CN108126710A - 一种抗硫除萘催化剂的制备及应用 - Google Patents
一种抗硫除萘催化剂的制备及应用 Download PDFInfo
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 24
- 239000011593 sulfur Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 37
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002604 ultrasonography Methods 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 241000264877 Hippospongia communis Species 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 239000010931 gold Substances 0.000 claims abstract description 7
- 239000010970 precious metal Substances 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
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- 238000000034 method Methods 0.000 claims description 16
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 11
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
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- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910017343 Fe2 (SO4)3 Inorganic materials 0.000 description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- -1 Benzene Toluene Acetone Naphthalene Chemical compound 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
本发明提供一种抗硫除萘催化剂的制备及应用,涉及环境保护催化剂技术领域。该催化剂以Al2O3或蜂窝陶瓷为载体,助剂元素和活性组分经过微波超声浸渍在载体上;助剂元素为铜、铁、锰、铈、镍中一种或者几种,助剂元素负载量为载体质量的2‑12%;活性组分为贵金属钯、金,活性组分负载量为载体质量的0.01‑0.20%,其中钯:金摩尔比为1:(0~3)。本发明可应用于催化氧化法处理含萘含硫有机废气治理领域,对萘转化效率高(高于99%),而且能够处理含丙酮、苯、甲苯和萘混合废气,处理后废气达到国家排放标准,不生成二次污染物,同时该催化剂有一定的抗硫中毒能力,进一步拓宽了其应用范围。
Description
技术领域
本发明属于催化氧化环境保护领域,特别涉及一种处理含萘含硫有机废气的催化剂及其制备和应用领域。
背景技术
多环芳烃(PAHs)是煤,石油,木材,烟草,有机高分子化合物等有机物不完全燃烧时产生的挥发性碳氢化合物,是重要的环境和食品污染物。他们的分子中含有两个及两个以上的苯环,是环境中普遍存在的一种致癌物,萘就是其中的一种,它在远低于沸点温度下,就具有很大的蒸气压,因而在加热时,固体萘能不经过液态直接变为萘蒸气,而萘蒸气在冷却时又不可经过液态而直接转变为银白色固体。目前治理含萘废气的方法主要是采用喷淋吸收法,一般是盐溶液或者洗油洗涤,这种物理处理方法效率不高(50%~60%),能耗大,消耗大量的盐溶液和洗油,而萘的挥发性极强,有一些萘蒸汽来不及处理就逸散到大气中,造成环境污染。本发明催化剂对多环芳烃中的萘作进行催化氧化处理后,萘转化率可以达到99%;同时该催化剂还能催化氧化含萘、苯、甲苯和H2S等的废气,处理后苯≦4mg/m3,甲苯≦15mg/m3,非甲烷总烃≦50mg/m3,H2S≦1mg/m3,符合国家排放标准。
CN106732621A公开了一种抗硫催化燃烧催化剂及制备方法和应用,该方法制备的催化剂可以处理含600ppm SO2有机废气,CN105964255A公开了一种一种高抗硫能力的催化燃烧催化剂的制备,制备的催化剂对二氧化硫有较大抗性。有研究表明,二氧化硫和硫化氢同属硫化物,但二氧化硫对催化剂活性的影响较低,S2-发生反应生成硫单质是催化剂中毒、活性下降的主要原因。而本发明提供的催化剂可将H2S高效转化为SO2,降低硫单质的生成量,提高催化剂的抗硫活性。
本发明抗硫除萘催化剂应用范围广,可用于处理VOCs废气和恶臭气体,能够应用在焦化、石油、橡胶加工等众多化工行业。
发明内容
本发明要解决的技术问题是,填补现有技术的空白,提供一种采用催化氧化处理含萘废气的催化剂,同时该催化剂还具有较高的抗硫化氢能力。本发明处理含萘废气具有绿色、高效等优点。
为实现上述目的,本发明采用的技术方案如下:
本发明提供一种抗硫除萘催化剂的制备,具体包括以下步骤:(1)取铜、锰、铈、铁、镍中一种或者两种以上的金属盐溶于水,配置成一定浓度的改性试剂,搅拌均匀后,将经过120℃抽真空处理之后的载体完全浸渍在该溶液中,常温下微波超声浸渍,90℃-120℃烘干2h,400℃-600℃焙烧3h-5h;
(2)按照比例配置贵金属钯、金的金属盐溶液,贵金属钯、金摩尔比为1:(0~3);将步骤(1)制得的催化剂浸渍于步骤(2)所配置的溶液中,常温下微波超声处理后滤出,90℃-120℃烘干2h,500℃焙烧3h;
(3)采用H2-N2混合气(H2体积分数由5%提高至50%)活化还原催化剂,常压下还原5h~8h。
一种抗硫除萘催化剂的应用,其工艺流程如下:催化剂对含萘废气催化氧化流程为空气自空气钢瓶1导出后,经过减压阀2减压后,一路气体经质量流量计3后进入萘蒸气发生装置6;或者该路气体先进入含苯/甲苯汽化罐5,再进入萘蒸汽发生器6;再或者该路气体先进入丙酮汽化罐4,再进入含苯/甲苯汽化罐5,最后进入萘蒸汽发生器6。另一路气体做为稀释气经过质量流量计7后与携带萘蒸气的空气进入缓冲罐8混合,进入缓冲罐8的气体还可以包括来自硫化氢气体钢瓶9中经减压阀14减压后的硫化氢,硫化氢由质量流量计12调节流量,来自缓冲罐8的混合气经过预热器10加热升温至150℃-250℃后进入固定床反应器11,在380-550℃连续反应,尾气经尾气吸收装置13后经通风橱放空处理。固定床反应器11反应前后分别连接气相色谱在线检测。见图1。
相对于现有技术,本发明取得了以下技术进步:
(1)本发明采用浸渍法制备、工艺简单、安全,适合大规模生产,工艺放大风险小;
(2)本发明使用的催化剂克服了传统催化剂易烧结、易结碳、易中毒等特点,不产生二次污染;
(3)本发明使用的催化剂,对含萘废气处理效率高,没有萘蒸汽逃逸,浓度范围广;
(4)本发明使用的催化剂可单独使用处理含萘废气,反应温度低,转化完全;
(5)本发明使用的催化剂既可以单独使用处理含萘废气,也可以用于含萘,芳烃、酮类等混合气体的处理,转化完全,能够达到国家排放标准,填补了现有技术的空白;
(6)本发明使用的催化剂具有良好的抗硫化氢能力。
附图说明
图1为本发明催化剂催化氧化处理含萘废气装置示意图;
其中:1为空气钢瓶,2和14均为减压阀,3、7、12均为质量流量计,4为丙酮汽化罐,5为苯/甲苯汽化罐,6为萘蒸气发生器,8为缓冲罐,9为硫化氢气体钢瓶,10为预热器,11为固定床反应器,13为尾气吸收装置,15为催化剂,16为各储罐伴热,17为管道伴热,18为取样阀门。
具体实施方式
下面结合实施例对本发明进一步详细说明,但本发明包括但不限于这些实例。
本发明中使用的原料均可以通过本领域公知的方法制得,或采用市售产品。
催化剂制备方法实施例如下:
实施例1
称取4.3258g Cu(NO3)2.3H2O,9.5746g Mn(NO3)2-50%wt水溶液,0.7795g Fe2(SO4)3,4.5032g Ni(NO3)2.6H2O溶于30ml去离子水中,搅拌均匀后,将20g经高温抽真空处理后的蜂窝陶瓷完全浸渍在该溶液中,常温下微波超声浸渍60min,90℃烘干,115℃干燥2h,400℃恒温焙烧3h。
按照0.15%的负载量配置PdCl2和AuCl3混合水溶液,其中Pd:Au摩尔比1:1,将上步所得的催化剂快速完全倒入混合盐溶液中,调节pH7-8,常温下微波超声浸渍60min后滤出,110℃烘干2h,500℃焙烧3h。
常压下使用H2体积含量5%~50%的H2-N2混合气,还原2h~5h,得到催化剂0.15%(Pd~Au)/Cu~Mn~Fe~Ni/蜂窝陶瓷。
实施例2
称取1.8875g Cu(NO3)2.3H2O,2.7968g Mn(NO3)2-50%wt水溶液,0.7795g Fe2(SO4)3,2.7756g Ce(NO3)3·6H2O溶于30ml去离子水中,搅拌均匀后,将20g高温抽真空处理后的氧化铝完全浸渍在该溶液中,常温下微波超声浸渍60min,90℃烘干,110℃干燥2h,400℃恒温焙烧3h。
按照0.05%Pd的负载量配置PdCl2水溶液,将上步所得快速完全倒入钯盐溶液中,调节pH7-8,常温下微波超声浸渍60min后滤出,110℃烘干2h,500℃焙烧3h。
常压下使用H2含量5%~50%的H2-N2混合气,120℃~300℃还原2h~5h,得到催化剂0.05%Pd/Cu~Mn~Fe~Ce/氧化铝。
实施例3
称取1.8875g Cu(NO3)2.3H2O,2.7968g Mn(NO3)2-50%wt水溶液,1.5203g Ce(NO3)3·6H2O溶于30ml去离子水中,搅拌均匀后,将20g高温抽真空处理的蜂窝陶瓷完全浸渍在该溶液中,常温下微波超声浸渍60min,90℃烘干,110℃干燥2h,400℃恒温焙烧3h。
按照0.2%的负载量配置PdCl2和AuCl3混合水溶液,其中Pd:Au摩尔比1:3,将上步所得的催化剂快速完全倒入盐溶液中,调节pH7-8,常温下微波超声浸渍60min后滤出,110℃烘干2h,500℃焙烧3h。
常压下使用H2体积分数为5%~50%的H2-N2混合气,120℃~300℃还原2h~5h,得到催化剂0.2%(Pd~Au)/Cu~Mn~Ce/蜂窝陶瓷。
实施例4
称取1.8875g Cu(NO3)2.3H2O,2.5670g Fe2(SO4)3,1.5203gCe(NO3)3·6H2O溶于30ml去离子水中,搅拌均匀后,将20g高温抽真空处理后的蜂窝陶瓷完全浸渍在该溶液中,常温下微波超声浸渍60min,90℃烘干,110℃干燥2h,400℃恒温焙烧3h。
按照0.1%Pd的负载量配置PdCl2水溶液,将上步所得的催化剂快速完全倒入钯盐溶液中,调节pH7-8,常温下微波超声浸渍60min后滤出,110℃烘干2h,500℃焙烧3h。
常压下使用H2体积分数为5%~50%的H2-N2混合气,120℃~300℃还原2h~5h,得到催化剂0.1%Pd/Cu~Fe~Ce/蜂窝陶瓷。
实施例5
将实施例1-4中制备得到的催化剂装填于固定床反应装置中,如图1所示(虚线处装置除外),在萘浓度5000mg/m3,空速25000h-1条件下进行催化氧化评价,结果见表1所示(T50,T99分别为萘分解率50%和99%的分解温度)。
表1本发明催化剂处理含萘废气催化活性
催化剂 | T50/℃ | T99/℃ |
实施例1 | 245 | 355 |
实施例2 | 250 | 360 |
实施例3 | 247 | 352 |
实施例4 | 254 | 370 |
由表1可知,对含萘废气进行催化氧化处理时,实施例3中催化剂的T50和T99为四组实施例中的最低值,此时催化剂活性最高,其配比为最优配比。
实施例6
为了进一步考察催化剂对含萘含硫有机废气的处理效果,同时最大限度的模拟工业有机废气的组成,于废气中引入苯、甲苯、丙酮等有机组分,在萘浓度5000mg/m3,苯1000mg/m3、甲苯500mg/m3、丙酮1500mg/m3,H2S 400mg/m3,空速25000h-1,催化氧化温度410℃的条件下对实施例3中制备得到的催化剂进行连续评价,考察其寿命和抗硫活性,已连续评价至1000h,详见表2。
表2含硫有机气体催化氧化处理数据
污染物 | 苯 | 甲苯 | 丙酮 | 萘 | H2S |
反应前浓度mg/m3 | 1000 | 500 | 1500 | 5000 | 400 |
反应后浓度mg/m3 | 2.04 | 0.40 | 0.3 | 5.03 | ≤1 |
去除率/% | 99.79 | 99.92 | 99.98 | 99.89 | ≥99.75 |
由表2可知,经过近1000h的连续运行,催化剂各组分去除率仍高于99%,催化剂活性未收到H2S的影响,抗硫能力强,各污染物反应后浓度后经在线检测分析符合GB31571-2015排放标准。
本发明催化剂可应用于催化氧化法处理含萘VOCs气体领域,对萘转化效率高(99%),而且能够处理含苯、甲苯和萘混合废气,处理后废气达到国家排放标准,不生成二次污染物,同时该催化剂有一定的抗硫中毒能力,进一步拓宽了其应用范围。
Claims (7)
1.一种抗硫除萘催化剂的制备,其特征在于:该催化剂以Al2O3或蜂窝陶瓷为载体,助剂元素和活性组分经过微波超声浸渍在载体上;所述助剂元素为铜、铁、锰、铈、镍中一种或者几种,助剂元素负载量为载体质量的2-12%;活性组分为贵金属钯、金,活性组分负载量为载体质量的0.01-0.20%,其中钯:金摩尔比为1:(0~3)。
2.根据权利要求1所述的一种抗硫除萘催化剂的制备,其特征在于,包括以下步骤:
1)载体首先浸渍在助剂元素的金属盐水溶液中,微波超声浸渍,浸渍后,烘干,焙烧;
2)将步骤1)制得的催化剂浸渍在活性组分的金属盐水溶液中,微波超声浸渍,浸渍后,烘干,焙烧;
3)在还原气下,活化还原步骤2)制得的催化剂,即得到抗硫除萘催化剂。
3.根据权利要求2所述的一种抗硫除萘催化剂的制备,其特征在于,步骤1)中,助剂元素的金属盐为氯化盐、草酸盐、硝酸盐、硫酸盐中的一种或几种;浸渍处理前,载体经过120℃抽真空处理,去除载体孔道中吸附的空气和水分,提高浸渍效果。
4.根据权利要求2所述的一种抗硫除萘催化剂的制备,其特征在于,步骤1)和2)中,采用微波超声浸渍:浸渍时间30-60min,频率40kHz;浸渍后,90℃-120℃烘干2h,400-600℃焙烧3h。
5.根据权利要求2所述的一种抗硫除萘催化剂的制备,其特征在于,步骤3)中,还原气为H2-N2混合气,并根据还原进度不断提高混合气中H2含量,其体积分数由5%提高至50%、还原气空速为1000h-1,温度由100℃提升至220℃,常压下还原5h-8h。
6.根据权利要求1-5任一项所述的一种抗硫除萘催化剂的制备得到的催化剂的应用,其特征在于,所述催化剂对含萘废气催化氧化流程为空气自空气钢瓶(1)导出后,经过减压阀(2)减压后,一路气体经质量流量计3后进入萘蒸气发生器(6);或者该路气体先进入含苯/甲苯汽化罐(5),再进入萘蒸汽发生器(6);又或者该路气体先进入丙酮汽化罐(4),再进入苯/甲苯汽化罐(5),最后进入萘蒸汽发生器(6);另一路气体做为稀释气经过质量流量计(7)后与携带萘蒸气的空气进入缓冲罐(8)混合,进入缓冲罐(8)的气体还可以包括来自硫化氢气体钢瓶(9)中经减压阀(14)减压后的硫化氢,硫化氢由质量流量计(12)调节流量,来自缓冲罐(8)的混合气经过预热器(10)加热升温后进入固定床反应器(11)进行连续催化氧化反应,已去除萘、H2S等组分,固定床反应器(11)反应前后分别连接气相色谱在线检测。
7.根据权利要求6所述的应用,其特征在于,萘蒸气发生器(6)及所有流通含萘气体的管道均设有加热保温设施,加热保温设施温度设定在50℃-100℃,以保证萘持续气化并且在管道中不冷凝;苯/甲苯汽化罐(5)上设有保温装置,保温装置温度设定在30℃-40℃,保证苯/甲苯能够持续气化;固定床反应器(11)前后取样位置至气相色谱进样口位置管线连接有伴热装置,伴热装置温度不低于120℃,保证萘呈气体状态。
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