CN110947375B - 用于制备环氧丙烷的催化剂及其制备方法 - Google Patents
用于制备环氧丙烷的催化剂及其制备方法 Download PDFInfo
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- CN110947375B CN110947375B CN201911169794.3A CN201911169794A CN110947375B CN 110947375 B CN110947375 B CN 110947375B CN 201911169794 A CN201911169794 A CN 201911169794A CN 110947375 B CN110947375 B CN 110947375B
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Classifications
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/14—Phosphorus; Compounds thereof
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
本申请公开了一种用于制备环氧丙烷的催化剂,其包含0.05~10wt%的TiO2、0.5~2.9wt%的M1、0.05~0.5wt%的M2,其余成分为SiO2;M1为Al2O3、SO3或Cr2O3中的至少一种;M2为P、W或Mo中的至少一种。还公开了该催化剂的制备方法,步骤为:(Ⅰ)将硅粉、增塑剂、胶粘剂、调胶剂及M2混合,然后成为成型物,将成型物干燥、焙烧后制得硅条;(Ⅱ)向反应器中加入硅条,并送入钛源进行反应,在用含M1的溶液浸泡,完成浸泡后排空;(Ⅲ)用酸液浸泡并排空后,进行清洗,干燥后即制得该催化剂。该催化剂极大提高中间产物异丙苯与α,α‑二甲基苄醇的纯度,以利于物料的充分使用。该方法能够顺利完成该催化剂的生产。
Description
技术领域
本发明涉及一种采用过氧化氢异丙苯氧化法制备环氧丙烷的催化剂及其制备方法,属于催化剂合成领域。
背景技术
环氧丙烷作为基础有机化工原料,广泛用于聚醚、胶黏剂等化工领域。在严峻的环保压力下,传统的氯醇法生产环氧丙烷工艺及设备正逐步替换淘汰乃至关停。在此契机下,工艺流程清洁经济的绿色制备、生产技术逐步开发和工业化。选用关联溶剂稀释有机过氧化物后氧化丙烯制备环氧丙烷工艺发展势态迅猛。过氧化氢异丙苯氧化丙烯制备环氧丙烷的工艺由日本住友化学公司最早开发。此法采用钛硅分子筛为催化剂、过氧化氢异丙苯为氧源,使丙烯环氧化生成环氧丙烷。该法为无污染且技术经济性良好的环境友好型清洁生产工艺。
采用过氧化氢异丙苯氧化氧化法制备环氧丙烷及相关工艺中,钛硅分子筛对烯烃类的选择性氧化具有良好的催化活性,环氧丙烷选择性高,过氧化氢异丙苯转化率好。在整个工艺流程中,原料环氧化反应完成后经分离丙烯和提取环氧丙烷,得到异丙苯和α,α-二甲基苄醇(DMBA)混合液,混合液经氢解还原、再氧化后生成过氧化氢异丙苯,有效实现物料循环使用。实际研究表明:伴随原料环氧化反应完成后的物料脱离钛硅分子筛催化剂进行后续工艺时,α,α-二甲基苄醇会分解成副产物苯乙酮及α-甲基苯乙烯,含有副产物的混合液极不利于循环使用。因此,为保障环氧丙烷制备工艺稳定,在不额外提纯情况下,开发一种环氧丙烷选择性高,过氧化氢异丙苯转化率好,异丙苯和α,α-二甲基苄醇(DMBA)混合液气相纯度高的催化剂极具意义。
发明内容
本申请旨在实现上述目标,提供一种用于过氧化氢异丙苯氧化丙烯制备环氧丙烷的催化机,该催化剂在保证高效的选择性及转化率的基础上,又极大提高中间产物异丙苯与α,α-二甲基苄醇的纯度,以利于物料的充分使用。具体的技术方案为:
一种用于制备环氧丙烷的催化剂,其包含0.05~10wt%的TiO2、0.5~2.9wt%的M1、0.05~0.5wt%的M2,其余成分为SiO2;M1为Al2O3、SO3或Cr2O3中的至少一种;M2为P、W或Mo中的至少一种;催化剂的孔径5~15nm,比表面积150~560m2/g,总量以100wt%计。
该催化剂孔径、比表面积适中,利于反应物与催化剂中活性金属接触及有效离去,提高催化效率,具有良好经济性能。为过氧化氢异丙苯氧化丙烯制备环氧丙烷提供一种高效金属复合型催化剂。
该催化剂添加辅助金属元素M2,既保证钛硅分子筛的高效稳定性又可有效抑制α,α-二甲基苄醇的氧化脱水。在保证催化剂具有良好催化效果的基础上,既不增加额外提纯工艺,又极大降低异丙苯和α,α-二甲基苄醇混合溶液中副产物的含量,确保环氧丙烷整体制备工艺高效稳定进行。
使用本催化剂,过氧化氢异丙苯转化率≥99.9%,环氧丙烷选择性≥99.5%,异丙苯和α,α-二甲基苄醇混合溶液气相纯度≧99.6%。
其次,本申请还提供上述催化剂的制备方法,包括以下步骤:
(Ⅰ)将硅粉、增塑剂、胶粘剂、调胶剂及M2按设定比例混合,挤塑或压塑为具有一定形状的成型物;将成型物于40~140℃干燥10~36h,然后在250~900℃焙烧2.5~17h,制得硅条;
(Ⅱ)向反应器中加入硅条,将反应器内的温度控制在200~900℃,由反应底部汽化器用氮气带入钛源,保持温度4~26h后降至室温;然后将反应器内的温度调整到30~190℃,由反应器顶部泵入含M1的溶液,对硅条进行浸泡,浸泡5~26h后排尽含M1的溶液;
(Ⅲ)将反应器内的温度调整到25~90℃,由反应器顶部泵入酸液,对硅条浸泡4~28h后排尽酸液;将反应器内的温度调整到80~400℃,泵入去离子水清洗至中性后保温干燥10~28h,即制得该催化剂。
该制备方法中选用硅粉,原料易得且廉价,相关指标稳定。调胶剂的加入能有效打破硅胶胶体的电荷平衡,加速凝胶固化。同时调胶剂具有一定的保水和润滑性能,防止水分快速蒸发,提高催化剂整体压碎强度。
汽化带入钛源可有效提高反应均一性,反应温度的有效控制,可降低回流现象造成钛过量堆积。MI从顶部进入能有效提高相关物质的脱除和离去。
酸液的浸泡能有效脱氯及游离的参与金属离子,提高催化剂整体稳定性。
优选地,在该催化剂的制备方法中,
步骤(Ⅰ)中,硅粉、增塑剂、胶粘剂、调胶剂及M2的质量比100:(0.5~10):(50~500):(0.5~5.0):(0.05~5.0)。
步骤(Ⅱ)中,硅条与钛源质量比100:(5~40);硅条与M1溶液质量比100:(400~8000)。
步骤(Ⅲ)中,硅条与酸液质量比100:(500~1000)。硅条与去离子水的质量比100:(500~50000)。
上述方案中,M1为相对稳定的离子溶液,具有良好的均一性,在浸渍过程中还有效交换吸附于硅条上,同时部分带离不稳定的二氧化钛。M2有效的溶解于胶粘剂的水溶液中,和硅粉有效的接触,提高整体分散性。
进一步,步骤(Ⅰ)中,硅粉的孔径5~15nm;比表面积360~820m2/g。
(Ⅰ)中,硅粉为柱层层析硅胶粉、大孔硅胶粉、白炭黑或气相白炭黑中的至少一种;
(Ⅰ)中,增塑剂为羟丙基甲基纤维素、田菁胶、聚乙二醇10000、木质素中的至少一种;
(Ⅰ)中,胶粘剂为硅溶胶或含1~3wt%拟薄水铝石的二氧化硅水溶液,该胶粘剂的二氧化硅的质量浓度在5~60wt%;
(Ⅰ)中,调胶剂为丙二醇、聚乙二醇400、聚乙二醇200或丙三醇中的至少一种;
(Ⅰ)中,M2为磷钨酸、磷钼酸、硅钨酸或硅钼酸中的至少一种;
(Ⅱ)中,钛源为四氯化钛、钛酸四乙酯、钛酸四丙酯或钛酸四丁酯中的至少一种;
(Ⅱ)中,M1的溶液为偏铝酸钠溶液、三氯化铝溶液、硫酸钠溶液、硫酸钾溶液或重铬酸钾溶液中的至少一种;
(Ⅲ)中,酸液为盐酸溶液、硫酸溶液、磷酸溶液或硝酸溶液中的至少一种,酸液的浓度为0.25~1.6moL/L。当酸液为多种酸的混合溶液时,酸液的浓度为各种酸的总浓度。
上述方案中,拟薄水铝石的加入既补充金属源,同时还可提高催化剂的强度,适量的M2均可有效溶解于胶粘剂的水溶液中,适量的酸液可有效交换脱除不稳定金属元素。
具体实施方式
实施例1
将柱层层析硅胶粉(孔径5nm,比表面积820m2/g)100g、羟丙基甲基纤维素3g、含20wt%二氧化硅水溶液500g、0.5g聚乙二醇400及5g磷钨酸充分混合后挤塑成型;将成型物于40℃干燥36h,然后在900℃焙烧2.5h,制得硅条。
其中的二氧化硅水溶液中含1wt%的拟薄水铝石,在使用前,预先将拟薄水铝石加入二氧化硅水溶液中并搅拌均匀。
向反应器中加入焙烧好的硅条100g,反应器控温200℃,由反应底部汽化器用氮气带入四氯化钛40g,保持26h后降温至室温。
再将反应器内的温度调整到30℃,由反应器顶部泵入400g 0.4wt%重铬酸钾溶液进行浸泡,浸泡26h后排尽该溶液。
反应器控温在90℃,由顶部泵入1.6mol/L的盐酸溶液500g,浸4h后排尽盐酸溶液,升温400℃,泵入去离子水50000g清洗至中性后保温干燥10h。所得催化剂标记为Cat1#。
在固定床反应器中装填本发明制备的催化剂,反应压力2MPa,反应温度150℃,过氧化氢异丙苯浓度55wt%,过氧化氢异丙苯体积空速4h-1,丙烯与过氧化氢异丙苯摩尔比15:1。反应完成后经分离器收集环氧丙烷,异丙苯与α,α-二甲基苄醇混合液取样气相分析百分含量后进入后续工艺使用。使用情况标记为CatP1*。此方案仅为评估催化剂方法,本专利不受限于此。
实施例2
将气相白炭黑(孔径15nm,比表面积360m2/g)100g、田菁胶10g、含60wt%二氧化硅水溶液50g、1.5g丙二醇及0.1g磷钼酸充分混合后挤塑成型;将成型物于140℃干燥10h,然后在250℃焙烧17h,制得硅条。
其中的二氧化硅水溶液中含3wt%的拟薄水铝石,在使用前,预先将拟薄水铝石加入二氧化硅水溶液中并搅拌均匀。
向反应器中加入焙烧好的硅条100g,反应器控温900℃,由反应底部汽化器用氮气带入钛酸四丁酯5g,保持4h后降温至室温。
再将反应器内的温度调整到30℃,由反应器顶部泵入8000g0.15wt%硫酸钠溶液进行浸泡,浸泡5h后排尽该溶液。
反应器控温在25℃,由顶部泵入0.2mol/L的硫酸溶液10000g,浸泡28h后排尽硫酸溶液,升温80℃,泵入去离子水500g清洗至中性后保温干燥28h。所得催化剂标记为Cat2#。
在固定床反应器中装填本发明制备的催化剂,反应压力8MPa,反应温度40℃,过氧化氢异丙苯浓度25wt%,过氧化氢异丙苯体积空速0.1-1,丙烯与过氧化氢异丙苯摩尔比5:1。反应完成后经分离器收集环氧丙烷,异丙苯与α,α-二甲基苄醇混合液取样气相分析百分含量后进入后续工艺使用。使用情况标记为CatP2*。
实施例3
将柱层层析硅胶粉(孔径10nm,比表面积590m2/g)100g、聚乙二醇10000和羟丙基甲基纤维素各占50wt的混合物6g、含30wt%二氧化硅的硅溶胶300g、2.25g丙三醇及0.26g硅钨酸充分混合后挤塑成型;将成型物于110℃干燥23h,然后在650℃焙烧4.5h,制得硅条。
向反应器中加入焙烧好的硅条100g,反应器控温550℃,由反应底部汽化器用氮气带入钛酸四乙酯26g,保持10h后降温至室温。
再将反应器内的温度调整到75℃,由反应器顶部泵入600g0.5wt%三氯化铝溶液进行浸泡,浸泡10h后排尽该溶液。
反应器控温在50℃,由顶部泵入0.4mol/L的磷酸溶液4000g,浸泡6h后排尽磷酸溶液,升温140℃,泵入去离子水7000g清洗至中性后保温干燥14h。所得催化剂标记为Cat3#。
在固定床反应器中装填本发明制备的催化剂,反应压力4MPa,反应温度100℃,过氧化氢异丙苯浓度35wt%,过氧化氢异丙苯体积空速2h-1,丙烯与过氧化氢异丙苯摩尔比10:1。反应完成后经分离器收集环氧丙烷,异丙苯与α,α-二甲基苄醇混合液取样气相分析百分含量后进入后续工艺使用。使用情况标记为CatP3*。
实施例4
本实施例与实施例3相同,仅把硅钨酸替换为硅钼酸,其它条件不变。所得催化剂标记为Cat4#。评估方法与实施例3相同,使用情况标记为CatP4*。
实施例5
将大孔硅胶粉(孔径12nm,比表面积470m2/g)100g、聚乙二醇10000和羟丙基甲基纤维素各占50wt%的混合物6g、含30wt%二氧化硅水溶液300g、2.25g丙三醇及0.26g硅钨酸充分混合后挤塑成型;将成型物于60℃干燥18h,然后在400℃焙烧10.5h,制得硅条。
其中的二氧化硅水溶液中含2wt%的拟薄水铝石,在使用前,预先将拟薄水铝石加入二氧化硅水溶液中并搅拌均匀。
向反应器中加入焙烧好的硅条100g,反应器控温350℃,由反应底部汽化器用氮气带入四氯化钛13g,保持12h后降温至室温。
再将反应器内的温度调整到100℃,由反应器顶部泵入600g0.5wt%三氯化铝溶液进行浸泡,浸泡15h后排尽该溶液。
反应器控温在70℃,由顶部泵入0.4mol/L的磷酸溶液2500g,浸泡12h后排尽磷酸溶液,升温200℃,泵入去离子水5000g清洗至中性后保温干燥20h。所得催化剂标记为Cat5#。评估方法与实施例3相同,使用情况标记为CatP5*。
实施例6
本实施例与实施例5相同,仅把磷酸替换为硫酸,四氯化钛的量为30g,硅钨酸的量为0.1g其它条件不变。所得催化剂标记为Cat6#。评估方法与实施例3相同,使用情况标记为CatP6*。
实施例7
该实施例7为对比例。
本实施例与实施例3相同,不同之处在于不再添加拟薄水铝石及硅钨酸,同时将0.5wt%三氯化铝溶液和0.4mol/L的磷酸溶液替换为等量去离子水。所得催化剂标记为Cat7#。评估方法与实施例3相同,使用情况标记为CatP7*。
各实施例催化剂检测结果如表1,使用效果如表2。
表1各实施例催化剂检测结果
表2各实施例催化剂使用效果
标记 | 转化率/% | 选择性/% | 混合溶液气相纯度/% |
CatP1* | 99.96 | 99.81 | 99.81 |
CatP2* | 99.98 | 99.63 | 99.63 |
CatP3* | 100 | 99.58 | 99.91 |
CatP4* | 99.97 | 99.55 | 99.86 |
CatP5* | 99.95 | 99.61 | 99.78 |
CatP6* | 99.99 | 99.72 | 99.90 |
CatP7* | 99.96 | 99.62 | 98.21 |
表2中的混合溶液气相纯度是指将反应产物中的环氧丙烷与丙烯分离后所得溶液在气相条件下进行检测时,异丙苯和α,α-二甲基苄醇的总体积在气相中的占比。其值越高,异丙苯和α,α-二甲基苄醇总含量越高,分解衍生的副产总量就越少。
综合可得:对比实施例虽然有效保证环氧化催化剂的高效性,但是异丙苯与α,α-二甲基苄醇混合液气相纯度下降,表明部分α,α-二甲基苄醇产生了分解,使得副产物的总含量明显上升。而本方案制备的催化剂在使用过程中既保证高效性,同时异丙苯与α,α-二甲基苄醇混合溶液的气相纯度高,副产物总含量少,有效解决实际问题。
Claims (9)
1.一种用于制备环氧丙烷的催化剂,其特征在于,包含0.05~10wt%的TiO2、0.5~2.9wt%的M1、0.05~0.5wt%的M2,其余成分为SiO2,总量以100wt%计;
M1为Al2O3或Cr2O3中的至少一种;
M2为P、W或Mo中的至少一种;
催化剂的孔径5~15nm,比表面积150~560m2/g。
2.一种催化剂的制备方法,其用于制备权利要求1所述的催化剂,其特征在于,包括以下步骤:
(Ⅰ)将硅粉、增塑剂、胶粘剂、调胶剂及M2按设定比例混合,挤塑或压塑为具有一定形状的成型物;将成型物于40~140℃干燥10~36h,然后在250~900℃焙烧2.5~17h,制得硅条;
(Ⅱ)向反应器中加入硅条,将反应器内的温度控制在200~900℃,由反应底部汽化器用氮气带入钛源,保持温度4~26h后降至室温;
然后将反应器内的温度调整到30~190℃,由反应器顶部泵入含M1的溶液,对硅条进行浸泡,浸泡5~26h后排尽含M1的溶液;
(Ⅲ)将反应器内的温度调整到25~90℃,由反应器顶部泵入酸液,对硅条浸泡4~28h后排尽酸液;
将反应器内的温度调整到80~400℃,泵入去离子水清洗至中性后保温干燥10~28h,即制得该催化剂。
3.根据权利要求2所述的制备方法,其特征在于,
步骤(Ⅰ)中,硅粉、增塑剂、胶粘剂、调胶剂及M2的质量比100:(0.5~10):(50~500):(0.5~5.0):(0.05~5.0)。
4.根据权利要求2所述的制备方法,其特征在于,
步骤(Ⅱ)中,硅条与钛源质量比100:(5~40)。
5.根据权利要求2所述的制备方法,其特征在于,
步骤(Ⅲ)中,硅条与M1溶液质量比100:(400~8000)。
6.根据权利要求2所述的制备方法,其特征在于,
步骤(Ⅲ)中,硅条与酸液质量比100:(500~1000)。
7.根据权利要求2所述的制备方法,其特征在于,
硅条与去离子水的质量比100:(500~50000)。
8.根据权利要求2所述的制备方法,其特征在于,
步骤(Ⅰ)中,硅粉的孔径5~15nm,比表面积360~820m2/g。
9.根据权利要求2所述的制备方法,其特征在于,
步骤(Ⅰ)中,硅粉为柱层层析硅胶粉、大孔硅胶粉或白炭黑中的至少一种;
增塑剂为羟丙基甲基纤维素、田菁胶、聚乙二醇10000、木质素中的至少一种;
胶粘剂为硅溶胶或含1~3wt%拟薄水铝石的二氧化硅水溶液,该胶粘剂中的二氧化硅的质量浓度在5~60wt%;
调胶剂为丙二醇、聚乙二醇400、聚乙二醇200或丙三醇中的至少一种;
步骤(Ⅰ)中,M2选自磷钨酸、磷钼酸、硅钨酸或硅钼酸中的至少一种;
钛源为四氯化钛、钛酸四乙酯、钛酸四丙酯或钛酸四丁酯中的至少一种;
M1的溶液为偏铝酸钠溶液、三氯化铝溶液或重铬酸钾溶液中的至少一种;
酸液为盐酸溶液、硫酸溶液、磷酸溶液或硝酸溶液中的至少一种,酸液的浓度为0.25~1.6moL/L。
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