CN109803747B - 用于清洁粘胶生产废气的方法和用于该方法的催化剂 - Google Patents
用于清洁粘胶生产废气的方法和用于该方法的催化剂 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 229920000297 Rayon Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 title claims abstract description 11
- 238000004140 cleaning Methods 0.000 title claims abstract description 7
- 239000002912 waste gas Substances 0.000 title description 5
- 239000007789 gas Substances 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003518 caustics Substances 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 239000003599 detergent Substances 0.000 abstract 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
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- 244000068988 Glycine max Species 0.000 description 1
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- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 125000000188 beta-D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
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- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种用于清洁来自粘胶生产的主要含有H2S和CS2的废气的方法，所述方法包括使气体通过含有直接氧化型催化剂(例如负载在二氧化硅上的V2O5)的催化反应器，以通过气体中存在的氧或通过添加到气流中的氧将气体中的H2S转化为元素硫、SO2或其混合物。从催化反应器的流出气体中除去元素硫和SO2，并将未转化的CS2再循环到粘胶生产工艺中。
Description
本发明涉及一种清洁来自粘胶生产的废气的方法和用于该方法的催化剂。
粘胶人造丝是再生纤维素的纤维；它的结构类似于棉，但可以由多种植物(如大豆、竹和甘蔗)生产。纤维素是β-D-葡萄糖单元的线性聚合物，具有经验式(C6H10O5)n。为了制备粘胶，将溶解的浆液用氢氧化钠水溶液(通常为16-19％w/w)处理以形成“碱纤维素”，其具有近似式[C6H9O4-ONa]n。然后，用二硫化碳处理碱纤维素，以形成黄原酸纤维素钠：
[C6H9O4-ONa]n+nCS2→[C6H9O4-OCS2Na]n
纤维素与组合的硫的比例越高，则黄原酸纤维素的溶解度越低。将黄原酸酯溶解在氢氧化钠水溶液(通常2-5％w/w)中并使其解聚至所需程度，由溶液的粘度指示。解聚(成熟或熟化)的速率取决于温度，并受多种无机和有机添加剂(如金属氧化物和氢氧化物)存在的影响。空气也影响成熟过程，因为氧气引起解聚。
通过用无机酸如硫酸处理，从成熟的溶液产生人造丝纤维。在此步骤中，黄原酸酯基团被水解以再生纤维素并释放二硫代碳酸，然后二硫代碳酸分解成二硫化碳和水：
[C6H9O4-OCS2Na]2n+nH2SO4→[C6H9O4-OH]2n+2nCS2+nNa2SO4
H2COS2→H2O+CS2
除了再生纤维素，酸化产生硫化氢、硫和二硫化碳。洗涤由再生纤维素制成的线以除去残留的酸。然后通过添加硫化钠溶液来除去硫，并通过用次氯酸钠溶液漂白来氧化杂质。
因此，在粘胶行业中，存在几种含有硫组分的废气。通常回收含有高含量H2S的流并转化成硫酸，如上所述，硫酸是生产粘胶纤维的原料。还存在源自烟气收集的气体，所述气体含有少于2％H2S和相关的硫化合物。H2S的水平通常在200至2000ppm的范围内，并且CS2水平为约200至1000ppm。在当前运行的大多数粘胶工厂中处理这种更贫的废气。在最常见的方法中，将气体通入苛性碱洗涤器(用NaOH操作)，其中从气相中除去H2S，在液体排出后形成NaHS和Na2S。
在洗涤器的下游，应用再生活性炭过滤器，其中CS2在过滤床中吸收并浓缩。然后使用温和的温度变化工艺解吸，并且任选地在浓缩(upconcentrate)后作为有价值的原料返回到粘胶装置。如果活性炭步骤的入口气体中存在H2S，则它将占据活性炭的容量并破坏对整个装置的经济性很重要的CS2循环过程。这是在活性炭床的上游使用基于NaOH的苛性碱洗涤器的主要原因。
H2S洗涤器将使用显著过量的苛性碱物质来捕获H2S，因为在这样的洗涤器中需要高pH值来捕获H2S。在水相中，将存在NaHS和Na2S的混合物，其在废水处理装置中处理是麻烦且昂贵的，并且如果不非常小心地控制温度或pH，则在H2S的释放方面也是不稳定的。
US 2005/0147554 A1描述了使用湿氧化方法来控制来自粘胶工艺的还原的硫化合物的浓度。湿氧化工艺将还原的硫化合物氧化，以将它们转化为碱金属硫酸盐和/或硫代硫酸盐物质。将碱金属硫酸盐流再循环到粘胶工艺中。氧化在升高的温度和压力条件下进行，使得废气的氧浓度为约2％至约18％，并且碱金属硫酸盐流的pH为约2至10。
在US 6.416.725 B1中，处理包含H2S和CS2的含硫气流，例如作为人造丝形成工艺的副产物产生的含硫气流，以回收可用形式的组分。首先，使气流与NaOH水溶液接触，以溶解出H2S和一些CS2。使溶解的CS2从溶液中排出并作为液体浓缩物冷凝出来。通过例如冷凝来回收保留在气流中的任何CS2。将除去CS2后剩余的硫化钠水溶液浓缩，并根据需要将pH调节至使硫化钠主要为二硫化钠形式的值。浓缩的二硫化钠溶液能够与CS2的液体浓缩物一起再用于人造丝形成工艺。
在中国实用新型和专利申请CN 204107303 U、CN 204134460 U、CN 201115810 Y和CN 101219319 A中描述了用于粘胶纤维生产的废气的废气回收和吸附系统的各种实施方案，通常采用碱清洗/吸附和冷凝方法。然而，尽管相关，但这些CN申请并未预期本发明。
本发明的思想是在活性炭过滤器上游使用直接氧化型催化剂，从而将H2S转化为元素硫、SO2或其混合物。元素硫可以在冷凝器中除去，并且与化学计量需求相比，以温和的过量使用标准苛性剂(例如NaOH或CaCO3)在苛性碱洗涤器中容易除去SO2，从而产生可以在液体排放系统中容易地处理的硫酸盐。包含负载在载体(如二氧化硅)上的催化活性材料(如V2O5)的直接氧化型催化剂是本领域已知的，并描述于例如WO 2015/082351、US4.277.458和US 2012/0014854中。
更具体地，本发明涉及一种用于清洁来自粘胶生产的废气的方法，所述废气主要含有空气和硫组分，主要是H2S和CS2，所述方法包括以下步骤：
-使废气通过含有直接氧化型催化剂的催化反应器，以通过气体中存在的氧或通过添加到气流中的氧将废气中的H2S转化为元素硫、SO2或其混合物，
-从催化反应器的流出气体中除去元素硫和SO2，以及
-将未转化的CS2再循环到粘胶生产工艺中。
来自粘胶生产的废气通常含有浓度为约200至2000ppm的H2S和浓度为约200至1000ppm的CS2。
可操作催化反应器以将H2S转化为元素硫、SO2或其混合物，同时使CS2基本上未转化。
优选地，在冷凝器中除去元素硫，并在苛性碱洗涤器中除去SO2。在苛性碱洗涤器下游的再生活性炭过滤器中吸收并浓缩CS2。
用于该方法的合适催化剂包括包含负载在二氧化硅、氧化铝、二氧化钛、二氧化铈、碳化硅或活性炭或其混合物上并且任选地被碱金属(优选Na2O)促进的Fe、Cr、Zn、Mn、V、Co、Ti、Bi、Sb、Cu或Mg的氧化物或混合物的催化剂。特别优选的催化剂包含负载在二氧化硅上的V2O5。
操作温度在100至300℃的范围内，优选在160至260℃的范围内。
Claims (7)
1.一种用于清洁来自粘胶生产的废气的方法，所述废气主要含有空气和硫组分，主要是H2S和CS2，所述方法包括以下步骤：
-使废气通过含有直接氧化型催化剂的催化反应器，以通过气体中存在的氧或通过添加到气流中的氧将废气中的H2S转化为元素硫、SO2或其混合物，
-从催化反应器的流出气体中除去元素硫、SO2或其混合物，以及
-将未转化的CS2再循环到粘胶生产工艺中。
2.根据权利要求1所述的方法，其中在冷凝器中除去元素硫，并在苛性碱洗涤器中除去SO2。
3.根据权利要求2所述的方法，其中在苛性碱洗涤器下游的再生活性炭过滤器中吸收并浓缩CS2。
4.根据权利要求3所述的方法，其中所吸收的CS2被解吸并且任选地在浓缩后作为原料返回到粘胶生产装置中。
5.根据权利要求1所述的方法，其中来自粘胶生产的废气含有浓度为200至2000ppm的H2S和浓度为200至1000ppm的CS2。
6.根据权利要求1-5中任一项所述的方法，其中操作温度在100至300℃的范围内。
7.根据权利要求1-5中任一项所述的方法，其中操作温度在160至260℃的范围内。
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| H2S-Selective Catalytic Oxidation: Catalysts and Processes;Xin Zhang等;《ACS Catal.》;20141226;第5卷(第2期);第1053-1054页，第1057-1065页以及表3-4 * |
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