CN100418884C - Process for raising producing aluminium oxide circulating efficiency by Bayer process - Google Patents
Process for raising producing aluminium oxide circulating efficiency by Bayer process Download PDFInfo
- Publication number
- CN100418884C CN100418884C CNB200610000862XA CN200610000862A CN100418884C CN 100418884 C CN100418884 C CN 100418884C CN B200610000862X A CNB200610000862X A CN B200610000862XA CN 200610000862 A CN200610000862 A CN 200610000862A CN 100418884 C CN100418884 C CN 100418884C
- Authority
- CN
- China
- Prior art keywords
- extraction
- bayer process
- liquid
- bayer
- circulation fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004131 Bayer process Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 48
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 45
- 238000000605 extraction Methods 0.000 claims abstract description 125
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 111
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 230000004087 circulation Effects 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000003518 caustics Substances 0.000 claims abstract description 25
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 22
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 21
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 6
- 238000000638 solvent extraction Methods 0.000 claims abstract description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 33
- 239000012530 fluid Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 12
- 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 claims description 11
- 150000002191 fatty alcohols Chemical class 0.000 claims description 11
- -1 alkyl hydroxybenzene Chemical compound 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960003742 phenol Drugs 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 230000001839 systemic circulation Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 229940072033 potash Drugs 0.000 claims 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 1
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- 238000001704 evaporation Methods 0.000 abstract description 10
- 230000008020 evaporation Effects 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005728 strengthening Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 229940083608 sodium hydroxide Drugs 0.000 description 25
- 239000000284 extract Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 235000008504 concentrate Nutrition 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 150000003983 crown ethers Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/28—Purification; Separation
- C01D1/34—Purification; Separation with selective solvents
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/0606—Making-up the alkali hydroxide solution from recycled spent liquor
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/144—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by precipitation due to cooling, e.g. as part of the Bayer process
Abstract
The present invention relates to a method of strengthening seed decomposition and increasing circulation efficiency of a Bayer process system by using a liquid-liquid extraction method for extracting sodium hydroxide from a concentrated Bayer process circulation liquid so as to reduce the caustic ratio of an evaporation mother liquid or a decomposition mother liquid. The present invention comprises the following steps: sodium hydroxide is extracted from a Bayer process circulation liquid by using extraction agents, such as n-octyl alcohol, C6-C20 fatty alcohol or a mixture of n-octyl alcohol and C6-C20 fatty alcohol, alkylphenol with the carbon chain length of C13-C18, fluoric alcohol, etc.; a concentrated sodium hydroxide solution without Al is prepared by back extraction with water, and the concentrated sodium hydroxide solution can be directly used for bauxite ore dissolution or recovery of aluminum oxide and caustic alkali from red mud; after the back extraction, the extraction agents are regenerated for circulation use, and the residual extraction liquid is continuously used for the seed decomposition to prepare aluminium hydroxide. The present invention increases the production yield of aluminum oxide in each circulation process, greatly improves the circulation efficiency of the Bayer process, and is favorable for the preparation of sandy aluminum oxide. The present invention can greatly increase the production yield of the aluminum oxide factories, and provide a novel method of efficiently processing medium grade and low grade bauxite ore resources containing high content of silicon by using a Bayer process.
Description
Technical field
A kind of method that improves producing aluminium oxide circulating efficiency by Bayer process, relate to a kind of liquid-liquid extraction method that utilizes and from spissated Bayer process circulation fluid, extract sodium hydroxide caustic alkali such as () aluminium hydroxide potassium reducing the causticity ratio of mother liquid evaporation or decomposition nut liquid, thereby strengthen the method that seed decomposes and improve Bayer process systemic circulation efficient and aluminum oxide productive rate.
Technical background
Bayer process is the main method of alumina producing.The stripping reaction takes place with bauxite and the Bayer process circulation fluid that contains sodium hydroxide in this method under high-temperature and high-pressure conditions, make the aluminum oxide in the bauxite enter solution formation sodium aluminate solution, then the sodium aluminate solution dilution is separated with red mud, in the situation that adds crystal seed sodium aluminate solution is decomposed and produce aluminium hydroxide, roasting becomes alumina product.The seed decomposition nut liquid evaporation back that contains sodium hydroxide and remaining sodium aluminate after the decomposition is reused for stripping bauxite as circulating mother liquor.The alumina producing of this method constitutes preceding half section of metallurgy of aluminium industry.
But Bayer process itself also has tangible weakness: (1) is because seed decomposition course hydrolysis reaction is incomplete, general only have the sodium aluminate about 50% to generate aluminium hydroxide, cause and still contain a large amount of sodium aluminates in the circulation fluid and circulate on stream, cause the solution circulated amount big, and still contain a large amount of sodium aluminates in the circulation fluid total alkali content, only some is the free sodium hydroxide that really can play stripping.Therefore dissolution efficiency is restricted; (2) China's bauxite is siliceous higher, and a large amount of aluminum oxide, sodium oxide enter the red mud loss during Bayer process stripping.People once imagined with connecting with Bayer process from the high pressure aquation law technology that red mud reclaims aluminum oxide, with the yield of raising aluminum oxide.But it is too high that the Bayer process circulation fluid contains concentration of sodium aluminate, can not be used for the high pressure aquation method stripping of red mud, and this difficulty becomes obstruction Bayer process and the placed in-line bottleneck of high pressure aquation method; (3) China's bauxite is mainly the diaspore type ore, and Bayer process leaching condition harshness is difficult to prepare causticity than low dissolution fluid, also causes certain difficulty to producing sandy alumina through decomposing seeds.Adopt the potentiality of strengthening dissolving-out technology reduction dissolution fluid causticity ratio little.(4) the Bayer process stripping is low because of the circulating mother liquor molecular ratio, thereby output capacity is lower.
Part free sodium hydroxide in the sodium aluminate solution is effectively separated, the causticity that makes Bayer process seed decomposition nut liquid is than reducing significantly, make it can proceed seed and decompose, just can strengthen or shorten seed and decompose production process, improve the productive rate of Bayer process cycle efficiency and aluminum oxide.Simultaneously, will isolate sodium-hydroxide treatment and obtain not aluminiferous soda-lye, replace original Bayer process circulation fluid stripping bauxite, just may reduce the internal circulating load of Bayer process circulation fluid significantly, strengthen the Bayer process process in leaching.And then can connect with high pressure aquation method for Bayer process and handle red mud, open up a new way for handle siliceous higher bauxite with Bayer process.Make the Bayer process flow process that great change take place, increase substantially the stripping and the seed decomposing efficiency of Bayer process, improve the aluminum oxide productive rate of each production cycle, enlarge the scope of the ore that is suitable for Bayer process production.Therefore, seek with cheap extraction agent and realize the Bayer process circulation fluid is made liquid-liquid extraction, make its causticity than reducing significantly, produce the strong solution of sodium hydroxide simultaneously by back extraction, significant for the alumina producer of the improvement of alumina producing technology and the efficient brand new technical of design and construction.
For separation of hydrogen sodium oxide technology, in recent years, a series of research work have been done in the Oak Ridge laboratory by United States Atomic Energy Commission, its objective is and will reclaim sodium hydroxide from the nuclear fuel waste liquid that contains sodium hydroxide.In patent that they apply for and the paper of delivering, recommending with fluorinated alcohols and some macrocyclic crown ethers is extraction agent, and their alkylphenol also on probation is an extraction agent, and they realize sodium hydroxide extraction with the kerosene of these extraction agents or the solution of alcohols.And they find that also water can back extraction obtain sodium hydroxide solution.Though the above-mentioned patented technology of the U.S. can realize extraction and back extraction, reach the purpose that reclaims sodium hydroxide from waste liquid.For the technological process of strengthening Bayer process, different with U.S. nuclear industry from the purpose of waste water reclamation sodium hydroxide because Bayer process produce in sodium hydroxide recycled originally.Production has at present reached wastewater zero discharge, does not reclaim the requirement of sodium hydroxide from waste water.The technical scheme that United States Patent (USP) is recommended is very not suitable to us.Its concrete reason is: the fluorinated alcohols cost that P.6322702 (1) U.S. Pat recommends higher (this patent document is pointed out: preparation fluorinated alcohols possibility cost is higher), macrocyclic crown ether also is valuable Chemicals.For the production of the so extensive cheap products of aluminum oxide, it is uneconomical economically to use too valuable extraction agent; (2) American technology is suitable for handling rarer sodium hydroxide solution, and strip liquor concentration is also lower.And we need back extraction to produce the sodium hydroxide solution of high density, just can reach to strengthen the requirement that Bayer process is produced; (3) the alkylphenol extraction agent of Americana suggestion adapts to the needs of nuke rubbish extracting and separating radiocesium, at patent USP3598547, stipulate among the USP3598548: the single side chain carbon number of alkylphenol molecule must not be above 12, because its side chain carbon number is little, water-soluble bigger, and because the seed decomposition of Bayer process is very responsive to organic impurity, this extraction agent is inapplicable.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art, provide a kind of can be effectively from the Bayer process circulation fluid caustic alkali such as extraction sodium hydroxide with the causticity that reduces mother liquid evaporation or decomposition nut liquid than, increase substantially Bayer process cycle efficiency method.
The objective of the invention is to be achieved through the following technical solutions.
A kind of method that improves producing aluminium oxide circulating efficiency by Bayer process adopts liquid-liquid extraction to extract sodium hydroxide from the Bayer process circulation fluid, reduces its causticity ratio, thereby strengthens the method that seed decomposes and improve Bayer process systemic circulation efficient and aluminum oxide productive rate; The operation steps that it is characterized in that method is followed successively by:
A. be 100-400g/L with the caustic alkali naoh concentration, caustic ratio is in the Bayer process circulation fluid of 2.0-4.2, adds extraction agent, and under 60-100 ℃ of temperature, the mechanical stirring extraction is 2-20 minute in extraction tank;
B. after extractive reaction is finished, oily water separation;
C. isolated oil phase is squeezed in the back extraction groove, as strippant, under 60-100 ℃ of temperature, stirred back extraction 2-20 minute with water;
D. after the back extraction reaction is finished, oily water separation; Isolated oil phase is squeezed in the extraction tank that step a carried again, once more extraction;
E. the order of a-d so circulates for several times set by step;
The caustic ratio of the bayer's process circulation fluid among the f. final step a is reduced to 1.4, and direct dilution is used for the seed decomposition and produces sandy alumina.
Method of the present invention when it is characterized in that back extraction water caustic alkali naoh concentration height is for 200-300g/L among the step c, is directly used in stripping bauxite or is used for high pressure aquation method exsolution red mud.
Method of the present invention is characterized in that the Bayer process circulation fluid is meant the sodium aluminate solution in the aluminum oxide production process, includes alkalimetal ions such as lithium, sodium, potassium in the solution.
Method of the present invention is characterized in that the extraction agent of the extraction process employing of adding extraction agent in the Bayer process circulation fluid is that carbon chain lengths is the Fatty Alcohol(C12-C14 and C12-C18) of 6-20 or their mixture.
Method of the present invention is characterized in that the extraction agent of the extraction process employing of adding extraction agent in the Bayer process circulation fluid is a n-Octanol.
Method of the present invention is characterized in that the extraction agent of the extraction process employing of adding extraction agent in the Bayer process circulation fluid is an induced by alkyl hydroxybenzene, and the position on the alkyl substituted benzene ring is ortho position, a position and contraposition, and in contraposition, single alkyl branches length is 13-18 carbon; The thinner of induced by alkyl hydroxybenzene extraction agent can be the alkane of 6-18 carbon or the mixture of kerosene and Fatty Alcohol(C12-C14 and C12-C18) for carbon chain lengths.
Method of the present invention is characterized in that the strippant that extraction process adopts is a pure water, also can be that concentration is less than the NaOH dilute solution of 7mol/L or the low neutralizing treatment waste liquid of aluminum oxide industry washing aluminium hydroxide product.
Show by experiment about of the present invention: (1) is with the suitable evaporation concentration of Bayer process seed decomposition nut liquid, just can be with cheap, industrial mass-produced Fatty Alcohol(C12-C14 and C12-C18) or n-Octanol high-level efficiency extraction sodium hydroxide, and the water back extraction can obtain the soda-lye of 300-400g/L; (2) in order to reduce the water-soluble of alkylphenol, with water-soluble little, kerosene-n-Octanol solution extraction that side chain contains the octadecyl phenol of 18 carbon atoms also can get good result.Adopt extraction scheme of the present invention, utilize n-Octanol, Fatty Alcohol(C12-C14 and C12-C18), alkylphenol, fluorinated alcohols extraction agent to realize liquid-liquid extraction, caustic alkali such as extraction sodium hydroxide etc. is to reduce the causticity ratio of mother liquid evaporation or decomposition nut liquid from spissated Bayer process circulation fluid, the seed decomposition nut liquid of causticity about than 2.0-4.2 through concentrating and extraction after, the causticity ratio can be reduced to about 1.4-1.5, can do further seed again and decompose.For increasing substantially Bayer process cycle efficiency and alumina producer output and opening up a new way with the siliceous higher middle-low bauxite resource of the efficient processing of Bayer process.
Discover with n-Octanol, C through us
6-C
20Fatty Alcohol(C12-C14 and C12-C18) or their mixture, carbon chain lengths are C
13-C
18Extraction agent such as alkylphenol, fluorinated alcohols can extract sodium hydroxide from the Bayer process circulation fluid after suitably concentrating, particularly (1) makes Na when Bayer process seed decomposition nut liquid concentrates by suitable
2O
kWhen reaching the above concentration of 360g/L, be that extraction agent extracts with the Fatty Alcohol(C12-C14 and C12-C18) of 8-10 cheap carbon, and the water back extraction obtains not aluminiferous soda-lye as circulation fluid, this circulation fluid can be directly used in the high pressure aquation method stripping of bauxite stripping or red mud.Extractant regeneration after the back extraction can be recycled.Raffinate continues to serve as the seed decomposition and produces aluminium hydroxide; (2) after Bayer process seed decomposition nut liquid suitably concentrates, with the n-Octanol solution or the n-Octanol-kerosin extraction of octadecyl phenol, and the water back extraction, can obtain not aluminiferous sodium hydroxide solution, can be used for the high pressure aquation method stripping of bauxite stripping or red mud.Extractant regeneration after the back extraction can be recycled.Raffinate can be used for the seed decomposition and produce aluminium hydroxide.
Originally Bayer process seed decomposition nut liquid is to be used for the high pressure stripping through circulation after the evaporation concentration.According to the present invention, then can obtain causticity than about 1.5 sodium aluminate solution with it by extraction, can continue the seed decomposition, to reclaim more aluminium hydroxide.The sodium hydroxide solution that is not contained sodium aluminate simultaneously by back extraction, circulation is used for the bauxite stripping.Because oxygen-free aluminium wherein, dissolution efficiency and stripping equipment utilization ratio might significantly improve, and the solution circulated amount may significantly reduce, and helps increasing substantially the Bayer process cycle efficiency.Therefore might cut down the consumption of energy because of internal circulating load reduces significantly.Also can make high pressure aquation method stripping recovery aluminum oxide and caustic alkali wherein with the soda-lye of gained to red mud earlier, obtain being used further to the bauxite stripping behind the solution of causticity than 9-10, thereby handle siliceous higher bauxite with Bayer process-high pressure aquation method and realize the high solubility rate of aluminum oxide.Enlarge the treatable bauxite grade scope of Bayer process.
Specific embodiments
Place the Bayer process sodium aluminate circulation fluid in extraction tank, sodium oxide concentration is at 100-400g/L, and caustic ratio is at 2.0-4.2, with n-Octanol, C
6-C
20Fatty Alcohol(C12-C14 and C12-C18) or their mixture, carbon chain lengths are C
13-C
18The extraction of extraction agent such as alkylphenol, fluorinated alcohols mechanical stirring, temperature is controlled at 60-100 ℃, and the extraction time was controlled at 2-20 minute, after reaction is finished, oily water separation.Separated oil phase is squeezed in another back extraction groove with the low alkaline solution of water or caustic sodium concentration as strippant, stirred back extraction equally, temperature is controlled at 60-100 ℃, and the back extraction time was controlled at 2-20 minute.After reaction is finished, oily water separation.This moment, the sodium hydroxide of extraction entered strip aqueous, and the regenerated oil phase can be recycled.Again squeeze into the regenerated oil phase in the extraction tank extraction agent recycle this moment.So circulation.The back extraction water that strip aqueous can more renew according to concentration requirement.For several times, the caustic ratio of raffinate is reduced.
Below just be illustrated in conjunction with specific embodiments.
Embodiment one:
With C
8-C
10Mixture (the weight percent C of Fatty Alcohol(C12-C14 and C12-C18)
8: C
10=51: 49) be extraction agent, the concentrated Bayer process mother liquid evaporation of 1 times of volume of extraction, the causticity ratio is 2.70, and caustic sodium concentration is 482g/L, and the extraction agent volume is 4 times of volumes.Extract under 95 ℃ of conditions, churning time was controlled at 10 minutes, after reaction is finished, and oily water separation.The water that isolated oil phase is squeezed in the back extraction groove with 1 times of volume stirs back extraction, and temperature is controlled at 95 ℃, and the back extraction time was controlled at 10 minutes equally.After reaction is finished, oily water separation.The regenerated extraction agent recycles.So circulation.Heating concentrates back continuation extraction, so circulation when the caustic sodium concentration of raffinate is lower than 10mol/L.Concentrate 2 times in the pilot process, 15 extracting-back extraction, final, raffinate causticity ratio is 1.40, can be used for seed and decomposes.The strip liquor caustic sodium concentration can reach more than the 300g/L.After measured, water base of back extraction can not detect aluminium, illustrates that the extraction agent that adopts does not extract aluminium.
Embodiment two:
With the n-Octanol is extraction agent, the concentrated Bayer process mother liquid evaporation of 1 times of volume of extraction, and the causticity ratio is 3.28, caustic sodium concentration is 499g/L, the extraction agent of 4 times of volumes.Extract under 90 ℃ of conditions, churning time was controlled at 10 minutes, after reaction is finished, and oily water separation.Isolated oil phase places the back extraction groove to stir back extraction with the water of 1 times of volume, and temperature is controlled at 90 ℃, and the back extraction time was controlled at 10 minutes equally.After reaction is finished, oily water separation.The regenerated extraction agent recycles.So circulation.Heating concentrates back continuation extraction, so circulation when the caustic sodium concentration of raffinate is lower than 10mol/L.Concentrate 3 times in the pilot process, 11 extracting-back extraction, final, raffinate causticity ratio is 1.68, can decompose by seed.The strip liquor caustic sodium concentration can reach more than the 300g/L.After measured, back extraction water can not detect aluminium, illustrates that the extraction agent that adopts does not extract aluminium.
Embodiment three:
Octadecyl phenol with 0.5mol/L is extraction agent, and n-Octanol-kerosene is thinner, the Bayer process mother liquid evaporation of 1 times of volume of extraction, and the causticity ratio is 3.18, caustic sodium concentration is 232g/L, the extraction agent of 5 times of volumes.Extract under 80 ℃ of conditions, churning time was controlled at 10 minutes, after reaction is finished, and oily water separation.Isolated oil phase places the back extraction groove to stir back extraction with the water of 1 times of volume, and temperature is controlled at 80 ℃, and the back extraction time was controlled at 10 minutes equally.After reaction is finished, oily water separation.The regenerated extraction agent recycles.So circulation is 4 times, and final, raffinate causticity ratio is 1.88, can be used for seed and decomposes.Back extraction water caustic sodium concentration is 115g/L, and by analysis, back extraction water can not detect aluminium, illustrates that the extraction agent that adopts does not extract aluminium.If Bayer process seed decomposition nut liquid is concentrated into Na in advance
2O
k360g/L, raffinate causticity ratio can reach 1.5, and then strip liquor concentration can reach more than the 300g/L.
Claims (8)
1. a method that improves producing aluminium oxide circulating efficiency by Bayer process is to adopt liquid-liquid extraction to extract sodium hydroxide from the Bayer process circulation fluid, reduces its causticity ratio, thereby strengthens the method that seed decomposes and improve Bayer process systemic circulation efficient and aluminum oxide productive rate; The operation steps that it is characterized in that method is followed successively by:
A. be 100-400g/L with the caustic alkali naoh concentration, caustic ratio is in the Bayer process circulation fluid of 2.0-4.2, add be selected from Fatty Alcohol(C12-C14 and C12-C18), be a kind of extraction agent in the induced by alkyl hydroxybenzene of mixture diluted dilution agent of the alkane of 6-18 carbon or kerosene and Fatty Alcohol(C12-C14 and C12-C18) with carbon chain lengths, under 60-100 ℃ of temperature, the mechanical stirring extraction is 2-20 minute in extraction tank;
B. after extractive reaction is finished, oily water separation;
C. isolated oil phase is squeezed in the back extraction groove, with water or concentration less than the low neutralizing treatment waste liquid of the NaOH dilute solution of 7mol/L or aluminum oxide industry washing aluminium hydroxide product as strippant, under 60-100 ℃ of temperature, stir back extraction 2-20 minute;
D. after the back extraction reaction is finished, oily water separation; Isolated oil phase is squeezed in the extraction tank that step a carried again, once more extraction;
E. the order of a-d so circulates for several times set by step;
The caustic ratio of the bayer's process circulation fluid among the f. final step a is reduced to 1.4, and direct dilution is used for the seed decomposition and produces sandy alumina.
2. a kind of method that improves producing aluminium oxide circulating efficiency by Bayer process according to claim 1, when it is characterized in that back extraction water caustic alkali naoh concentration height is for 200-300g/L among the step c, be directly used in stripping bauxite or be used for high pressure aquation method exsolution red mud.
3. a kind of method that improves producing aluminium oxide circulating efficiency by Bayer process according to claim 1 is characterized in that the Bayer process circulation fluid is meant the sodium aluminate solution in the aluminum oxide production process, includes lithium, sodium, potash metal ion in the solution.
4. a kind of method that improves producing aluminium oxide circulating efficiency by Bayer process according to claim 1 is characterized in that in the Bayer process circulation fluid adding extraction agent that the extraction process of extraction agent adopts and is carbon chain lengths and be 6～20 Fatty Alcohol(C12-C14 and C12-C18) or their mixture.
5. a kind of method that improves producing aluminium oxide circulating efficiency by Bayer process according to claim 1 is characterized in that the extraction agent of the extraction process employing of adding extraction agent in the Bayer process circulation fluid is a n-Octanol.
6. a kind of method that improves producing aluminium oxide circulating efficiency by Bayer process according to claim 1, it is characterized in that in the Bayer process circulation fluid adding extraction agent that the extraction process of extraction agent adopts and be carbon chain lengths and be the induced by alkyl hydroxybenzene after the mixture diluted of the alkane of 6-18 carbon or kerosene and Fatty Alcohol(C12-C14 and C12-C18), position on the alkyl substituted benzene ring is ortho position, a position and contraposition, and single alkyl branches length is 13-18 carbon; The thinner of induced by alkyl hydroxybenzene extraction agent is that carbon chain lengths is the alkane of 6-18 carbon or the mixture of kerosene and Fatty Alcohol(C12-C14 and C12-C18).
7. a kind of method that improves producing aluminium oxide circulating efficiency by Bayer process according to claim 1, it is characterized in that adding in the Bayer process circulation fluid in the extraction process of extraction agent, it is pure water that isolated oil phase is squeezed into the strippant that back extraction is adopted in the back extraction groove.
8. a kind of method that improves producing aluminium oxide circulating efficiency by Bayer process according to claim 1, it is characterized in that adding in the Bayer process circulation fluid in the extraction process of extraction agent, it is that concentration is less than the NaOH dilute solution of 7mol/L or the low neutralizing treatment waste liquid of aluminum oxide industry washing aluminium hydroxide product that isolated oil phase is squeezed into the strippant that back extraction is adopted in the back extraction groove.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610000862XA CN100418884C (en) | 2006-01-16 | 2006-01-16 | Process for raising producing aluminium oxide circulating efficiency by Bayer process |
| PCT/CN2006/003313 WO2007082447A1 (en) | 2006-01-16 | 2006-12-06 | Method for improving cycle efficiency of bayer process alumina production |
| AU2006336147A AU2006336147B2 (en) | 2006-01-16 | 2006-12-06 | Method for improving cycle efficiency of Bayer process alumina production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610000862XA CN100418884C (en) | 2006-01-16 | 2006-01-16 | Process for raising producing aluminium oxide circulating efficiency by Bayer process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1792799A CN1792799A (en) | 2006-06-28 |
| CN100418884C true CN100418884C (en) | 2008-09-17 |
Family
ID=36804472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610000862XA Active CN100418884C (en) | 2006-01-16 | 2006-01-16 | Process for raising producing aluminium oxide circulating efficiency by Bayer process |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100418884C (en) |
| AU (1) | AU2006336147B2 (en) |
| WO (1) | WO2007082447A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336424A (en) * | 2010-07-16 | 2012-02-01 | 中国科学院过程工程研究所 | Method for separating sodium and aluminum in circulation lye of Bayer process |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398446C (en) * | 2006-08-14 | 2008-07-02 | 中国铝业股份有限公司 | Method of reducing aluminium oxide production refined liquid alpha k by liquid-liquid extraction |
| CN100412012C (en) * | 2006-10-13 | 2008-08-20 | 中国铝业股份有限公司 | Method of treating red mud by extracting Bayer method mother liquid |
| CN101607724B (en) * | 2008-06-19 | 2010-12-15 | 北京化工大学 | Method for dissolving out alumina in bauxite by using sodium hydroxide |
| CN102336423B (en) * | 2010-07-16 | 2013-07-10 | 中国科学院过程工程研究所 | Method for alumina separation in chromium salt clean production |
| CN104803392B (en) * | 2015-05-08 | 2017-08-25 | 南京大学 | Sodium hydroxide efficiently separates the method with circulating and recovering in a kind of alkaline sodium silicate |
| CN104973607B (en) * | 2015-07-30 | 2017-10-20 | 江苏南大环保科技有限公司 | A kind of method that continuous extraction from flyash produces quick dissolved sodium silicate |
| CN107986308B (en) * | 2017-12-29 | 2019-10-01 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of workshop system and technique stewing mould liquid production aluminium hydroxide |
| CN110040752A (en) * | 2019-04-29 | 2019-07-23 | 贵州大学 | A method of improving digesting efficiency of alumina in high titanium bauxite |
| CN113912093B (en) * | 2021-09-29 | 2022-09-09 | 靖西天桂铝业有限公司 | Method for thickening evaporation mother liquor and discharging sodium carbonate salt in alumina production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380253A (en) * | 2002-05-17 | 2002-11-20 | 中国铝业股份有限公司 | Alumina production process by using monohydrate bauxite lime Bayer process |
| CN1405088A (en) * | 2002-11-12 | 2003-03-26 | 中国铝业股份有限公司 | Alkali-compensating method in process of aluminium oxide |
| CN1594093A (en) * | 2004-06-25 | 2005-03-16 | 中国铝业股份有限公司 | Red mud dealkalization method at normal pressure by Bayer process |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB748610A (en) * | 1952-07-16 | 1956-05-09 | Diamond Alkali Co | Improvements in or relating to a method for treating alkali metal chromates |
| GB749097A (en) * | 1953-04-21 | 1956-05-16 | Diamond Alkali Co | Improvements in or relating to a method for treating alkali metal chromates |
| FR2614887B1 (en) * | 1987-05-06 | 1990-11-30 | Rhone Poulenc Chimie | LIQUID-LIQUID EXTRACTION GALLIUM RECOVERY PROCESS |
| US6322702B1 (en) * | 1999-09-23 | 2001-11-27 | U.T. Battlle, Llc | Solvent and process for recovery of hydroxide from aqueous mixtures |
-
2006
- 2006-01-16 CN CNB200610000862XA patent/CN100418884C/en active Active
- 2006-12-06 AU AU2006336147A patent/AU2006336147B2/en active Active
- 2006-12-06 WO PCT/CN2006/003313 patent/WO2007082447A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380253A (en) * | 2002-05-17 | 2002-11-20 | 中国铝业股份有限公司 | Alumina production process by using monohydrate bauxite lime Bayer process |
| CN1405088A (en) * | 2002-11-12 | 2003-03-26 | 中国铝业股份有限公司 | Alkali-compensating method in process of aluminium oxide |
| CN1594093A (en) * | 2004-06-25 | 2005-03-16 | 中国铝业股份有限公司 | Red mud dealkalization method at normal pressure by Bayer process |
Non-Patent Citations (2)
| Title |
|---|
| 强化过饱和铝酸钠溶液种分过程的研究进展. 赵继华，陈启元，张平民，李洁.轻金属，第4期. 2000 |
| 强化过饱和铝酸钠溶液种分过程的研究进展. 赵继华，陈启元，张平民，李洁.轻金属，第4期. 2000 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336424A (en) * | 2010-07-16 | 2012-02-01 | 中国科学院过程工程研究所 | Method for separating sodium and aluminum in circulation lye of Bayer process |
| CN102336424B (en) * | 2010-07-16 | 2013-10-16 | 中国科学院过程工程研究所 | Method for separating sodium and aluminum in circulation lye of Bayer process |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2006336147B2 (en) | 2011-05-12 |
| AU2006336147A1 (en) | 2007-07-26 |
| WO2007082447A1 (en) | 2007-07-26 |
| CN1792799A (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100418884C (en) | Process for raising producing aluminium oxide circulating efficiency by Bayer process | |
| AU2013351773B2 (en) | Monazite ballast separation and recovery method | |
| CN102557085B (en) | Method for extracting sodium salt in cesium salt and rubidium salt production process | |
| CN102127642B (en) | Method for enriching rare-earth elements from red mud | |
| CN106319218A (en) | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum and silicon wastes | |
| WO2022116870A1 (en) | Method for recovering rare earths from waste cerium-based rare-earth polishing powder by two-step acid leaching stepwise separation | |
| CN103215463B (en) | Method for decomposing bastnaesite through calcification transformation-leaching | |
| CN102815844B (en) | Method for pretreating coal chemical industry production waste water and recycling resources of waste water | |
| CN103146921A (en) | Method for removing aluminum in rare-earth solution | |
| CN105293806A (en) | T acid separation mother liquor waste water comprehensive treatment method | |
| CN107475540A (en) | A kind of technique of titanium white devil liquor recovery vanadium and titanium | |
| CN102757062B (en) | Method for extracting boron from magnesium-containing saline lake bittern | |
| CN101353213B (en) | Method for treating octanol waste lye by miscellaneous alcohol acidization-extraction method | |
| CN110407686A (en) | A method of the separating naphthenic acid from mixing organic matter | |
| CN104803392B (en) | Sodium hydroxide efficiently separates the method with circulating and recovering in a kind of alkaline sodium silicate | |
| CN102320620B (en) | Method for preparing 4A zeolite by using alumina red mud | |
| CN102874848A (en) | Method for recovering sodium bicarbonate and organic acid sodium salt from cyclohexanone waste alkali solution | |
| CN106745444B (en) | Treatment method of T acid industrial wastewater | |
| CN105420521A (en) | Organic phase extraction and rare-earth separation process | |
| CN106892479A (en) | A kind of method that oxalic acid and hydrochloric acid are reclaimed in the waste water from rare earth oxalate precipitate | |
| CN107758719A (en) | A kind of environmentally friendly extracting process of high-purity ceria | |
| CN103589861B (en) | Method for microwave sulfating roasting-water leaching treatment of jarosite slag | |
| CN102336424B (en) | Method for separating sodium and aluminum in circulation lye of Bayer process | |
| CN100398446C (en) | Method of reducing aluminium oxide production refined liquid alpha k by liquid-liquid extraction | |
| CN111944998A (en) | Method for removing aluminum from rare earth feed liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20151223 Address after: 450041 No. 82, Jiyuan Road, Zhengzhou District, Henan Patentee after: ZHENGZHOU NON-FERROUS METALS RESEARCH INSTITUTE CO., LTD. OF CHALCO Address before: 100814, Haidian District, Fuxing Road, Beijing No. 12, China Aluminum Limited by Share Ltd Patentee before: Aluminum Corporation of China Limited |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 450041 No. 82, Jiyuan Road, Zhengzhou District, Henan Patentee after: China Aluminum Zhengzhou Research Institute of Nonferrous Metals Co., Ltd. Address before: 450041 No. 82, Jiyuan Road, Zhengzhou District, Henan Patentee before: ZHENGZHOU NON-FERROUS METALS RESEARCH INSTITUTE CO., LTD. OF CHALCO |
|
| CP01 | Change in the name or title of a patent holder |