CN113213578A - 一种处理尾矿库废水中丁基黄药的方法 - Google Patents
一种处理尾矿库废水中丁基黄药的方法 Download PDFInfo
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- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002351 wastewater Substances 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000006731 degradation reaction Methods 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000012991 xanthate Substances 0.000 claims abstract description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000004005 microsphere Substances 0.000 claims description 21
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 13
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 13
- 239000001099 ammonium carbonate Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 101000610640 Homo sapiens U4/U6 small nuclear ribonucleoprotein Prp3 Proteins 0.000 description 1
- 101001110823 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L6-A Proteins 0.000 description 1
- 101000712176 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L6-B Proteins 0.000 description 1
- 102100040374 U4/U6 small nuclear ribonucleoprotein Prp3 Human genes 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000001339 gustatory effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
本发明涉及一种处理尾矿库废水中丁基黄药的方法,包括以下步骤:向含丁基黄药的尾矿库废水中加入催化剂MgFe2O4‑ZnO及氯酸钠,于避光条件下混合不低于30min,废水中含有的丁基黄药、催化剂MgFe2O4‑ZnO及氯酸钠的质量比为1:(30~100):(5~10);再将混合溶液置于光照条件降解。该方法基本能够去除废水中丁基黄药,具有反应条件温和、处理效率高和无二次污染等优点,光催化剂在应用时便于与反应体系分离,具有较高的重复利用率,具有良好的应用前景。
Description
技术领域
本发明涉及水处理技术领域,尤其涉及一种处理尾矿库废水中丁基黄药的方法。
背景技术
在有色金属硫化矿浮选中常常使用丁基黄药作为捕收剂,导致矿山尾矿库的溢流水中往往含有大量丁基黄药,若直接排放,会严重污染水体,抑制水生生物生长,对矿山周围生态环境造成较严重破坏。因此,必须对尾矿库溢流水中丁基黄药进行处理,以达到排放标准。
丁基黄药具有刺激性臭味和毒性,且易溶于水,嗅觉阀为0.005mg/L,味觉阀为0.1mg/L。我国地面水中黄原酸盐的最高容许浓度为0.005mg/L,按照《铜、钴、镍工业污染物排放标准》(GB25467-2010)要求,尾矿库溢流水COD值必须小于50mg/L。因此,在对尾矿库溢流水中丁基黄药进行降解处理时,须同时满足丁基黄药浓度小于0.005mg/L和处理后溶液COD小于50mg/L这两个指标。
虽然有研究者利用次氯酸钠、Fenton试剂等对选矿废水中的丁基黄药进行了处理,也取得了一定的去除效果,但并未达到丁基黄药浓度小于0.005mg/L这一指标。此外,在次氯酸钠的使用过程中,普遍存在溶质刺激性强、反应液中残留率较高、易分解为有毒氯气等物化性质和安全方面的缺陷。
发明内容
有鉴于此,有必要提供一种处理尾矿库废水中丁基黄药的方法,用以解决上述问题。
本发明提供一种处理尾矿库废水中丁基黄药的方法,包括以下步骤:
(1)向含丁基黄药的尾矿库废水中加入催化剂MgFe2O4-ZnO及氯酸钠,于避光条件下混合不低于30min,所述废水中含有的丁基黄药、催化剂MgFe2O4-ZnO及氯酸钠的质量比为1:(30~100):(5~10);
(2)再将混合溶液置于光照条件降解。
其中,所述催化剂MgFe2O4-ZnO的制备包括以下步骤:合成MgFe2O4微球,超声分散于聚乙烯吡咯烷酮溶液中,加入硬酸酯锌,于165~175℃反应水解,得到所述催化剂MgFe2O4-ZnO。
进一步的,所述合成MgFe2O4微球包括以下步骤:称取FeCl3·6H2O、MgCl2·6H2O、碳酸氢铵和1,4丁二醇混合于蒸馏水中,待完全溶解后于200℃下反应12h,得到MgFe2O4微球。
所述MgFe2O4微球的合成步骤中,FeCl3·6H2O、MgCl2·6H2O、碳酸氢铵和1,4丁二醇的加入配比依次为1mmol:(0.5~1.0)mmol:(0.01~0.05)mmol:(40~70)ml。
进一步的,所述水解反应时间不低于8h。
进一步的,所述水解反应温度为165~175℃。
其中,所述步骤(1)中,控制pH值为2~3。
其中,所述步骤(2)的处理时间不低于30min。
有益效果:
本发明提供的处理尾矿库废水中丁基黄药的方法,采用光催化剂进行处理,具有普适性,该光催化剂为多孔的微粒结构,比表面积高。经超声分散-暗黑吸附平衡-光催化反应处理后,基本能够去除废水中丁基黄药,具有反应条件温和、处理效率高和无二次污染等优点。另外,由于本发明提供的MgFe2O4-ZnO催化剂为磁性光催化剂,同时具有磁性和光催化性能,在应用时便于与反应体系分离,具有较高的重复利用率,具有良好的应用前景;该磁核作为光催化剂的载体可使磁性光催化剂同时具有负载型催化剂和悬浮态催化剂的优势。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例对本发明进行进一步详细说明。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。
本发明实施例提供一种处理尾矿库废水中丁基黄药的方法,包括以下步骤:
(1)向含丁基黄药的尾矿库废水中加入催化剂MgFe2O4-ZnO及氯酸钠,于避光条件下混合不低于30min,所述废水中含有的丁基黄药、催化剂MgFe2O4-ZnO及氯酸钠的质量比为1:(30~100):(5~10);
(2)再将混合溶液置于光照条件降解。
本发明提供的处理尾矿库废水中丁基黄药的方法,采用光催化剂进行处理,具有普适性,该光催化剂为多孔的微粒结构,比表面积高。经超声分散-暗黑吸附平衡-光催化反应处理后,基本能够去除废水中丁基黄药,具有反应条件温和、处理效率高和无二次污染等优点。另外,由于本发明提供的MgFe2O4-ZnO催化剂为磁性光催化剂,同时具有磁性和光催化性能,在应用时便于与反应体系分离,具有较高的重复利用率,具有良好的应用前景;该磁核作为光催化剂的载体可使磁性光催化剂同时具有负载型催化剂和悬浮态催化剂的优势。
其中,所述催化剂MgFe2O4-ZnO的制备包括以下步骤:合成MgFe2O4微球,超声分散于聚乙烯吡咯烷酮溶液中,加入硬酸酯锌,于165~175℃反应水解,得到所述催化剂MgFe2O4-ZnO。其中,MgFe2O4微球可采用共沉淀法、溶剂热法和溶胶凝胶法,具体的,溶剂热法制得的MgFe2O4微球具有分散性好,粒径大小均一和比饱和强度大的优点。
更进一步的,本发明提供的合成MgFe2O4微球方法具体包括:
称取FeCl3·6H2O、MgCl2·6H2O、碳酸氢铵和1,4丁二醇混合于蒸馏水中;待完全溶解后200℃下反应12h,得到MgFe2O4微球,用乙醇和蒸馏水反复冲洗,以便保存和使用。
为了更好地吸附污染物,采用溶剂热法制备MgFe2O4-ZnO磁性纳米材料是利用碳酸氢铵受热易分解的特性得到中孔结构的微球。当体系达到一定温度时,碳酸氢铵会分解为NH3和CO2气体,这些气体在体系中形成大量微泡,这些气泡具有较大的比表面积,可作为气/液成核界面使MgFe2O4纳米晶粒在其表面聚集,形成具有中孔结构的紧密微球。
为更好地制备MgFe2O4微球,其中各原料加入量,按照FeCl3·6H2O、MgCl2·6H2O、碳酸氢铵和1,4丁二醇的配比依次为1mmol:0.5~1.0mmol:0.01~0.05mmol:40~70ml。
具体的,所述水解反应时间不低于8h。
具体的,所述水解反应温度为165~175℃。
进一步的,所述步骤(1)中,控制pH值为2~3。
进一步的,所述步骤(2)的处理时间不低于30min。
为便于对催化剂MgFe2O4-ZnO的合成过程及其处理含丁基黄药的尾矿库废水的处理过程进行具体描述,将这两个过程中的具体条件和参数进行列表,并将具体实施例和对比例列入表1中。表1中,对催化剂合成中,MgFe2O4微球合成中是否加入碳酸氢铵(加入碳酸氢铵注为“+”,未加入注为“-”)、原料配比(依次为FeCl3·6H2O、MgCl2·6H2O、碳酸氢铵和1,4丁二醇的配比,单位依次为mmol、mmol、mmol、ml)、水解反应温度进行列举;还在利用该催化剂出含丁基黄药废水进行处理过程中,对步骤(1)中控制的pH值及步骤(2)中处理时间进行了列举。
表1
使用本发明上述实施例和对比例提供的催化剂和处理方法,对某含丁基黄药浓度为60mg/L(COD值为100mg/L)的选矿厂尾矿库溢流水进行处理后,考察了该催化剂的稳定性,对丁基黄药的降解率或去除率,以及处理后废水中丁基黄药含量。
丁基黄药的浓度测定方法:采用HPLC进行检测,LiChrosorb RP18(5μm),200×4.0mm,流动相为甲醇-水(85:15,V/V),流速0.8ml/min,检测波长240nm,进样量6μl。样品处理,取一定量的废水样品,用含0.010mol/L的KI溶液(含0.20mo1/L KI)氧化样品至淡黄色,加入5mL正己烷,充分振荡至下层清亮,取6μl上层萃取液注入色谱系统,在波长301nm处检测,作色谱图。根据丁基黄药标准品制作标准曲线,再通过标准曲线的拟合方程进行样品中丁基黄药含量的检测。
丁基黄药降解效果评价方法:以丁基黄药吸附前后的浓度变化来计算其降解率,降解率=(初始浓度-处理后浓度)/初始浓度×100%。
催化剂的稳定性评价方法:
为了考察所制备的光催化剂MgFe2O4-ZnO的稳定性,对其进行重复使用实验。每次光催化反应结束后,将反应混合液离心,弃去上清液得到光催化剂,再依次用水和乙醇清洗3~5次,之后放入烘箱在60℃下烘干,然后再对废水进行光催化反应,按此方法将光催化剂重复使用10次,通过上述方法检测其降解率,降解率下降的程度越低,说明该光催化剂具有优良的稳定性。
表2
由表2可知:
1、实施例1-14处理后废水中丁基黄药浓度均小于的0.005mg/L,COD值均小于32mg/L,均达到GB25467-2010的要求,初始降解率均高于99.9917%,而且使用10次后催化剂的降解率仍然大于92.4%。而对比例1-9在初始降解率、处理后废水中丁基黄药浓度、COD值或使用10次后催化剂的降解率三者至少一种效果不及实施例。
2、具体而言,实施例1在初始降解率和使用10次后催化剂的降解率均高于对比例1,而对比例1处理后废水中丁基黄药浓度达到1.464677mg/L,这表明在合成MgFe2O4微球过程中加入碳酸氢铵有助于提高MgFe2O4-ZnO催化剂的降解率,可能与其形成MgFe2O4微球过程中产生气泡的作用有关。
3、实施例2-9进一步优化了合成MgFe2O4微球中原料配比,实施例10-12进一步优化了催化剂合成过程中水解反应的温度,使得其处理废水的效果得以进一步提升;实施例13-14则对步骤(1)中pH值和步骤(2)中处理时间进行了改变,但都在限定范围内,使得其初次使用时的降解率保持在99.9936%以上。而对比例2-5相对于实施例1,其合成MgFe2O4微球的其他原料不在上述限定的范围内,对比例8、9其步骤(1)中pH值和步骤(2)中处理时间均不在上述限定范围内,使得其处理废水时对丁基黄药降解率或催化剂的稳定性产生了负面影响。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种处理尾矿库废水中丁基黄药的方法,其特征在于,包括以下步骤:
(1)向含丁基黄药的尾矿库废水中加入催化剂MgFe2O4-ZnO及氯酸钠,于避光条件下混合不低于30min,所述废水中含有的丁基黄药、催化剂MgFe2O4-ZnO及氯酸钠的质量比为1:(30~100):(5~10);
(2)再将混合溶液置于光照条件降解。
2.根据权利要求1所述的方法,其特征在于,所述催化剂MgFe2O4-ZnO的制备包括以下步骤:合成MgFe2O4微球,超声分散于聚乙烯吡咯烷酮溶液中,加入硬酸酯锌,于165~175℃反应水解,得到所述催化剂MgFe2O4-ZnO。
3.根据权利要求2所述的方法,其特征在于,所述MgFe2O4微球的合成包括以下步骤:称取FeCl3·6H2O、MgCl2·6H2O、碳酸氢铵、1,4丁二醇混合于蒸馏水中,待完全溶解后于200℃下反应12h,得到MgFe2O4微球。
4.根据权利要求3所述的方法,其特征在于,所述MgFe2O4微球的合成步骤中,FeCl3·6H2O、MgCl2·6H2O、碳酸氢铵和1,4丁二醇的加入配比依次为1mmol:(0.5~1.0)mmol:(0.01~0.05)mmol:(40~70)ml。
5.根据权利要求2所述的方法,其特征在于,所述水解反应时间不低于8h。
6.根据权利要求3所述的方法,其特征在于,所述水解反应温度为165~175℃。
7.根据权利要求1-6任一项所述的方法,其特征在于,所述步骤(1)中,控制pH值为2~3。
8.根据权利要求1-6任一项所述的方法,其特征在于,所述步骤(2)的处理时间不低于30min。
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