid is high, and the alkali content is low. It is conducive to the subsequent circulation and aluminum removal process, while retaining the original lye concentration to the greatest extent, greatly improving the efficiency of the direct recycling of the medium.
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Abstract
Description
Claims (17)
- 一种动静组合搅拌系统,包括搅拌器(1),其特征在于,还包括与所述搅拌器(1)的搅拌轴(2)平行设置的多个静态搅拌桨(12),多个所述静态搅拌桨(12)围绕搅拌轴(2)设置,所述搅拌轴(2)的底部安装有搅拌桨叶(4)。A combined dynamic and static stirring system, comprising a stirrer (1), characterized in that it also comprises a plurality of static stirring paddles (12) arranged in parallel with the stirring shaft (2) of the stirrer (1), and a plurality of said The static stirring blade (12) is arranged around the stirring shaft (2), and a stirring blade (4) is installed at the bottom of the stirring shaft (2).
- 根据权利要求1所述的一种动静组合搅拌系统,其特征在于,多个所述静态搅拌桨(12)距搅拌轴(2)的距离均不相等。A combined dynamic and static stirring system according to claim 1, characterized in that the distances between the plurality of static stirring paddles (12) and the stirring shaft (2) are all unequal.
- 根据权利要求1或2所述的一种动静组合搅拌系统,其特征在于,所述静态搅拌桨(12)为板条状搅拌桨、圆柱状搅拌桨或棱柱状搅拌桨。A combined dynamic and static stirring system according to claim 1 or 2, characterized in that the static stirring paddle (12) is a slat-shaped stirring paddle, a cylindrical stirring paddle or a prismatic stirring paddle.
- 根据权利要求2所述的一种动静组合搅拌系统,其特征在于,以搅拌器(1)的搅拌轴(2)为圆心,所述静态搅拌桨(12)的安装半径与搅拌所用容器的半径之比为1∶7.5~1∶16。The dynamic and static combined stirring system according to claim 2, characterized in that, with the stirring shaft (2) of the stirrer (1) as the center, the installation radius of the static stirring paddle (12) is the same as the radius of the container used for stirring. The ratio is 1:7.5 to 1:16.
- 一种利用如权利要求1、2或4所述动静组合搅拌系统进行铬铁矿液相氧化制备铬盐的工艺,其特征在于,包括:A process for preparing chromium salt by liquid-phase oxidation of chromite by using the dynamic and static combined stirring system of claim 1, 2 or 4, which is characterized in that it comprises:将铬铁矿、氢氧化钠和水加入安装有动静组合搅拌系统的高压反应釜内,在搅拌条件下向高压反应釜内通入氧气进行液相氧化反应,反应结束后泄压冷却,然后将高压反应釜内物料转移至恒温箱内保温沉降,对保温沉降后的物料进行固液分离,得到上清液和反应渣;Add chromite, sodium hydroxide and water into the autoclave equipped with a dynamic and static mixing system. Under agitation, oxygen is introduced into the autoclave for liquid phase oxidation. After the reaction, the pressure is released and cooled, and then the The materials in the high-pressure reactor are transferred to the thermostat for heat preservation and sedimentation, and solid-liquid separation of the materials after heat preservation and sedimentation is carried out to obtain the supernatant liquid and the reaction residue;将所述反应渣经逆流洗涤后分离,得到洗渣液和铁渣;Separating the reaction slag after countercurrent washing to obtain washing slag liquid and iron slag;向所述上清液中加入氢氧化钡进行沉淀反应,反应结束后分离得到铬酸钡沉淀A和含铝的碱液B;Adding barium hydroxide to the supernatant to perform a precipitation reaction, after the reaction is completed, barium chromate precipitate A and aluminum-containing lye B are obtained separately;向所述洗渣液中加入氢氧化钡进行沉淀反应,反应结束后分离得到铬酸钡沉淀C和含铝的碱液D;Adding barium hydroxide to the washing slag liquid to perform a precipitation reaction, after the reaction is completed, barium chromate precipitation C and aluminum-containing lye D are obtained separately;将所述铬酸钡沉淀A和铬酸钡沉淀C用盐酸溶解,然后加入还原剂,还原反应得到氯化铬和氯化钡的混合溶液,调节所述混合溶液的pH值,使铬以氢氧化铬的形式完全沉淀,固液分离得到氢氧化 铬产品。The barium chromate precipitate A and the barium chromate precipitate C are dissolved in hydrochloric acid, and then a reducing agent is added to reduce the reaction to obtain a mixed solution of chromium chloride and barium chloride. The pH value of the mixed solution is adjusted so that the chromium is replaced with hydrogen. The form of chromium oxide is completely precipitated, and solid-liquid separation is used to obtain chromium hydroxide product.
- 根据权利要求5所述的方法,其特征在于,所述液相氧化反应的反应温度为180℃~270℃,氧气分压为1.2MPa~2.6MPa,搅拌转速为500rpm~900rpm,反应时间为1h~5h。The method according to claim 5, wherein the reaction temperature of the liquid phase oxidation reaction is 180° C. to 270° C., the oxygen partial pressure is 1.2 MPa to 2.6 MPa, the stirring speed is 500 rpm to 900 rpm, and the reaction time is 1 h ~5h.
- 根据权利要求5所述的方法,其特征在于,氢氧化钠和铬铁矿的质量比为(2~5)∶1,氢氧化钠的质量为氢氧化钠和水的总质量的30%~60%。The method according to claim 5, wherein the mass ratio of sodium hydroxide and chromite is (2-5):1, and the mass of sodium hydroxide is 30% to 30% of the total mass of sodium hydroxide and water. 60%.
- 根据权利要求5所述的方法,其特征在于,所述保温沉降的温度为70℃~150℃,时间为120min~210min。The method according to claim 5, wherein the temperature of the heat preservation and sedimentation is 70°C to 150°C, and the time is 120min to 210min.
- 根据权利要求5所述的方法,其特征在于,向所述上清液中加入氢氧化钡进行沉淀反应时,氢氧化钡与上清液中铬酸钠的摩尔比为(1~1.2)∶1,反应时间为1h~2h,反应温度60~80℃;The method according to claim 5, wherein when barium hydroxide is added to the supernatant for precipitation reaction, the molar ratio of barium hydroxide to sodium chromate in the supernatant is (1 to 1.2): 1. The reaction time is 1h~2h, and the reaction temperature is 60~80℃;向所述洗渣液中加入氢氧化钡进行沉淀反应时,氢氧化钡与洗渣液中铬酸钠的摩尔比为(1~1.2)∶1,反应时间为1h~2h,反应温度60~80℃。When barium hydroxide is added to the washing residue for precipitation reaction, the molar ratio of barium hydroxide to sodium chromate in the washing residue is (1~1.2):1, the reaction time is 1h~2h, and the reaction temperature is 60~ 80°C.
- 根据权利要求5所述的方法,其特征在于,还包括向所述含铝的碱液D中加入硅酸钠浆料进行沉淀反应,反应结束后分离得到低铝碱液和硅铝酸钠沉淀。The method according to claim 5, further comprising adding sodium silicate slurry to the aluminum-containing lye D to perform a precipitation reaction, and after the reaction is completed, low-aluminum lye and sodium aluminosilicate precipitation are obtained separately .
- 根据权利要求10所述的方法,其特征在于,所述硅酸钠与含铝的碱液D中的铝酸钠摩尔比为(1~1.2)∶1。The method according to claim 10, wherein the molar ratio of the sodium silicate to the sodium aluminate in the aluminum-containing lye D is (1 to 1.2):1.
- 根据权利要求10所述的方法,其特征在于,还包括将分离得到的低铝碱液补碱后返回高压反应釜内循环利用。The method according to claim 10, characterized in that it further comprises the step of returning the separated low-aluminum lye to the high-pressure reactor for recycling.
- 根据权利要求5所述的方法,其特征在于,还包括将含铝的碱液B返回高压反应釜内循环利用。The method according to claim 5, characterized in that it further comprises returning the alkali solution B containing aluminum to the autoclave for recycling.
- 根据权利要求5所述的方法,其特征在于,所述铬酸钡沉淀A和铬酸钡沉淀C的物质的量之和与盐酸中HCl的物质的量之比为1∶(2~5),盐酸的体积为铬酸钡沉淀A和铬酸钡沉淀C质量之和的4~8倍,其中体积的单位为mL,质量的单位为g,所述还原剂为小分子 醇类有机物,还原剂的摩尔量为与铬酸钡理论反应摩尔量的1~5倍。The method according to claim 5, wherein the ratio of the sum of the amount of the barium chromate precipitate A and the amount of the barium chromate precipitate C to the amount of HCl in the hydrochloric acid is 1: (2-5) , The volume of hydrochloric acid is 4-8 times the sum of the masses of barium chromate precipitation A and barium chromate precipitation C, where the unit of volume is mL and the unit of mass is g. The reducing agent is a small molecular alcohol organic substance, which reduces The molar amount of the agent is 1 to 5 times the theoretical reaction molar amount with barium chromate.
- 根据权利要求5所述的方法,其特征在于,还原反应的搅拌转速为200rpm~400rpm,反应温度为50℃~80℃,反应时间为1h~2h。The method according to claim 5, wherein the stirring speed of the reduction reaction is 200 rpm to 400 rpm, the reaction temperature is 50° C. to 80° C., and the reaction time is 1 h to 2 h.
- 根据权利要求5所述的方法,其特征在于,还原反应后采用氢氧化钡调节所述混合溶液的pH值至8~9。The method according to claim 5, characterized in that barium hydroxide is used to adjust the pH value of the mixed solution to 8-9 after the reduction reaction.
- 根据权利要求5所述的方法,其特征在于,还包括向铬以氢氧化铬的形式完全沉淀后固液分离得到的液相中加入硫酸至钡沉淀完全,得到硫酸钡产品。The method according to claim 5, characterized in that it further comprises adding sulfuric acid to the liquid phase obtained by the solid-liquid separation after the chromium is completely precipitated in the form of chromium hydroxide until the barium precipitation is complete, to obtain a barium sulfate product.
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