CN114261979B - Method for producing industrial-grade soda ash by treating arsenic-alkali residue through composite freezing separation of arsenic-alkali - Google Patents
Method for producing industrial-grade soda ash by treating arsenic-alkali residue through composite freezing separation of arsenic-alkali Download PDFInfo
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- CN114261979B CN114261979B CN202111642144.3A CN202111642144A CN114261979B CN 114261979 B CN114261979 B CN 114261979B CN 202111642144 A CN202111642144 A CN 202111642144A CN 114261979 B CN114261979 B CN 114261979B
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- 239000003513 alkali Substances 0.000 title claims abstract description 85
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 48
- 238000007710 freezing Methods 0.000 title claims abstract description 41
- 230000008014 freezing Effects 0.000 title claims abstract description 41
- 238000000926 separation method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 235000017550 sodium carbonate Nutrition 0.000 title claims description 20
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 96
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000011734 sodium Substances 0.000 claims abstract description 80
- 239000013078 crystal Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000001704 evaporation Methods 0.000 claims abstract description 26
- 230000008020 evaporation Effects 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- ILQVBBLTJMJIPG-UHFFFAOYSA-N arsoric acid;hydrate Chemical compound O.O[As](O)(O)=O ILQVBBLTJMJIPG-UHFFFAOYSA-N 0.000 claims abstract description 18
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 claims abstract description 8
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000012452 mother liquor Substances 0.000 claims description 29
- 239000002893 slag Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 21
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 9
- 238000004537 pulping Methods 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 238000010009 beating Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229940047047 sodium arsenate Drugs 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229940001593 sodium carbonate Drugs 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000012432 intermediate storage Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229940018038 sodium carbonate decahydrate Drugs 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 yield about 45% Substances 0.000 description 1
Images
Classifications
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- 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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A process for preparing industrial sodium carbonate from the As-alkali dregs generated by treating As-alkali dregs by composite freezing separation includes such steps as adding water to As-alkali dregs, beating cyclically, depositing impurities, press filtering, crystallizing the As-contained alkali liquid by stirring at controlled temp to obtain arsenate hydrate crystal, freezing, laying aside, crystallizing and separating Na 2 CO 3 ·10H 2 Wet crystal of O, arsenate hydrate crystal and Na 2 S solution precipitating arsenic and Na 2 CO 3 ·10H 2 Carrying out multi-effect evaporation after redissolving O wet crystals to precipitate Na in a supersaturated manner 2 CO 3 ·1H 2 And (4) carrying out centrifugal separation on the O crystals, and drying the crystals to obtain the industrial-grade sodium carbonate, so that the alkali in the arsenic alkali residue is harmless and is recycled. The method of the invention treats the arsenic alkali residue, forms an independent system, can comprehensively recover valuable alkali in the arsenic alkali residue, non-ferrous metal and rare metal, and the rest arsenic can produce arsenic trioxide products, and no waste water, waste residue and waste gas are discharged in the process, more importantly, the method can be used for large-scale low-cost industrialized production.
Description
Technical Field
The invention belongs to the environmental protection and inorganic chemical technology, relates to the soda production, freezing crystallization and multi-effect evaporation technology, and particularly relates to a method for producing industrial soda by treating arsenic-alkali residue through composite freezing separation of arsenic-alkali.
Background
The arsenic alkali slag is arsenic-antimony-containing slag produced in the antimony industry during the arsenic removal of crude antimony refining, is commonly called as 'primary' high-antimony arsenic alkali slag, and comprises the following typical components in parts by weight: 4 to 12 percent of As, 10 to 35 percent of Sb and the balance of Na 2 CO 3 And Na 2 O, and the like. When smelting in a reverberatory furnace for recovering antimony and arsenic smoke dust, a large amount of soda ash is used to produce 'rare slag' to produce low-antimony and arsenic alkaline slag, commonly called 'secondary' arsenic alkaline slag, which comprises the following typical components (by weight): 4 to 8 percent of As, 2 to 6 percent of Sb, 0.5 to 1.5 percent of Pb, 0.6 to 1.5 percent of Sn, 0.05 to 0.2 percent of Te, 0.02 to 0.06 percent of In, 0.005 to 0.03 percent of Ag and the balance of Na 2 Co 3 And Na 2 O, the output of the former is about 20-30% of that of the latter, and in order to recover precious antimony resources, the primary arsenic alkali slag is generally reduced and smelted in a reverberatory furnace to recover antimony, and the produced slag is changed into secondary arsenic alkali slag.
In the past, a great deal of research and exploration are made by predecessors aiming at 'primary' arsenic alkali slag, while the research on 'secondary' arsenic alkali slag is rare, and a classical process method comprises a 'Hunan tin mine mixed sodium arsenate open-circuit method', and the method exits the market because the sales market of the produced mixed sodium arsenate is strictly controlled and protected in an environment-friendly way; the method for separating arsenic and alkali from sodium carbonate in south-depression in Guangdong is difficult to industrialize due to high production cost and low recovery rate; the water of Hunan Chenxi mining industry is used for leaching arsenic alkali, desulfurizing smelting flue gas, adding iron salt to remove arsenic, and the arsenic-iron slag is safely solidified to remove arsenic, and then is sent to landfill, and the method has the waste treated and waste treatedGood benefits, but still has the inherent hidden trouble of the landfill method. Recent patent CN111118301B of Leishui corporation, a method for recycling and treating alkaline residue resources by arsenic and alkali in a freezing separation alkaline residue water leaching solution, introduces a method for treating arsenic-alkaline residue by physically separating arsenic and alkali, and finds that Na separated by primary and secondary freezing of the method is found in the large-scale industrialized application process 2 CO 3 ·10Na 2 The O wet crystals contain high arsenic (As is 0.5-1.5%), wherein the arsenic cannot be reduced to below the 0.05% standard in the subsequent water-soluble freezing recrystallization purification process; the produced sodium carbonate decahydrate product is self-dissolved into a liquid state at the temperature of over 30 ℃ due to containing a large amount of crystal water, and is not easy to store and use; after the waste water produced in the process is converted by lime, the produced gypsum slag contains trace arsenic and cannot be stockpiled like common solid waste, and the technology has the need of iterative upgrading.
Disclosure of Invention
The invention aims to provide a method for producing industrial-grade calcined soda by treating arsenic-alkali residue through composite freezing separation of arsenic-alkali residue, aiming at the problems in the research on secondary arsenic-alkali residue in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for producing industrial-grade soda ash by treating arsenic-alkali residue through composite freezing separation of arsenic-alkali, which comprises the following steps:
the method comprises the following steps: adding water into the arsenic alkali residue, performing ball milling and circular pulping in a ball mill, wherein the weight ratio of the arsenic alkali residue to the water is 1: 1 to 2.5, all Na in the arsenic alkali residue 2 CO 3 And a portion of the arsenate is dissolved in water; wherein the pulping temperature is 20-55 ℃, and the ball milling fineness is 20-100 meshes.
The raw material arsenic alkali residue in the method of the invention is secondary arsenic alkali residue, and the composition of the components is shown in the background technology.
Step two: adding Na accounting for 0.05 to 0.2 percent of the weight of the slurry 2 Continuously pulping S solid, stirring for reaction for 10-30 min, and then performing filter pressing to enable heavy metal salts such as Sb, Pb and Zn dissolved in the S solid to generate sulfide precipitate which is filtered and removed, and sending filter residues to a fuming furnace for recycling, wherein the obtained filtrate is arsenic-containing alkali liquor, and generally5 to 18g/L, Na of As 2 CO 3 100-180 g/L for standby.
Step three: cooling the arsenic-containing alkaline liquor obtained by filtering to 20 +/-1.5 ℃, slowly stirring (the rotation speed of a main shaft is 5-10 rpm) for a long time (6-12 hours) at the constant temperature of 20 +/-1.5 ℃ until partial arsenate hydrate crystals (containing 12-16 wt%) are separated out, and separating out the crystals and mixing Na into the arsenic-containing hydrate crystals under the subsequent freezing condition 2 CO 3 ·10H 2 In the separation of the arsenic from the alkali, the separation effect of the arsenic from the alkali is seriously influenced. Performing centrifugal separation to obtain arsenate hydrate wet crystals containing 12-16% of As, wherein the yield is 2-4%, temporarily storing the wet crystals for subsequent dearsenization treatment, and obtaining clear liquid for later use;
step four: freezing the clear liquid at the freezing point (0-1 ℃) in batches, standing and crystallizing to separate arsenic alkali for about 0.2-1.5 hours to produce Na 2 CO 3 ·10H 2 The size of the O crystal grains reaches 0.2-2 mm; centrifugal separation to produce primary Na containing As 0.05-0.1 wt% 2 CO 3 ·10H 2 O wet crystal, the yield is 40-45%, and the separated mother liquor is evaporated and concentrated to ensure that Na in the mother liquor 2 CO 3 The content is 180-200 g/L, and the arsenic concentration is increased.
Step five: cooling the concentrated mother liquor to 20 +/-1.5 ℃, slowly stirring for a long time (6-12 hours) at the constant temperature of 20 +/-1.5 ℃ at the main shaft rotating speed of 5-10 rpm to separate out partial arsenate hydrate crystals (containing 12-16% of As), and centrifugally separating to obtain wet crystals and clear liquid of secondary arsenate hydrate;
step six: freezing the clear liquid obtained in the step five at a freezing point (0-1 ℃) in batches, standing and crystallizing, and separating arsenic alkali for about 0.2-1.5 hours; centrifugal separation to separate out frozen mother liquor and secondary Na containing As 0.5% -1% (wt) 2 CO 3 ·10H 2 O wet crystal, wherein the wet crystal yield is 30-35%;
step seven: mixing the centrifugal separation freezing mother liquor produced in the sixth step with the primary arsenate hydrate wet crystal produced in the third step and the secondary arsenate hydrate wet crystal produced in the fifth step, and firstly adding H under the stirring condition 2 SO 4 Adjusting the pH value1-2, and then adding Na with the mass concentration of 10-15 percent 2 S solution, yield yellow As immediately 2 S 5 Precipitation, the chemical reaction formula of which is as follows: 2Na 3 AsO 4 +5Na 2 S+8H 2 O＝As 2 S 5 ↓ +16NaOH is produced in the arsenic deposition process, which causes the pH value of the solution to rise, and H needs to be added continuously 2 SO 4 Adjusting the pH value to maintain the pH value between 1 and 2 all the time to ensure the produced As 2 S 5 Can not re-dissolve, and when the solution is clarified, Na is dripped into the solution again 2 And S solution, no yellow precipitate is produced, which indicates that arsenic is completely precipitated and reaches the end point of the reaction.
The solution after arsenic precipitation is filtered and separated to obtain arsenic slag As 2 S 5 And dearsenicating clear solution. Arsenic slag As 2 S 5 Containing 15-35 wt% As, and feeding into an oxidation roasting furnace to produce arsenic trioxide product, harmless and recycling open-circuit treatment. The arsenic-removing clear liquid separated by filter pressing contains a large amount of Na 2 SO 4 And 0.001 g-0.05 g/L of As, and carrying out multi-effect evaporation to evaporate, concentrate and oversaturate to separate out Na 2 SO 4 A crystal; centrifuging to obtain Na 2 SO 4 Wet crystal and mother liquor, the mother liquor is repeatedly multi-effect evaporated, closed circulation treatment is carried out, no waste water discharge is ensured, and Na is ensured 2 SO 4 The As content of the product meets the requirement. Na (Na) 2 SO 4 Drying the wet crystal (the drying temperature is controlled to be 160-180 ℃), and obtaining Na 2 SO 4 The product contains water 1-1.5 wt% and Na 2 SO 4 94 to 96 percent (weight) and 0.001 to 0.005 percent (weight) of As, which are qualified sodium sulfate products, meet the technical requirements of related products and are sold on the market for open circuit.
Step eight: adding primary Na in the fourth step 2 CO 3 ·10H 2 O wet crystal and secondary Na in step six 2 CO 3 ·10H 2 Carrying out multi-effect evaporation after the O wet crystals are re-dissolved together to evaporate, concentrate, oversaturate and separate out Na 2 CO 3 ·1H 2 O crystal, control of Na in heavy solution 2 CO 3 The mass concentration is 26-30%, and the evaporation concentration multiplying power is 4-6 times;
step nine: centrifugally separating the crystal slurry obtained after the eight-effect evaporation to obtain heavy wet crystal Na with the water content of about 4 percent 2 CO 3 ·1H 2 O, drying the wet crystal (160-180 ℃) to obtain an industrial-grade sodium carbonate product, wherein the product contains Na 2 CO 3 92-96 wt% and As 0.005-0.05 wt%, and centrifuging to separate wet crystal Na 2 CO 3 ·1H 2 And D, returning the mother liquor of the O to the step five for cyclic closed-loop treatment with the concentrated mother liquor due to arsenic enrichment, removing arsenic and recovering alkali.
The method of the invention uses composite freezing to separate arsenic alkali and uses a re-dissolving evaporation recrystallization purification process to produce the product containing 0.005-0.05% (weight) of arsenic and Na 2 CO 3 92-96 wt% of heavy industrial soda ash can be safely and widely used for fluxing and slagging in the smelting industry, so that the alkali in the arsenic alkali slag is harmlessly recycled, and the rest of the alkali accounting for about 15-25 wt% can produce international Na 2 SO 4 And (3) after the arsenic alkali slag is soaked in water, filter pressing residues are sent into a fuming furnace of a smelting enterprise, colored and rare and scattered metals are further recovered, the high-arsenic vulcanized slag produced in the process is sent to a professional arsenic enterprise, and an international arsenic trioxide product produced by oxidizing roasting is sold and opened. Compared with the prior art, such as a 'water gap mountain method', a 'Guangdong Yunan method' and a 'Hunan Xixi method', has obvious technical advantages, can treat arsenic-alkali slag in a harmless and resource way at low cost on a large scale, has no hidden danger of waste water and waste residue discharge, and does not depend on SO of smelting flue gas 2 Compared with CN111118301B, the method for recycling arsenic alkali residue by arsenic and alkali in the water extract of freezing separation alkali residue can avoid the problems that the product is not easy to transport, store and use, the produced paste residue has secondary pollution hidden trouble and the like. The method of the invention disposes the arsenic alkali slag, forms an independent system, can comprehensively recover valuable alkali in the arsenic alkali slag, non-ferrous metal and rare metal contained in the arsenic alkali slag, can produce arsenic trioxide products from the rest arsenic, does not discharge waste water, waste residue and waste gas in the process, and more importantly, can implement large-scale low-cost industrialized production.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
The method is implemented in an enterprise of Leishui river Yang, and the details are as follows:
the method comprises the following steps: the enterprise has a production workshop for daily processing 150 tons of arsenic alkaline residue, and the main equipment comprises a storage bin, a groove type feeder, a belt conveyor, a hammer crusher (800X 800 type), a ball mill (220KW type), and a circulating stirring tank (50 m) 3 X 3), plunger pump, filter press (120 square meters × 2), middle storage tank (150 m) 3 ) Main pump for delivery of fine pressure filter (40 square meters) and transfer storage tank (50 m) 3 Type/h.30 m). Adding water into the arsenic alkali residue, adding the water into a ball mill, performing circulating pulping water leaching, and controlling the operation conditions: the weight ratio of the arsenic alkali slag to the water is 1: 1.75, abrasive particle size 60 mesh, temperature 30 ℃.
Step two: adding Na in an amount of 0.1% by weight based on the weight of the slurry to the slurry 2 S solid is continuously and circularly pulped and stirred to react for about 30 minutes, the dissolved impurity metal salts of Sb, Pb, Zn and the like are precipitated, filter pressing is carried out, filter pressing residues are sent to a fuming furnace of an enterprise to recover colored and scattered metals, and the product containing As 6g/L, Na is produced 2 CO 3 180g/L of arsenic-containing alkali liquor is conveyed to an intermediate storage tank for temporary storage for later use after being subjected to filter pressing by a secondary fine filter press.
Step three: the enterprise has a compound arsenic-alkali freezing and separating workshop, and the main equipment comprises a large alkali liquor storage tank 150m 3 Arsenic separating tank (25 m) with temperature-controlled stirring 3 X 2), vertical freezing crystallization unit (phi 600X 3000X 96), screw refrigerating unit, stirring coil evaporator (20 m) 3 X 2 pieces), horizontal centrifuge (phi 500X 1 pieces), arsenic precipitating stirring tank (20 m) 3 X 2), arsenic slag filter press (60 square meters x 1), two-effect evaporation tower and one-effect stirring coil evaporation kettle (5T H) 2 o/h type), horizontal centrifuge (phi 400X 1), dryer, stirring coil evaporation kettle (2T H) 2 o/h × 2 stands), soda horizontal centrifuges (Φ 500 × 1 stands), steam dryers, and the like. Pumping the arsenic-containing alkaline solution in the intermediate storage tank into a temperature-controlled stirring arsenic-separating tank, controlling the temperature at 20 +/-1.5 ℃, and startingAnd (3) separating out sodium arsenate hydrate crystals after about 10 hours by using a stirrer with a main shaft rotating speed of 5-10 rpm. The produced arsenic-containing crystal slurry is put into a centrifuge to separate solid and liquid, primary sodium arsenate hydrate crystals containing 14.5 percent (weight) of As are produced, the yield is about 3.2 percent, and the As in the centrifugal clear liquid is about 3g/L, Na 2 CO 3 About 160 g/L.
Step four: injecting the clear liquid into a freezing crystallizer for freezing, standing and crystallizing, wherein the freezing temperature is 0-1 ℃, crystal is produced in 4 batches at time intervals of 0.5 hour, and the produced Na 2 CO 3 ·10H 2 The size of the O crystal grains reaches 0.2-2 mm; centrifugally separating the produced crystal slurry to obtain primary Na with the As content of less than or equal to 0.1 percent (weight) 2 CO 3 ·10H 2 O wet crystal, yield about 45%, Na in separated mother liquor 2 CO 3 The concentration is reduced to 80 g/L; pumping the mother liquor into a stirring coil evaporation kettle for evaporation and concentration to ensure that Na in the mother liquor 2 CO 3 The concentration was increased to 180g/L and As was increased to 6g/L, and evaporation was stopped.
Step five: pumping the concentrated mother liquor to a temperature-controlled stirring arsenic-separating tank, controlling the temperature to be 20 +/-1.5 ℃, starting a stirrer, separating sodium arsenate hydrate crystals after 10 hours when the main shaft rotates at a speed of 5-10 r/min, and performing centrifugal separation to obtain secondary arsenate hydrate wet crystals and clear liquid; the wet crystal of the secondary arsenate hydrate contains 14 percent (weight) of As and is temporarily stored for standby; clear liquid contains As4.5g/L (weight), Na 2 Co 3 170g/L。
Step six: putting the clear liquid obtained in the fifth step into a freezing crystallizer for freezing, standing and crystallizing, wherein the freezing temperature is 0-1 ℃, and crystal is discharged for 3 batches at time intervals of 0.5 hour; the resulting slurry was centrifuged to separate secondary Na containing 0.6% by weight of As 2 CO 3 ·10H 2 O wet crystal, and simultaneously, producing the frozen alkali-containing mother liquor enriched with arsenic.
Step seven: mixing the centrifugal separation freezing mother liquor produced in the sixth step with the primary arsenate hydrate wet crystal produced in the third step and the secondary arsenate hydrate wet crystal produced in the fifth step, putting the mixture into an arsenic precipitation stirring tank, and firstly adding H under the stirring condition 2 SO 4 When the pH value is reduced to 7-8, the adding speed is slowed down, and a large amount of produced CO is avoided 2 The bubbles emerge from the overflow tank, and Na is added when the pH value is reduced to 1-2 2 The S aqueous solution (the mass concentration is 10-15 percent) immediately produces yellow As 2 S 5 Precipitation and new NaOH formation, raising the pH of the solution and requiring the additional addition of H 2 SO 4 Neutralizing to maintain pH value between 1-2 to ensure the produced As 2 S 5 Can not be redissolved; when the solution is clear, Na is again dropped 2 And when no yellow precipitate is generated in the S solution, the arsenic is completely precipitated and the arsenic precipitation endpoint is reached.
The solution after arsenic precipitation is filtered and separated to obtain high arsenic slag As 2 S 5 And dearsenicating clear liquid; high arsenic slag As 2 S 5 Sending the arsenic trioxide to an oxidation roasting furnace to produce qualified arsenic trioxide products for recycling open-circuit sales. Pumping the arsenic-removed clear liquid into a multi-effect evaporator for multi-effect evaporation to oversaturate and separate out Na by evaporation concentration 2 SO 4 Centrifuging the crystal with a centrifuge to obtain Na with water content of about 4% 2 SO 4 Wet crystallization and mother liquor, and the mother liquor is repeatedly subjected to multi-effect evaporation, concentration and crystallization to be subjected to closed cycle treatment. Na (Na) 2 SO 4 Drying the wet crystal in a dryer at 160-180 deg.C to obtain Na 2 SO 4 Product containing Na 2 SO 4 95% (weight), As 0.003% (weight), water 1.2% (weight), is qualified sodium sulfate product, market open circuit.
Step eight: adding primary Na in the fourth step 2 CO 3 ·10H 2 O wet crystal and secondary Na of step six 2 CO 3 ·10H 2 Dissolving O wet crystal into the stirring coil evaporation kettle again, evaporating to concentrate and oversaturate to separate out Na 2 CO 3 ·1H 2 O crystal, control of Na in heavy solution 2 CO 3 The mass concentration is 28 percent, and the evaporation concentration multiplying power is 5 times;
step nine: centrifugally separating the crystal mush obtained after the eight-effect evaporation to obtain Na 2 CO 3 ·H 2 O wet crystal and mother liquor, drying the wet crystal at 160-180 ℃ to obtain industrial-grade sodium carbonate containing Na 2 CO 3 94% by weight, As 0.03% by weight;the mother liquor obtained by the centrifugation in the step returns to the step five to be pumped to a temperature-controlled stirring arsenic-separating tank for arsenic enrichment, and the concentrated mother liquor is subjected to circulation closed-loop treatment.
Example 2
In this example, in order to compare the production effects of different parameter conditions, H is not supplemented in time in step seven 2 SO 4 The pH value is increased to 5-6, the conditions of other parameters are completely the same as those of the example 1, at the moment, the solution is turbid after arsenic precipitation and is not easy to clarify, the mother solution contains 0.5g/L of arsenic after filter pressing, and the produced Na 2 SO 4 The product contains 0.8 percent of As (weight), far exceeds the quality standard requirement, and the importance of strictly controlling the arsenic precipitation condition can be seen.
Claims (10)
1. A method for producing industrial-grade soda ash by treating arsenic-alkali residue through composite freezing separation of arsenic-alkali is characterized by comprising the following steps:
the method comprises the following steps: adding water into the arsenic alkali residue for ball milling and circular pulping, wherein the weight ratio of the arsenic alkali residue to the water is 1: 1-2.5, wherein the pulping temperature is 25-55 ℃;
step two: adding Na accounting for 0.05 to 0.2 percent of the weight of the slurry 2 S, continuously pulping and stirring the solid, enabling heavy metal impurities Sb, Pb and Zn leached out by pulping water to generate sulfide precipitates, carrying out filter pressing to obtain arsenic-containing alkali liquor and filter residues, and taking the arsenic-containing alkali liquor for later use;
step three: cooling the arsenic-containing alkali liquor to 20 +/-1.5 ℃, slowly stirring for a long time to separate out partial arsenate hydrate crystals at the constant temperature of 20 +/-1.5 ℃, and performing centrifugal separation to obtain primary arsenate hydrate wet crystals and clear liquid;
step four: freezing the clear liquid at 0-1 ℃, standing for crystallization, and then performing centrifugal separation to obtain primary Na 2 CO 3 ·10H 2 O wet crystal and mother liquor; evaporating the mother liquor to concentrate Na in the mother liquor 2 CO 3 The content is 180-200 g/L;
step five: cooling the concentrated mother liquor to 20 +/-1.5 ℃, slowly stirring for a long time to separate out partial arsenate hydrate crystals at the constant temperature of 20 +/-1.5 ℃, and performing centrifugal separation to obtain wet crystals and clear liquid of secondary arsenate hydrate;
step six: freezing the clear liquid obtained in the step five at 0-1 ℃, standing for crystallization, and then performing centrifugal separation to obtain secondary Na 2 CO 3 ·10H 2 O wet crystal and freezing mother liquor;
step seven: mixing the frozen mother liquor obtained in the step six with the wet crystals of the primary arsenate hydrate obtained in the step three and the wet crystals of the secondary arsenate hydrate obtained in the step five, and adding H under the stirring condition 2 SO 4 Adjusting the pH value to 1-2, and then adding 10-15% of Na in mass concentration 2 S solution of arsenic to As 2 S 5 Precipitating until the solution is clear, and adding Na again 2 S solution without precipitation output, reaction is finished, and H is added in the arsenic precipitation process 2 SO 4 Adjusting the pH value to be 1-2 all the time; the solution after arsenic precipitation is filtered and separated to obtain arsenic slag As 2 S 5 And a dearsenifying clear solution;
step eight: adding primary Na in the fourth step 2 CO 3 ·10H 2 O wet crystal and secondary Na in step six 2 CO 3 ·10H 2 Carrying out multi-effect evaporation after the O wet crystals are re-dissolved together to evaporate, concentrate and supersaturate to separate out Na 2 CO 3 ·H 2 O crystal, control of Na in heavy solution 2 CO 3 The mass concentration is 26-30%, and the evaporation concentration multiplying power is 4-6 times;
step nine: centrifugally separating the crystal mush obtained after the eight-effect evaporation to obtain Na 2 CO 3 ·H 2 O wet crystal and mother liquor, the mother liquor returns to the step five for circular closed-loop treatment, and the wet crystal is dried to obtain the industrial grade sodium carbonate.
2. The method for producing the industrial-grade soda ash by using the composite freezing separation arsenic-alkali residue to treat the arsenic-alkali residue as claimed in claim 1, wherein in the second step, the filter residue obtained by pressure filtration is sent to a smelting furnace for resource recovery and treatment.
3. The method for producing the industrial-grade soda ash by treating the arsenic-alkali residue through the composite freezing separation of the arsenic-alkali residue As claimed in claim 1, wherein the arsenic-removed clear solution obtained after pressure filtration in the seventh step contains 0.001-0.05 g/L of As.
4. The method for producing the industrial-grade soda ash by treating the arsenic-alkali residue through composite freezing separation of arsenic and alkali as claimed in claim 1, wherein the arsenic-removed clear solution obtained in the seventh step is subjected to multi-effect evaporation to concentrate and oversaturate by evaporation to separate Na 2 SO 4 A crystal; centrifuging to obtain Na 2 SO 4 Wet crystallization and mother liquor, adding Na 2 SO 4 Drying the wet crystal to obtain Na 2 SO 4 The mother liquid returns to the product and is circulated together with the dearsenifying clear liquid to be evaporated in a closed loop and multiple effects.
5. The method for producing industrial-grade soda ash by treating arsenic-alkali residue through composite freezing separation of arsenic-alkali as claimed in claim 4, wherein Na is used as the Na 2 SO 4 The product contains Na 2 SO 4 94％～96％、As 0.001％～0.005％。
6. The method for producing the industrial-grade soda ash by treating the arsenic-alkali residue through the composite freezing separation of the arsenic-alkali as claimed in claim 1, wherein the ball milling fineness during the ball milling pulping in the first step is 20-100 meshes.
7. The method for producing the industrial-grade soda ash by treating the arsenic-alkali residue through the composite freezing separation of the arsenic-alkali as claimed in claim 1, wherein the stirring time in the third step and the fifth step is 6-12 h, and the rotation speed of a main shaft is 5-10 rpm.
8. The method for producing the industrial-grade soda ash by treating the arsenic-alkali residue through composite freezing separation of arsenic alkali as claimed in claim 1, wherein the standing crystallization time in the fourth step and the sixth step is 0.2-1.5 hours, and Na is added 2 CO 3 ·10H 2 The grain size of O is 0.2 to 2 mm.
9. The method for producing industrial-grade soda ash by treating arsenic-alkali residue through composite freezing separation of arsenic and alkali as claimed in claim 1, wherein the arsenic obtained after filter pressing in the seventh step is obtainedSlag As 2 S 5 15-35% of As, and feeding the arsenic trioxide into an oxidation roasting furnace to produce an arsenic trioxide product.
10. The method for producing the industrial-grade soda ash by treating the arsenic-alkali residue through composite freezing separation of the arsenic and the alkali as claimed in claim 1, wherein the product of the industrial-grade soda ash contains Na 2 CO 3 92％～96％、As 0.005％～0.05％。
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