CN116675249A - 一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺 - Google Patents
一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺 Download PDFInfo
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 36
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 28
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 28
- 238000000944 Soxhlet extraction Methods 0.000 title claims abstract description 14
- 239000006227 byproduct Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 239000013067 intermediate product Substances 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 abstract description 28
- 239000011593 sulfur Substances 0.000 abstract description 28
- 238000002386 leaching Methods 0.000 abstract description 17
- 239000010936 titanium Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052719 titanium Inorganic materials 0.000 abstract description 13
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 abstract description 12
- 235000010215 titanium dioxide Nutrition 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 238000006386 neutralization reaction Methods 0.000 abstract description 6
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- AQGDXJQRVOCUQX-UHFFFAOYSA-N N.[S] Chemical compound N.[S] AQGDXJQRVOCUQX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 239000001038 titanium pigment Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺,以硫酸法钛白生产中廉价的中间品偏钛酸(TiO2·xH2O·ySO3)为钛源,以氨水为浸硫剂,以索氏提取法中和、分离工业偏钛酸的夹杂硫,后经低温煅烧脱水获得低结晶度的TiO2。该低结晶度TiO2具有松散的晶体结构,更利于钛锂电池、钛锂离子筛、钛酸钾晶须等材料的无机钛源需求;该工艺可实现氨‑硫中和、夹杂硫浸取、产物硫酸铵分离操作的同步进行;大大降低偏钛酸→TiO2转变的煅烧温度从而节省热能;同时可副产硫酸铵理论上无污染物排放。
Description
技术领域
本发明属于提取领域,具体涉及一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺。
背景技术
含钛氧类材料是具有广泛用途、重要价值及科技前景的新型高技术材料,比如钛基晶须、钛锂电极、钛锂离子筛等材料。钛基晶须合成通常由“烧结-离子交换-二次热处理”构成,例如TiO2和K2CO3通过高温固相反应生成K2Ti4O9,后经水合工艺,在水或酸溶液中交换出部分或全部的钾离子,再经二次热处理后,可分别制得各类钛酸钾晶须材料。尖晶石型钛酸锂(Li4Ti5O12)是一种“零应变”材料,具有充放电电压平台稳定、循环性能优良、成本低等优点,是锂离子电池行业非常重要的电极材料。钛锂离子筛对锂离子具有较高的饱和交换容量及循环稳定性,其制备主要是通过洗脱剂对前驱体进行适当的处理,作为钛锂离子筛前驱体最常见的是Li2TiO3(偏钛酸型)和Li4Ti5O12(尖晶石型)。当前该类含钛材料工业化生产的重要方法之一是高温固相合成法,具有设备要求低、工艺操作简单、成本低的优势,该方法多以目前钛白粉行业的颜料型锐钛TiO2、金红石TiO2为钛源原料。
目前化工行业中,硫酸法钛白是规模化、工业化颜料型钛白粉的重要来源。该工艺的中间品为偏钛酸(TiO2·xH2O·ySO3),为“黑钛液”(硫酸氧钛、硫酸亚铁、游离硫酸等组成的粘稠水溶液)中硫酸氧钛水解反应形成的沉淀,可认为是“夹杂硫”、少量锐钛型TiO2掺杂的无定形TiO2水合物。该偏钛酸被洗涤除酸、除铁后,在煅烧过程中经约200~600℃脱水,约600~850℃逐渐实现硫分解,TiO2晶型结构转变为:偏钛酸→无定形TiO2→锐钛型TiO2→金红石型TiO2。事实上目前的TiO2生产主要以颜料性能为导向,即钛白粉型TiO2,必须要求高结晶度锐钛及以上的晶型结构才能表现出优异的颜料性能,而且现工艺必须在约800℃以上高温下才能实现偏钛酸中“夹杂硫”以SO3或SO2气体形式分解溢出。无定形或低结晶度TiO2虽然不具备颜料性能,但是完全可以满足钛锂电池材料、钛锂离子筛、钛酸钾晶须等材料的钛源需求,且松散的晶体结构更利于该类钛材料的高温固相反应合成。
发明内容
本发明以硫酸法钛白粉行业低廉的中间品偏钛酸为钛源、氨水为硫浸取剂,以索氏提取法中和、浸取、分离工业偏钛酸的夹杂硫,后经低温煅烧脱水获得低结晶度的TiO2,同时可副产硫酸铵。该低结晶度TiO2产品区别于目前以颜料性能为导向的锐钛型、金红石型钛白粉类TiO2,具有松散的晶体结构,更利于钛锂电池、钛锂离子筛、钛酸钾晶须等材料的无机钛源需求;该工艺可实现氨-硫中和、夹杂硫浸取、产物硫酸铵分离操作的同步进行;大大降低偏钛酸→TiO2转变的煅烧温度从而节省热能;同时可副产硫酸铵理论上无污染物排放。
本发明通过以下技术方案实现的:
一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺,包括以下步骤:
(1)取硫酸法钛白生产中“二洗”工段的中间品偏钛酸再次精洗,控制至洗涤滤液Fe离子浓度≤10ppm;将洗涤后的偏钛酸在105℃干燥至无明显水分的粉末状;该过程可以去除少量游离硫酸,却难以去除“夹杂硫”。
(2)将50g偏钛酸粉末加入索氏提取器滤纸筒中,将300g氨水(质量分数20%)分成两份,一份缓慢加入索氏提取器中淹没偏钛酸粉末但液面低于虹吸管顶端,剩余氨水加入索氏提取器烧瓶中。
(3)加热回流6小时;
该过程中氨水经蒸发、冷凝滴落至偏钛酸物料中,偏钛酸夹杂硫和NH3发生中和反应生成硫酸铵,被“剥离”出偏钛酸“骨架”,即夹杂硫的浸出过程。
TiO2·xH2O·ySO3 + NH3·nH2O → TiO2·zH2O + (NH4)2SO4 + tH2O (式1)
当提取器中氨水液面高于虹吸管时,产物硫酸铵被氨水携带抽吸至釜底。由于硫酸铵无法蒸发,被保留在釜底的氨水中,氨水继续被蒸发、冷凝、滴落至偏钛酸中继续反应。
上述过程循环反复,产物硫酸铵被周期性移除出反应体系,大大促进了化学反应的正向进行及浸取夹杂硫脱离偏钛酸骨架的效力,该操作实现了氨-硫中和反应、夹杂硫浸出、产物硫酸铵分离的同步进行,最终的产物为提取器中氨水浸湿的偏钛酸以及釜底含有硫酸铵的氨水。
(4)移出氨水浸湿的偏钛酸并加热至105℃,氨水被蒸发、冷凝收集后回用;将干燥后的偏钛酸煅烧,冷却后即为低结晶度TiO2产品。
TiO2·zH2O → TiO2(低结晶度) + zH2O (式2)
进一步地,步骤(1)中用40℃~50℃脱盐水真空抽滤洗涤,控制至洗涤滤液Fe离子浓度≤10ppm(磺基水杨酸分光光度法测定)。
进一步地,氨水回流滴落速率5ml/min。
进一步地,干燥后的偏钛酸在350℃下煅烧3小时脱水。
本发明的有益效果为:
1、本发明制备的低结晶度TiO2区别于目前主流以颜料性能为导向的锐钛型、金红石型钛白粉类TiO2,具有更松散的晶体结构更适当于钛锂电池、钛锂离子筛、钛酸钾晶须等材料的无机钛源需求。
2、上述行业使用的锐钛、金红石钛白粉型TiO2因脱硫需求,煅烧温度通常大于800℃,本发明以氨水浸取偏钛酸夹杂硫后,偏钛酸煅烧温度可减低至300~400℃完成脱水即可成为产品,大大降低热能消耗。
3、本发明的索氏提取法可实现中和反应、夹杂硫浸取、硫酸铵分离同步实现。由于硫酸铵被同步移除出,减少浸取夹杂硫后偏钛酸滤饼洗涤操作,节省洗涤用水。
4、本发明中夹杂硫被即时剥离出偏钛酸“骨架”,产物硫酸铵被周期性虹吸至釜底,产物硫酸铵的移除促进了化学反应正向进行及硫浸取效力。
5、以硫酸吸收索氏提取、烘干等操作中的含氨尾气,合并、中和釜底液中氨水为硫酸铵,经减压蒸馏可获得副产硫酸铵,理论上无污染物产生。
附图说明
图1为氨水浸取偏钛酸夹杂硫的索氏工艺图;
图2为浸取夹杂硫前、后偏钛酸TG分析图;
图3为釜底液结晶物XRD图谱;
图4低结晶度TiO2产品XRD图谱对比图。
具体实施方式
为了使技术领域的人员更好地理解本发明方案,并使本发明的上述目的、特征和优点更加明显易懂,下面结合实施例对本发明作进一步的详细说明。
实施例1
一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺,包括以下步骤:
1、取硫酸法钛白生产中“二洗”工段的中间品偏钛酸再次精洗,用40℃~50℃脱盐水真空抽滤洗涤,控制至洗涤滤液Fe离子浓度≤10ppm(磺基水杨酸分光光度法测定);将洗涤后的偏钛酸在105℃干燥至无明显水分的粉末状。
2、将上述50g偏钛酸粉末加入索氏提取器滤纸筒中,将300g氨水(质量分数20%)分成两份,一份缓慢加入索氏提取器中淹没偏钛酸粉末但液面低于虹吸管顶端,剩余氨水加入索氏提取器烧瓶中。
3、安装冷凝回流装置、防尾气氨逃逸装置(以25%硫酸为吸收液)及整套提取装置。控制加热沸腾、回流强度,氨水回流滴落速率约5ml/min,持续约6小时。
TiO2·xH2O·ySO3 + NH3·nH2O → TiO2·zH2O + (NH4)2SO4 + tH2O (式1)
4、移出氨水浸湿的偏钛酸并加热至105℃,氨水被蒸发、冷凝收集后回用。将干燥后的偏钛酸在350℃下煅烧3小时脱水,冷却后即为低结晶度TiO2产品。
TiO2·zH2O → TiO2(低结晶度) + zH2O (式2)
5、合并回收氨水及釜底液,进行下一次偏钛酸浸取夹杂硫操作。
为验证产物情况,进行了如下分析测试:
1、对未浸取夹杂硫105℃干燥偏钛酸及浸取夹杂硫105℃干燥偏钛酸进行热重分析(TG),结果如图2所示:未经浸取夹杂硫的偏钛酸需要在~800℃煅烧完成脱水、硫分解,本发明可将煅烧温度降低至~350℃即可获得低结晶度氧化钛。
2、未加硫酸中和、直接将负载釜底液蒸发结晶,对结晶物进行X射线衍射分析(XRD),如图3所示,表明产物确实为(NH4)2SO4晶体(PDF97-005-2383)。
3、对未浸取夹杂硫的偏钛酸直接350℃煅烧产物、浸取夹杂硫后350℃煅烧产物(本发明产品,低结晶度TiO2)样品进行含量分析对比,如表1所示。表明原偏钛酸中夹杂硫被基本清除,产品TiO2含量大于99%,S含量低于0.5‰(GB/T 1706-2006二氧化钛颜料-7.1二氧化钛含量的测定-铝还原法、红外碳硫分析仪)。
表1各物料TiO2及S含量
样品 | 未浸取夹杂硫偏钛酸350℃煅烧产物 | 浸取夹杂硫后偏钛酸350℃煅烧(本发明产品) |
TiO2,% | 88.21 | 99.25 |
S,% | 1.791 | 0.042 |
4、对未浸取夹杂硫105℃干燥偏钛酸、浸取夹杂硫后350℃煅烧低结晶度氧化钛(本发明产品)、市场锐钛型钛白粉氧化钛样品进行X射线衍射对比分析如图4所示。
本发明制备的低结晶度氧化钛产品(图4,2号样品)X射线衍射峰近乎“馒头峰”且衍射强度略强于中间品偏钛酸,但远低于目前市场上以颜料性能为导向的锐钛型TiO2产品,表明本发明制备的产品为低结晶度TiO2,可能是少量锐钛型TiO2掺杂的无定形TiO2。
Claims (4)
1.一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺,其特征在于,包括以下步骤:
(1)取硫酸法钛白生产中“二洗”工段的中间品偏钛酸再次精洗,控制至洗涤滤液Fe离子浓度≤10ppm;将洗涤后的偏钛酸在105℃干燥至粉末状;
(2)将50g偏钛酸粉末加入索氏提取器滤纸筒中,将300g氨水分成两份,一份缓慢加入索氏提取器中淹没偏钛酸粉末但液面低于虹吸管顶端,剩余氨水加入索氏提取器烧瓶中;
(3)加热回流6小时;
(4)移出氨水浸湿的偏钛酸并加热至105℃,氨水被蒸发、冷凝收集后回用;将干燥后的偏钛酸低温煅烧,冷却后即为低结晶度TiO2产品。
2.根据权利要求1所述的一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺,其特征在于,步骤(1)中用40℃~50℃脱盐水真空抽滤洗涤。
3.根据权利要求1所述的一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺,其特征在于,氨水回流滴落速率5ml/min。
4.根据权利要求1所述的一种制备低结晶度TiO2及副产硫酸铵的索氏提取工艺,其特征在于,干燥后的偏钛酸在350℃下煅烧3小时脱水。
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