CN106564916B - Prepared using high chromium slag and chromium slag filler production method of recovering sodium carbonate - Google Patents

Prepared using high chromium slag and chromium slag filler production method of recovering sodium carbonate Download PDF

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CN106564916B
CN106564916B CN 201611023887 CN201611023887A CN106564916B CN 106564916 B CN106564916 B CN 106564916B CN 201611023887 CN201611023887 CN 201611023887 CN 201611023887 A CN201611023887 A CN 201611023887A CN 106564916 B CN106564916 B CN 106564916B
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chromium
chromium slag
slag
step
sodium carbonate
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CN 201611023887
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CN106564916A (en )
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许开华
张云河
郭苗苗
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荆门市格林美新材料有限公司
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Abstract

本发明公开了一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法,将干燥的无钙铬渣球磨完成后筛分至150~200目;以液固比3:1~5:1将去离子水和无钙铬渣加入到水热高压釜中,通入CO2气体,反应时间12~24h;反应结束后,停止通入CO2气体,卸压后,将物料进行过滤、洗涤,收集滤渣和滤液;将滤液加热到90~100℃进行蒸发结晶,待溶液中Na+浓度大于190g/L时,冷却至30~40℃,通过过滤得到的白色固体在150℃下进行烘干即得碳酸钠固体;把滤渣放入矿渣干燥机里进行烘干,烘干后即得高熔点尖晶石铬渣填料。 The present invention discloses a method for preparing the preparation of high quality chromium slag and chromium slag filler recovered using sodium carbonate, dried calcium-free after milling is completed chromium slag sieved to 150 to 200 mesh; solid to liquid ratio of 3: 1 to 5 : 1 deionized water and calcium-chromium slag is added to the hydrothermal autoclave, into CO2 gas, reaction time 12 ~ 24h; after completion of the reaction, stopping the flow of CO2 gas, after pressure relief, the material was filtered, washed collecting residue and a filtrate; when the filtrate was heated to 90 ~ 100 ℃ evaporated crystallization, to be a solution of Na + concentration greater than 190g / L, cooled to 30 ~ 40 ℃, by filtration and the resulting white solid was dried ie at 150 ℃ sodium carbonate to obtain a solid; the residue into slag be dried in a dryer, to give after drying a refractory spinel chromium slag filler. 本发明能够对铬渣中的钠铝硅酸盐及含钠铝的低熔无定形粘结物等相进行解离,钠元素以碳酸钠的形式得以回收,把铬渣颗粒上的附着物去掉,利于铬渣粗颗粒的分选,得到高质量填料。 The present invention can be sodium aluminosilicate chromium slag and sodium aluminum low-melting binder and the like amorphous phase dissociation sodium element in the form of sodium carbonate is recovered, the particles deposit on the chromium slag removed , chromium slag facilitate separation of coarse particles, to obtain a high quality filler.

Description

利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法 Prepared using high chromium slag and chromium slag filler production method of recovering sodium carbonate

技术领域 FIELD

[0001] 本发明属于铬渣的清洁处理及资源的循环再利用技术领域,具体涉及一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法。 Circulating the cleaning process resources and [0001] the present invention are chromium slag recycling technology, and in particular relates to a method for preparing the preparation of high quality chromium slag and chromium slag filler recovered using sodium carbonate.

背景技术 Background technique

[0002] 铬及铬化合物是重要无机化工原料,在电镀、鞣革、印染、医药、颜料、催化剂、氧化剂及金属缓蚀剂等方面有着广泛的应用,涉及国民经济15%的商品品种。 [0002] Chromium and chromium compounds is an important inorganic chemicals, has been widely used in electroplating, tanning, dyeing, pharmaceutical, a pigment, a catalyst, an oxidizing agent and a metal corrosion inhibitor, to a variety of goods 15% of the national economy.

[0003] 铬盐目前主要生产方法是铬铁矿无钙焙烧法,每生产一吨铬盐产品产生0.6〜08 吨的铬渣,无钙铬渣中具有铬含量高(Cr2O3,8〜18 %)的特点,为了避免铬渣污染(Cr6+剧毒)及提高资源利用率,铬渣一般经分选后得到粗渣作为填料返回焙烧进行再次提取,但是由于铬渣反复回填焙烧中Na、Al、Si等元素的积累,形成一些钠铝硅酸盐及含钠铝的低熔无定形物,这些物相在返回焙烧时不但易形成偏析液相造成结窑,而且在渣中的尖晶石颗粒间粘结,不能在铬渣分选时使渣中的尖晶石相和钠铝硅酸盐相有效分离,降低了铬渣填料的质量,不利于炉窑顺行。 [0003] The chromium salt is present, the production method of roasting calcium chromite, chromium salt for every ton of product produced 0.6~08 tons chromium slag, chromium slag calcium having a high chromium content (Cr2O3,8~18% ) features, in order to avoid pollution of chromium residue (Cr6 + toxic) and improve resource utilization, generally chromium slag after separation to give the crude residue as a filler was extracted again returns firing, but since the chromium slag backfill repeated calcination Na, Al, and Si is accumulated to form some of the sodium aluminosilicate and sodium aluminum amorphous low melting, easy to form such segregated phase only liquid junction caused when returning firing kiln, and the spinel particles in the slag between the bonding, can not chromium slag in the slag separation of the spinel phase and the effective separation of sodium aluminum silicate phase, reducing the quality of chromium slag filler is not conducive to the furnace along the line.

发明内容 SUMMARY

[0004] 有鉴于此,本发明的主要目的在于提供一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法。 [0004] In view of this, the main object of the present invention is to provide a high-quality prepared using chromium slag and chromium slag filler preparation of sodium carbonate recovery.

[0005] 为达到上述目的,本发明的技术方案是这样实现的: [0005] To achieve the above object, the technical solution of the present invention is implemented as follows:

[0006] 本发明实施例人提供一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法,该方法通过以下步骤实现: [0006] Example embodiments provide a human prepared using high chromium slag and chromium slag filler preparation of sodium carbonate recovered according to the present invention, the method is implemented by the following steps:

[0007] 步骤1:球磨筛分:将干燥的无钙铬渣放入球磨罐中,通过行星球磨进行球磨,球磨完成后筛分至150〜200目; [0007] Step 1: Milling Screening: The dry calcium chromium slag into a ball mill jar, a ball mill planetary ball mill, milled and sieved to complete 150~200 mesh;

[0008] 步骤2:碳化反应:以液固比3:1〜5:1将去离子水和步骤1球磨后的无钙铬渣加入到水热高压釜中,向所述水热高压釜内通入C〇2气体,反应时间12〜24h; [0008] Step 2: carbonation: a liquid to solid ratio of 3: 1 ~ 5: 1 deionized water and calcium Step 1 chromium slag was added after milling to a hydrothermal autoclave, the autoclave to heat the water C〇2 gas into the reaction time 12~24h;

[0009] 步骤3:过滤分离:反应结束后,停止通入CO2气体,所述水热高压釜卸压后,将所述水热高压釜中的物料进行过滤、洗涤,同时收集滤渣和滤液; [0009] Step 3: separated by filtration: After completion of the reaction, stopping the flow of CO2 gas, hydrothermal autoclave after the pressure relief, the hydrothermal autoclave batch was filtered, washed, while collecting the filtrate and residue;

[0010] 步骤4:蒸发结晶:将步骤3所得滤液加热到90〜100°C进行蒸发结晶,待溶液中Na+ 浓度大于190g/L时,将溶液冷却至30〜40°C,进行过滤,把过滤得到的白色固体在150°C下进行烘干即得碳酸钠固体; [0010] Step 4: evaporative crystallization: When the filtrate obtained in step 3 was heated to 90~100 ° C for evaporative crystallization until the Na + concentration in the solution greater than 190g / L, the solution was cooled to 30~40 ° C, filtered, the the resulting white solid was filtered at 150 ° C for drying to give the solid sodium carbonate;

[0011] 步骤5:滤渣烘干:把步骤3所得滤渣放入矿渣干燥机里进行烘干,烘干后即得高熔点尖晶石铬渣填料。 [0011] Step 5: digesting: The residue obtained in step 3 into the slag be dried in a dryer, to give after drying a refractory spinel chromium slag filler.

[0012] 上述方案中,所述步骤2中,选取球料比6 :1〜9 :1,球磨机的转速为300〜400r/ min〇 [0012] In the above embodiment, in the step 2, select the Charge Ratio 6: 1~9: 1, ball mill speed is 300~400r / min〇

[0013] 上述方案中,所述步骤3中,通入CO2气体的压强为0.2〜IMPa,所述水热高压釜的温度为100〜150°C,搅拌速度为200〜500r/min。 [0013] In the above embodiment, the step 3, the CO2 gas into the pressure of 0.2~IMPa, the hydrothermal autoclave temperature of 100~150 ° C, stirring speed 200~500r / min.

[0014] 上述方案中,所述步骤5还包括:通过干燥机布袋收尘器对铬渣细微粉进行收集。 [0014] In the above embodiment, the 5 further comprising the step of: collection of chromium slag fine powders by a dryer bag filter.

[0015] 上述方案中,所述步骤1之前还包括:将称取的铬渣在100〜120°C下烘干10-14h, 获得干燥的无钙铬渣。 [0015] In the above embodiment, before the step 1 further comprising: a chromium slag weighed 10-14h drying at 100~120 ° C, the obtained dried calcium-free chromium slag.

[0016] 与现有技术相比,本发明的有益效果: [0016] Compared with the prior art, the beneficial effects of the invention:

[0017] 本发明能够铬渣中的钠铝硅酸盐及含钠铝的低熔无定形粘结物进行解离,钠元素以碳酸钠的形式得以回收,同时把主相尖晶石表面的附着物去掉,利于铬渣粗颗粒的分选, 得到高质量填料。 [0017] The present invention can chromium slag sodium aluminosilicate and sodium aluminum low-melting amorphous adhesive was dissociated sodium element in the form of sodium carbonate is recovered, while the main surface of the spinel phase removing deposits, chromium slag facilitate separation of coarse particles, to obtain a high quality filler.

附图说明 BRIEF DESCRIPTION

[0018] 图1为本发明实施例提供一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法的流程图; [0018] Example 1 provides a high-quality prepared using chromium slag and chromium slag filler flowchart of a method of preparation of the present invention for recovering sodium carbonate;

[0019] 图2为本发明实施例1提供一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法铬渣XRD物相图。 [0019] FIG 2 Example 1 provides a high-quality prepared using chromium slag and chromium slag filler recovering chromium slag preparation XRD phase sodium carbonate to the present invention of FIG.

具体实施方式 detailed description

[0020] 为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。 [0020] To make the objectives, technical solutions and advantages of the present invention will become more apparent hereinafter in conjunction with the accompanying drawings and embodiments of the present invention will be further described in detail. 应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。 It should be understood that the specific embodiments described herein are only intended to illustrate the present invention and are not intended to limit the present invention.

[0021] 本发明实施例提供一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法, 如图1所示,该方法通过以下步骤实现: [0021] Example embodiments provide a method for preparing a filler using a high chromium slag and chromium slag recovery of sodium carbonate was prepared, and the present invention shown in FIG. 1, the method is implemented by the following steps:

[0022] 步骤1:球磨筛分:将干燥的无f丐络渣放入球磨罐中,通过行星球磨进行球磨,球磨完成后筛分至150〜200目; [0022] Step 1: Milling Screening: The dry residue free envelope f hack into a ball mill jar, a ball mill planetary ball mill, milled and sieved to complete 150~200 mesh;

[0023] 具体地,所述步骤1之前还包括:将称取的铬渣在100〜120°C下烘干10_14h,获得干燥的无钙铬渣。 [0023] Specifically, before the step 1 further comprises: weighing the dried residue chromium 10_14h at 100~120 ° C, the obtained dried calcium-free chromium slag.

[0024] 步骤2:碳化反应:以液固比3:1〜5:1将去离子水和步骤1球磨后的无钙铬渣加入到水热高压釜中,向所述水热高压釜内通入CO2气体,反应时间12〜24h; [0024] Step 2: carbonation: a liquid to solid ratio of 3: 1 ~ 5: 1 deionized water and calcium Step 1 chromium slag was added after milling to a hydrothermal autoclave, the autoclave to heat the water CO2 gas into the reaction time 12~24h;

[0025] 具体地,所述步骤2中,选取球料比6:1〜9:1,球磨机的转速为300〜400r/min。 [0025] Specifically, in the step 2, select the Charge Ratio 6: 1~9: 1, ball mill speed is 300~400r / min.

[0026] 步骤3:过滤分离:反应结束后,停止通入CO2气体,所述水热高压釜卸压后,将所述水热高压釜中的物料进行过滤、洗涤,同时收集滤渣和滤液; [0026] Step 3: separated by filtration: After completion of the reaction, stopping the flow of CO2 gas, hydrothermal autoclave after the pressure relief, the hydrothermal autoclave batch was filtered, washed, while collecting the filtrate and residue;

[0027] 具体地,所述步骤3中,通入⑶2气体的压强为0.2〜IMPa,所述水热高压釜的温度为100〜150°C,搅拌速度为200〜500r/min。 [0027] Specifically, in the step 3, into the pressure of the gas ⑶2 0.2~IMPa, the hydrothermal autoclave temperature of 100~150 ° C, stirring speed 200~500r / min.

[0028] 步骤4:蒸发结晶:将步骤3所得滤液加热到90〜100°C进行蒸发结晶,待溶液中Na+ 浓度大于190g/L时(即溶液出现较多的白色沉淀时),将溶液冷却至30〜40°C,进行过滤,把过滤得到的白色固体在150°C下进行烘干即得碳酸钠固体; [0028] Step 4: evaporative crystallisation: (i.e. more white precipitate was present) The filtrate obtained in step 3 was heated to 90~100 ° C for evaporative crystallization until the Na + concentration in the solution greater than 190g / L, the solution was cooled to 30~40 ° C, filtered, the white solid was filtered to give dried at 150 ° C for give the solid sodium carbonate;

[0029] 步骤5:滤渣烘干:把步骤3所得滤渣放入矿渣干燥机里进行烘干,烘干后即得高熔点尖晶石铬渣填料。 [0029] Step 5: digesting: The residue obtained in step 3 into the slag be dried in a dryer, to give after drying a refractory spinel chromium slag filler.

[0030] 具体地,所述步骤5还包括:通过干燥机布袋收尘器对铬渣细微粉进行收集,以便另行回收处理。 [0030] In particular, said step 5 further comprising: a collection of chromium slag fine powders by a dryer bag filter, in order to separate recycling.

[0031] 实施例1: [0031] Example 1:

[0032] 本发明实施例提供一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法, 该方法为:取某铬盐厂无钙焙烧法产生的铬渣300g,在110°C下烘干12h测试成分如表1所示。 [0032] The embodiments of the present invention provides a high-quality prepared using chromium slag and chromium slag filler production method of recovering sodium carbonate, which is: 300g of chromium slag produced taking a chromium salt calcium roasting method, at 110 ° C 12h drying under test components shown in table 1. 将干燥的络渣放入球磨罐子中,选取球料比6:1用行星球磨机进行球磨,球磨机的转速选择300r/min,球磨完成,过150目的分样筛备用;取150g筛分后铬渣和450ml水,一起加入到2L的水热高压釜中,封上水热高压釜的釜盖,往水热高压釜内通入CO2气体,压强IMPa,水热高压釜的温度为120°C,搅拌300r/min,反应时间12h;反应完成后卸压拆釜,取出反应物料烧杯中,当料液还处于浑浊时,立刻把含有微细颗粒的液相悬浊液倒出过滤,得到过滤渣1,此时烧杯底部已沉淀的粗颗粒单独过滤,得到滤渣2,把滤渣1和滤渣2分别收集烘干后测得成分如表2和表3所示。 The dried residue envelope into a ball mill jar, 6 to select the ball material: 1 planetary ball milling, mill speed selection 300r / min, the completion of ball milling, through a 150-mesh sieve-like back; 150g taken after screening Chromium and 450ml water, was added together 2L hydrothermal autoclave, the autoclave was sealed hydrothermal reactor lid, to heat water within the CO2 gas into the autoclave, the pressure of IMPA, hydrothermal autoclave temperature was 120 ° C, stirring 300r / min, reaction time 12h; after completion of the reaction vessel relief removed, the reaction mass was taken in a beaker, when the material is still in the turbid liquid, a liquid phase immediately decanted suspension containing fine particles was filtered to obtain a filtration residue in this case the bottom of the beaker separate coarse particles precipitated was filtered, to give residue 2 to residue 1 and residue 2 were collected and dried components were measured as shown in table 2 and table 3. 把收集的滤液进行浓缩蒸发,当Na+浓度大于190g/L时即(有大量白色固体出现时)进行冷却结晶,过滤烘干后即得到白色碳酸钠固体。 The filtrate was collected and concentrated by evaporation, when the Na + concentration greater than 190g / L i.e. (with a large amount of white solid appears) crystallization cooled and filtered to give after drying a white solid sodium carbonate. 把干燥原铬渣样品和粗颗粒滤渣2进行XRD物相分析,结果如图2所示,图中a为铬渣原样品、b为粗颗粒滤渣2干料样品;由图2可以看出,经过碳化、粗细颗粒分选后,所得滤渣2为较为纯净的Mg (Fe,Cr,Al) 2〇4的尖晶石相,为高熔点、高质量的焙烧填料。 The dried sample of the original chromium slag and coarse particles residue subjected to XRD phase analysis 2, the results shown in Figure 2, is a chromium slag in FIG original sample, b 2 dry residue sample is coarse material; can be seen from Figure 2, after carbonization, the thickness of the particle sorting, the resulting residue is relatively pure spinel 2 Mg (Fe, Cr, Al) 2〇4 phase, high melting point, high quality calcined filler.

[0033] 表1为干燥原铬渣样品组分表(XRF) [0033] TABLE 1 Chromium sulfate original sample component table (XRF)

[0034] [0034]

Figure CN106564916BD00051

[0035] 表2为细微粉滤渣1组分表(XRF) [0035] Table 2 Table 1 Component fine powder residue (XRF)

[0036] [0036]

Figure CN106564916BD00052

[0037] 表3为粗颗粒滤渣2组分表(XRF) [0037] Table 3 Table 2 Component coarse residue (XRF)

[0038] [0038]

Figure CN106564916BD00053

[0039] 本发明能对返回的铬渣填料进行清洁化处理,回收渣中碳酸钠的同时,得到高熔点含铬尖晶石填料,有助于铬渣中铬的进一步提取及炉窑顺行;通过碳化反应,可使铬渣中含钠物相、无定形物等低熔物中的大部分钠转化为碳酸钠进入溶液,同时把主相含铬尖晶石和钠铝硅酸盐等副相剥离,溶液中的碳酸钠结晶回收;滤渣通过热风炉进行烘干及布袋收尘,相当于进行粗细颗粒的分选,能很好除去铬渣中的硅铝酸盐等副相,避免返回焙烧时与钠再形成低熔物相; [0039] The present invention is capable of cleaning process returns filler chromium slag, slag recovery, while sodium carbonate, to give high-melting chromium-containing spinel filler, and help to further extraction of chromium and chromium anterograde furnace slag ; by carbonizing the reaction, the low-melt slag sodium chromium phase, amorphous, etc. most of the sodium carbonate is converted into solution, while the main phase and a chromium-containing sodium aluminum silicate spinel sub stripping phase, recovering the crystalline sodium carbonate solution; residues by drying stove and dust collector bag, corresponding to the thickness of the particles for sorting, chromium slag in the well was removed aluminosilicates like Kim, avoid returning when the sodium form and then firing the low-melting phase;

[0040] 本发明的设备简单、流程短,所用的CO2原料要求不严格,可取自工厂的炉窑尾气, 实现废气资源高值化利用。 [0040] The present invention is a simple, short process, CO2 required starting material used is not critical and may be taken from the kiln off-gas plant off-gas to achieve efficient utilization of resources.

[0041] 实施例2: [0041] Example 2:

[0042] 本发明实施例提供一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法, 该方法为:取某铬盐厂无钙焙烧法产生的铬渣400g,在120 °C下烘干14h。 [0042] The embodiments of the present invention provides a high-quality prepared using chromium slag and chromium slag filler production method of recovering sodium carbonate, the method: take a chromium salt to produce calcium roasting method chromium slag 400g, 120 ° C for under dry 14h. 将干燥的铬渣放入球磨罐子中,选取球料比6:1用行星球磨机进行球磨,球磨机的转速选择350r/min,球磨完成,过170目的分样筛备用;取200g筛分后铬渣和800ml水,一起加入到2L的水热高压釜中, 封上水热高压釜的釜盖,往水热高压釜内通入CO2气体,压强0.5MPa,水热高压釜的温度为120°C,搅拌350r/min,反应时间12h;反应完成后卸压拆釜,取出反应物料烧杯中,当料液还处于浑浊时,立刻把含有微细颗粒的液相悬浊液倒出过滤,得到过滤渣1,此时烧杯底部已沉淀的粗颗粒单独过滤,得到滤渣2。 The dried chromium slag into a ball mill jar, 6 to select the ball material: 1 planetary ball milling, mill speed selection 350r / min, the completion of ball milling, sieve-like object 170 through the standby; 200g taken after screening Chromium and 800ml water, was added together 2L hydrothermal autoclave, the autoclave was sealed hydrothermal reactor lid, to heat water within the CO2 gas into the autoclave, the pressure of 0.5MPa, hydrothermal autoclave temperature of 120 ° C stirred 350r / min, reaction time 12h; after completion of the reaction vessel relief removed, the reaction mass was taken in a beaker, when the material is still in the turbid liquid, a liquid phase immediately decanted suspension containing fine particles by filtration, the residue was filtered to give 1, appears at the bottom of the beaker coarse particles precipitated was filtered separately, to give residue 2. 把收集的滤液进行浓缩蒸发,当Na+浓度大于190g/L时即(有大量白色固体出现时)进行冷却结晶,过滤烘干后即得到白色碳酸钠固体。 The filtrate was collected and concentrated by evaporation, when the Na + concentration greater than 190g / L i.e. (with a large amount of white solid appears) crystallization cooled and filtered to give after drying a white solid sodium carbonate. 经过碳化、 粗细颗粒分选后,所得滤渣2为较为纯净的Mg (Fe,Cr,Al) 2〇4的尖晶石相,为高熔点、高质量的焙烧填料。 After carbonization, the thickness of the particle sorting, the resulting residue is relatively pure spinel 2 Mg (Fe, Cr, Al) 2〇4 phase, high melting point, high quality calcined filler.

[0043] 实施例3: [0043] Example 3:

[0044] 本发明实施例提供一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法, 该方法为:取某铬盐厂无钙焙烧法产生的铬渣200g,在110°C下烘干10h。 [0044] An embodiment provides a high-quality prepared using chromium slag and chromium slag filler production method of recovering sodium carbonate, the method of the present invention: Take a chromium salt produced calcium roasting method chromium slag 200g, at 110 ° C under dry 10h. 将干燥的铬渣放入球磨罐子中,选取球料比9:1用行星球磨机进行球磨,球磨机的转速选择400r/min,球磨完成,过200目的分样筛备用;取IOOg筛分后铬渣和500ml水,一起加入到2L的水热高压釜中, 封上水热高压釜的釜盖,往水热高压釜内通入CO2气体,压强IMPa,水热高压釜的温度为150 °C,搅拌500r/min,反应时间12h;反应完成后卸压拆釜,取出反应物料烧杯中,当料液还处于浑浊时,立刻把含有微细颗粒的液相悬浊液倒出过滤,得到过滤渣1,此时烧杯底部已沉淀的粗颗粒单独过滤,得到滤渣2。 The dried chromium slag into a ball mill jar, select Charge Ratio 9: 1 ball milled with a planetary ball mill, a ball mill speed selection 400r / min, the completion of ball milling, through a 200-mesh sieve-like back; chromium residue taken after screening IOOg 500ml of water and added to 2L with hydrothermal autoclave, the autoclave was sealed hydrothermal reactor lid, to heat water within the CO2 gas into the autoclave, the pressure of IMPA, hydrothermal autoclave temperature was 150 ° C, stirring 500r / min, reaction time 12h; after completion of the reaction vessel relief removed, the reaction mass was taken in a beaker, when the material is still in the turbid liquid, a liquid phase immediately decanted suspension containing fine particles was filtered to obtain a filtration residue in this case the bottom of the beaker separate coarse particles precipitated was filtered, to give residue 2. 把收集的滤液进行浓缩蒸发,当Na+浓度大于190g/L时即(有大量白色固体出现时)进行冷却结晶,过滤烘干后即得到白色碳酸钠固体。 The filtrate was collected and concentrated by evaporation, when the Na + concentration greater than 190g / L i.e. (with a large amount of white solid appears) crystallization cooled and filtered to give after drying a white solid sodium carbonate. 经过碳化、粗细颗粒分选后,所得滤渣2为较为纯净的Mg (Fe,Cr,Al) 2〇4的尖晶石相,为高熔点、高质量的焙烧填料。 After carbonization, the thickness of the particle sorting, the resulting residue is relatively pure spinel 2 Mg (Fe, Cr, Al) 2〇4 phase, high melting point, high quality calcined filler.

[0045] 以上所述,仅为本发明的较佳实施例而已,并非用于限定本发明的保护范围。 [0045] The above descriptions are merely preferred embodiments of the present invention but are not intended to limit the scope of the present invention.

Claims (5)

  1. 1. 一种利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法,其特征在于,该方法通过以下步骤实现: 步骤1:球磨筛分:将干燥的无I丐络渣放入球磨罐中,通过行星球磨进行球磨,球磨完成后筛分至150〜200目; 步骤2:碳化反应:以液固比3:1〜5:1将去离子水和步骤1球磨后的无钙铬渣加入到水热高压釜中,向所述水热高压釜内通入CO2气体,反应时间12〜24h; 步骤3:过滤分离:反应结束后,停止通入CO2气体,所述水热高压釜卸压后,将所述水热高压釜中的物料进行过滤、洗涤,同时收集滤渣和滤液; 步骤4:蒸发结晶:将步骤3所得滤液加热到90〜IOOtC进行蒸发结晶,待溶液中Na+浓度大于190g/L时,将溶液冷却至30〜40 °C,进行过滤,把过滤得到的白色固体在150 °C下进行烘干即得碳酸钠固体; 步骤5:滤渣烘干:把步骤3所得滤渣放入矿渣干燥机里进行烘干,烘干后即 A method for preparing high chromium slag and recovering sodium carbonate filler was prepared using chromium slag, characterized in that the method implemented by the following steps: Step 1: Milling Screening: The dry residue free I hack into the network milling cans, followed by milling by the planetary ball mill, milled and sieved to complete 150~200 mesh; step 2: carbonation: a liquid to solid ratio of 3: 1 ~ 5: 1 deionized water calcium and chromium in the milling step 1 residue was added to hot water in an autoclave to heat water within the CO2 gas into the autoclave, the reaction time 12~24h; step 3: separated by filtration: after completion of the reaction, stopping the flow of CO2 gas, the hydrothermal autoclave after depressurizing, the hydrothermal autoclave batch was filtered, washed, while collecting the filtrate and residue; step 4: evaporative crystallization: the filtrate obtained in step 3 was heated to 90~IOOtC evaporated crystallization, the solution until the concentration of Na + greater than 190g / L, the solution was cooled to 30~40 ° C, filtered, the solid was filtered and the resulting white solid was dried to obtain sodium carbonate at 150 ° C; step 5: digesting: the resulting step 3 slag residue into the dryer for drying, after drying 高熔点尖晶石铬渣填料。 Chromium high melting spinel filler.
  2. 2. 根据权利要求1所述的利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法,其特征在于,所述步骤1中,选取球料比6:1〜9:1,球磨机的转速为300〜400r/min。 The preparation of high quality using chromium slag and chromium slag filler production method of recovering sodium carbonate according to claim 1, wherein, in the step 1, select the Charge Ratio 6: 1~9: 1, ball mill speed of 300~400r / min.
  3. 3. 根据权利要求1或2所述的利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法, 其特征在于,所述步骤2中,通入CO2气体的压强为0.2〜IMPa,所述水热高压釜的温度为100〜 150°C,搅拌速度为200〜500r/min。 The preparation of high quality using Chromium Chromium production method of claim 1 or 2 and recovering the sodium carbonate filler claim, wherein, in the step 2, into the pressure of CO2 gas 0.2~IMPa, the said temperature hydrothermal autoclave is 100~ 150 ° C, the stirring speed is 200~500r / min.
  4. 4. 根据权利要求3所述的利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法,其特征在于,所述步骤5还包括:通过干燥机布袋收尘器对铬渣细微粉进行收集。 The preparation method using high chromium slag and recovering sodium carbonate filler according to claim 3 prepared chromium slag, characterized in that, said step 5 further comprising: chromium slag fine powders by a dryer bag filter collect.
  5. 5. 根据权利要求4所述的利用铬渣制备高质量铬渣填料和回收碳酸钠的制备方法,其特征在于,所述步骤1之前还包括:将称取的铬渣在100〜120 °C下烘干10-14h,获得干燥的无钙铬渣。 The preparation of high quality using Chromium Chromium filler 4 and the preparation process for recovering sodium carbonate claim, wherein, before the step 1 further comprising: a chromium slag weighed at 100~120 ° C drying under 10-14h, obtained dried calcium-free chromium slag.
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US7128886B2 (en) * 1999-01-08 2006-10-31 Solvay Chemicals, Inc. Sodium carbonate and sodium bicarbonate production from nahcolitic oil shale
CN101767825A (en) * 2009-11-23 2010-07-07 中国科学院过程工程研究所;河南永通镍业有限公司 Method for preparing chromium hemitrioxide by red-soil nickel ore
CN101824530A (en) * 2010-04-08 2010-09-08 白向南;吴龙武;白振轩 Process for roasting chromite resources in ring kiln through pure oxygen by using low-temperature method and harmlessly and deeply utilizing chromium residue
CN102191374A (en) * 2010-03-10 2011-09-21 中国科学院过程工程研究所 Method for recycling traditional chromium residue
CN104762637A (en) * 2015-02-13 2015-07-08 于志远 Comprehensive utilization method and device for acid dissolution extraction of valuable element chromium silicon iron magnesium aluminum nickel from chromite

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US7128886B2 (en) * 1999-01-08 2006-10-31 Solvay Chemicals, Inc. Sodium carbonate and sodium bicarbonate production from nahcolitic oil shale
CN101767825A (en) * 2009-11-23 2010-07-07 中国科学院过程工程研究所;河南永通镍业有限公司 Method for preparing chromium hemitrioxide by red-soil nickel ore
CN102191374A (en) * 2010-03-10 2011-09-21 中国科学院过程工程研究所 Method for recycling traditional chromium residue
CN101824530A (en) * 2010-04-08 2010-09-08 白向南;吴龙武;白振轩 Process for roasting chromite resources in ring kiln through pure oxygen by using low-temperature method and harmlessly and deeply utilizing chromium residue
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