TWI835968B - 由烴類流中移除硫醇類的催化劑及方法 - Google Patents
由烴類流中移除硫醇類的催化劑及方法 Download PDFInfo
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- TWI835968B TWI835968B TW109100451A TW109100451A TWI835968B TW I835968 B TWI835968 B TW I835968B TW 109100451 A TW109100451 A TW 109100451A TW 109100451 A TW109100451 A TW 109100451A TW I835968 B TWI835968 B TW I835968B
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- Prior art keywords
- catalyst
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- mercaptans
- butene
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 73
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 47
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 39
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000001993 dienes Chemical class 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 150000002019 disulfides Chemical class 0.000 claims abstract description 17
- 238000005732 thioetherification reaction Methods 0.000 claims abstract description 16
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 43
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 35
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 34
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 22
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 10
- 238000006317 isomerization reaction Methods 0.000 claims description 10
- 150000003573 thiols Chemical class 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical group CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 44
- 239000000203 mixture Substances 0.000 description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 32
- 229910052717 sulfur Inorganic materials 0.000 description 32
- 239000011593 sulfur Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 22
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical class CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 17
- 150000001336 alkenes Chemical class 0.000 description 15
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 14
- 238000009835 boiling Methods 0.000 description 14
- 239000001273 butane Substances 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 150000003568 thioethers Chemical class 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012876 carrier material Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000003464 sulfur compounds Chemical class 0.000 description 6
- 238000011144 upstream manufacturing Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- -1 C5 dienes Chemical class 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical compound C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-NJFSPNSNSA-N oxygen-18 atom Chemical compound [18O] QVGXLLKOCUKJST-NJFSPNSNSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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Abstract
本發明涉及一種催化劑,用於在高級二烯類(特別是C5二烯類)存在下,從烴類流(特別是C4流)中移除硫醇類及任選的二硫化物類(若存在)的方法。同時,本發明亦涉及在一個具體實例中,在1-丁烯存在下,藉由硫醇類與多不飽和烴類的硫醚化反應,從烴類流(特別是C4流)中移除硫醇類及二硫化物類(若存在)的方法,其中該方法是在高級二烯類(特別是C5
二烯類)存在下,在添加氫氣的反應器中進行。
Description
本發明涉及一種催化劑,用於在高級二烯類(特別是C5二烯類)存在下,從烴類流(特別是C4流)中移除硫醇類及任選的二硫化物類的方法。同時,本發明亦涉及在一個具體實例中,在1-丁烯存在下,藉由硫醇類與多不飽和烴類的硫醚化反應,從烴類流(特別是C4流)中移除硫醇類的方法,其中該方法是在高級二烯類(特別是C5二烯類)存在下,在添加氫氣的反應器中進行。
C4烴類的混合物為下游石油化學的原料。其來自蒸汽裂解器(所謂的「裂解C4」),或來自流體催化裂解器(所謂的「FCC C4」)。也交換了不同來源的C4烴類的混合物,即所謂的「C4餾分」。為了利用各個組分,需要將C4混合物分成盡可能高純度的組分。
硫醇類為R-SH類的化合物,其中R為烴基,S為硫,且H為氫。硫醇類也稱為巰類(thiol)。硫醇類的重要代表是甲硫醇及乙硫醇,分別稱為甲硫醇(methanethiol)及乙硫醇(ethanethiol)。在本發明的上下文中,二硫化物類為具有S-S鍵的有機化合物。重要代表是二硫化二甲基。至高為200ppm的硫醇類在C4烴混合物中作為不受歡迎的伴生物質出現。
來自催化裂解器(FCC C4)或蒸汽裂解器(裂解C4)的工業用C4烴類混合物通常不僅含有飽和及單不飽和化合物,且也含有多不飽和化合物。
在可從此等混合物中分離出單個化合物之前,通常必須盡可能徹底移除其他化合物。可藉由物理方法,例如蒸餾、萃取蒸餾或萃取,也可藉著對要移除的組分進行選擇性化學轉化來完成。在此須對最大程度地移除存在於C4烴類混合物中的汙染物(例如含氧、含氮及含硫的組分)特別注意,因為此等汙染物會對作為催化劑毒物的各個製程步驟產生不利影響。此等汙染物通常僅以微量形式存在於裂解C4中,而其也可能以較高濃度存在FCC C4流中。
原料的組成可根據原料的來源顯著變化。列出的C4組分也額外伴有具有更少或更多碳原子的烴類及少量汙染物,諸如硫醇類、硫化物類、二硫化物類,以及含氮與含氧的化合物。
在一個變體中,可對FCC C4進行加工(workup),使得首先藉由蒸餾步驟降低異丁烷的濃度。同時,混合物中存在的低沸物(例如C3烴類、輕度含氧、含氮及含硫的化合物)被移除或減至最少。在後續於塔中進行的步驟中,所有的高沸物(例如C5烴類、重度的含氧、含氮及含硫的化合物)經由塔底移除。在下一步中,例如藉由使異丁烯類與甲醇反應得到甲基三級丁基醚(MTBE),接著藉由蒸餾將異丁烯類移除。若要獲得純的異丁烯類,則可以隨後裂解甲基三級丁基醚以得到異丁烯類及甲醇。
為了進一步加工C4混合物,必須藉由選擇性氫化方法將仍殘留的多不飽和化合物轉化為相應的單不飽和化合物。接著,可藉由蒸餾以足夠的純度移除1-丁烯及剩餘的異丁烷,並對剩餘的2-丁烯及正丁烷進一步加工。通常,藉由二聚合將2-丁烯類轉化為辛烯類,接著藉由氫甲醯化反應及氫化將其轉化為塑化劑醇類。飽和的C4烴類可例如用作霧劑的推進劑。
若在移除1-丁烯之前進行的選擇性加氫製程未將多不飽和化合物的濃度降低到小於10ppm的值,則不能滿足聚合中使用的1-丁烯的純度要求。多不飽和化合物也抑制了催化劑對2-丁烯類二聚合的催化活性。
對多不飽和烴類進行選擇性氫化的製程中對選擇性的要求特別高,這是因為過度氫化(即單不飽和化合物的氫化,或末端雙鍵異構化為內雙鍵)會導致有價值產物的破壞。在已具有低含量的多不飽和化合物的流的精緻純化中,必須同時將多不飽和化合物的濃度進一步降低至低於10重量ppm的值。
就催化性C4流而言,現今可能發生的情況為,除了在低沸物的去除過程中已藉由蒸餾移除的輕度含硫組分(例如H2S、COS或MeSH)及之後在C5管柱中移除的高沸點硫化合物(諸如二甲基二硫化物)以外,仍存在硫醇型中沸物(例如乙硫醇)。此等不易藉由蒸餾從C4流中移除。在C4流的加工過程中,硫醇類的存在為不受歡迎的或會對加工造成干擾。
若饋料中存在硫醇類(例如乙硫醇)及任選的二硫化物類以進行選擇性氫化,則其會抑制1,3-丁二烯的催化轉化。這表示支鏈的多不飽和化合物可能存在於後續產物(例如1-丁烯)中,並危害其純度。若由於硫醇類含量引起的選擇性氫化轉化率不足,多不飽和化合物通入正丁烯類低聚合反應的饋料中,則會使低聚合催化劑鈍化。
已知將含硫組分饋料到選擇性氫化催化劑可導致加氫異構化活性催化劑的形成。饋料中存在的用於選擇性氫化的硫醇類可導致此加氫異構化催化劑的形成,導致1-丁烯不意欲地異構化為2-丁烯類。
因此,DE 10 2012 212 317 A1提出了一種使用非均相催化劑將多不飽和烴類與硫醇類進行硫醚化反應的方法,該非均相催化劑含有鈀作為催化活性金屬並添加氫,該氫與多不飽和烴類以確定的比例使用。在DE 10 2012 212 317 A1中同樣給出了關於從烴類流中移除硫醇類的其他現有技術的詳細描述。
然而,那其中使用的催化劑的缺點在於,硫醇類的硫醚化反應受限於高級二烯類(諸如C5二烯類,特別是異戊二烯類)的存在,且反應未進行完全。這表示硫醇類(諸如乙硫醇及/或甲硫醇)殘留在烴類流中,並可能導致已
描述的問題。
此外,若異戊二烯類及/或其他長鏈多不飽和烴類同時存在,則可能存在於C4流中的二硫化物類(諸如二甲基二硫化物)會被裂解成兩當量的甲硫醇。這導致硫醇類含量實際上增加,而並非藉由硫醚化反應降低。
因此,本發明的目的為提供一種催化劑,即使在高級二烯類存在下,該催化劑也能夠(幾乎)完全轉化烴類流中存在的硫醇類及任選的二硫化物類(若存在),即包括可能藉由二硫化物類裂解原位形成的硫醇類。另一個目的為提供一種不受上述問題困擾的方法,其使得硫醇類的硫醚化反應特別可進行到完全。
目的藉由如請求項1的本發明的催化劑及如請求項6的方法實現。較佳的具體實例在附屬項中具體說明。
本發明提供一種非均相催化劑,用於在高級二烯類存在下從烴類流中移除硫醇類及任選的二硫化物類(若存在),其中該催化劑為核殼催化劑,其中該催化劑包含氧化鋁、矽膠或活性碳作為載體材料以及鈀和鉑作為催化活性金屬,且其中該催化劑的鈀濃度至高為2.0重量%,較佳至高為1.0重量%,更佳至高為0.5重量%,鉑濃度至高為1.0重量%,較佳至高為0.5重量%,更佳至高為0.2重量%,且金屬總分散度至少為70%。鈀和鉑濃度的設定值(stated value)
在每種情況下均指總催化劑。「核殼催化劑」乙詞是指催化劑的形式,其中核由載體材料組成,在載體材料上藉由噴塗製程及接續的煅燒來塗覆Pd/PdO及Pt/PtO的殼,該殼的層厚及滲透深度在每種情況下僅為幾微米。
烴類流較佳包含C2至C8烯烴類,更佳包含C3至C6烯烴類,且最佳包含C4烯烴類。待純化的硫醇類及二硫化物類(若存在)的烴類流特別為C4烴類流(C4流)。合適的烯烴類包括α-烯烴類、n-烯烴類及環烯烴類,較佳包括n-烯烴類。在一個較佳的具體實例中,烯烴類為正丁烯類。烯烴類通常不以純淨形式使用,而是以工業上可獲得的混合物形式使用,諸如上述的裂解C4或FCC C4。因此,在本發明中另外使用的烴類流乙詞應理解為意指包含相關烯烴類的任何類型的混合物,其含量使得可經濟上進行下游純化可能的製程步驟。
在本發明的上下文中,「高級二烯類」乙詞是指至少C5二烯類或具有多於5個碳原子的二烯類。高級二烯類較佳為C5二烯類,特別是異戊二烯類。根據本發明,二烯類通常以低濃度存在於要純化的硫醇類的工業用烴類流中。與例如丁二烯類相比,高級二烯類在選擇性氫化中的反應難度更大(請另參見WO 2012/004081 A1),這表示C5二烯類對反應的抑制在硫醚化反應中也是合理的。
在本發明的方法中使用的催化劑是由載體材料及作為催化活性金屬的鈀和鉑組成的核殼催化劑,藉由該核殼催化劑可將烴類流中的硫醇類完全轉化為硫醚類。載體材料例如為氧化鋁、矽膠或活性碳。所使用的載體材料較佳為氧化鋁。
催化劑的鈀濃度至高為2.0重量%,較佳至高為1.0重量%,且更佳至高為0.5重量%。同時,催化劑的鉑濃度至高為1.0重量%,較佳至高為0.5重量%,且更佳為0.2重量%。
催化劑的內表面積(根據DIN ISO 9277藉氣體吸附測定)較佳為50至400m2/g,更佳介於100與300m2/g之間,且特別較佳介於200與300m2/g之間。
在一個較佳的具體實例中,催化劑亦具有至少0.5m2/g,較佳至少1.0m2/g,更佳為至少1.5m2/g的總金屬表面積(其根據AN-SOP 1954 version 1藉由CO脈衝化學吸附法測定)。總金屬表面積小於所示出的那些會導致催化劑活性降低。
根據本發明的催化劑具有至少70%,較佳至少80%的金屬總分散度。金屬總分散度表明金屬/金屬氧化物在表面上的分散程度。可藉由在催化劑的製備過程中,以Pd/Pt鹽溶液噴射載體材料的持續時間及強度來控制表面上的分散程度。此處分散度是指分散相(Pd/Pt)及分散介質(載體)的非均相混合物。在表面上的分散度越高,則催化劑的活性越高。令人驚訝地發現,若金屬總分散度低於70%,則硫醇類無法完全轉化。
本發明進一步提供了一種在至少一種高級二烯類存在下藉由硫醇類與多不飽和烴類的硫醚化反應從烴類流中移除硫醇類及二硫化物類(若存在)的方法,其中該方法在添加氫氣的反應器中進行,其中氫與多不飽和烴類的莫耳比不大於1。該方法使用前述的包含鈀和鉑作為催化活性金屬的非均相催化劑,其中該催化劑的鈀濃度至高為2.0重量%,較佳至高為1.0重量%,更佳至高為0.5重量%,鉑濃度至高為1.0重量%,較佳至高為0.5重量%,更佳至高為0.2重量%,且金屬總分散度為至少70%,較佳為至少80%。鈀和鉑濃度的設定值(stated value)在每種情況下均指總催化劑。
烴類流較佳包含C2至C8烯烴類,更佳包含C3至C5烯烴類,且最佳包含C4烯烴類。待純化的硫醇類的烴類流特別為C4烴類流(C4流)。合適的烯烴類包括α-烯烴類、n-烯烴類及環烯烴類,較佳包括n-烯烴類。在一個較佳的具體實例中,烯烴類為正丁烯類。烯烴類通常不以純淨形式使用,而是以工業上可獲得的混合物形式使用,諸如上述的裂解C4或FCC C4。因此,在本發明中另外使用的烴類流乙詞應理解為意指包含相關烯烴類的任何類型的混合物,其含量
使得可經濟上進行下游純化可能的製程步驟。
在本發明的上下文中,「高級二烯類」乙詞是指至少C5二烯類或具有多於5個碳原子的二烯類。高級二烯類較佳為C5二烯類,特別為異戊二烯類。根據本發明,二烯類通常以低濃度存在於要純化的硫醇類的工業用烴類流中。與丁二烯類相比,高級二烯類在選擇性氫化中的反應難度更大(請另參見WO 2012/004081 A1),這表示C5二烯類對反應的抑制在硫醚化反應中也是合理的。
藉由使用包含鈀和鉑作為催化活性金屬的非均相催化劑,根據本發明的方法能夠將硫醇類完全轉化為高沸點硫醚類,同時幾乎完全抑制了1-丁烯顯著異構化成內丁烯類,且完全防止丁烯類的氫化。若該烴類流中1-丁烯的濃度高於1-丁烯雙鍵異構化為2-丁烯的熱力學平衡時的濃度,則藉由異構化及/或氫化成正丁烷而將1-丁烯轉化為2-丁烯類的比例較佳小於5%,更佳小於3%,且最佳小於2%。
已發現到,在多不飽和烴類及氫氣的存在下,可將硫醇類轉化成高沸點的硫醚類以低於檢測極限,而大大抑制1-丁烯的異構化且完全防止丁烯類的氫化。硫醇類的檢測極限目前約為50ppbw,即重量比例為50*10-9。
在本發明的上下文中,相對於烴類混合物中存在的多不飽和烴類而言,為一(等莫耳),方法中必須遵守的使用的氫氣量最大為1(等莫耳)。氫氣與多不飽和烴類的莫耳比較佳介於0.01與0.8之間。更佳介於0.1與0.5之間。
此方法的主要優點為氫氣含量低,這表示存在於C4流中的1-丁烯幾乎不會發生異構化,且仍可作為有價值的產品使用。只有藉由嚴格限制饋料中存在的氫氣量的限制,才有可能將硫醇類與多不飽和C4烴類醚化成高沸點硫醚類,使其濃度低於50ppbw,而不伴隨饋料中同樣存在的單不飽和丁烯類的氫化及1-丁烯的顯著異構化。然而,不可能完全省略氫氣,這是因為若沒有氫氣則無硫醇類的轉化。
根據本發明的方法的另一個優點為,即使在高級二烯類存在下,也可使硫醇類完全轉化。
與硫醇類進行硫醚化反應的多不飽和烴類較佳為1,3-丁二烯及/或3-丁烯-1-炔及/或1,2-丁二烯。此等二烯類及炔類特別僅以少量存在於FCC C4中,且在任何情況下都必須在下游完全氫化,因此不再可作為有價值的產品使用。在具有高1,3-丁二烯含量的裂解C4流中,首先在單獨製程中將1,3-丁二烯移除並加以利用。接著可將殘留在C4流中的殘留丁二烯類用於硫醚化反應。
該方法的另一個特別的優點為,除了高反應性硫醇類(甲硫醇類)之外,高級硫醇類(例如乙硫醇類)也可進行反應從而被移除。
一氧化碳可任選地在該方法中另外添加到烴類混合物中。在這種情況下,饋料中一氧化碳的含量以烴類混合物的質量計為0.05至20ppm。一氧化碳的添加量較佳介於0.5與5ppm之間。超過20ppm的定量計量並不會進一步改善結果。一氧化碳分別計量加入反應器中,或與饋入的C4流混合。一氧化碳可作為額外的調節劑以減少1-丁烯異構化為2-丁烯類。
反應器饋料的入口溫度較佳在0-180℃的範圍內,更佳在60-150℃的範圍內,特別較佳在80-130℃的範圍內。壓力較佳在2到50bar的範圍內,更佳在6到40bar的範圍內,特別較佳在10到30bar的範圍內。在一個較佳的具體實例中,氫氣已完全溶解在烴類流中。在這種情況下,必須選擇壓力以使氫氣保持完全溶解,且在反應器中不產生氣相。
硫醚化反應較佳以液相方法操作。這表示所有組分都以液相形式存在於催化劑中,或以液態形式引入反應器中。特別地,這表示氫氣以及任選的一氧化碳皆完全溶解在液相中。因此,氫氣以細分散的形式及一定量添加到待氫化的烴類混合物中,使得液相在被送入反應器之前總是均相的。
待醚化的烴類混合物可含有0.01至200重量ppm的硫醇類及二硫
化物類(若存在)。硫醚化反應可在一或多個反應階段中進行。若饋料中硫醇類及二硫化物類(若存在)的含量很高,以致所需的氫氣量不再溶於饋料中,則可藉由循環稀釋饋料。或者,可以以分佈在反應器長度上或各個反應階段上的多個部分添加氫氣。
在硫醇類(包括由任選存在的二硫化物類形成的硫醇類)轉化成高沸點硫醚類之後,可藉由蒸餾移除此等硫醚類。藉由這種方式,可將剩餘C4烴類混合物中的硫醚類含量降低到50重量ppb以下。連同可能硫醚化反應器上游的低沸物移除與硫醚化反應器下游的高沸物蒸餾,這表示可從C4烴類混合物中完全移除所有含硫組分。
可藉由氣相層析法在線測量多不飽和烯烴類的濃度,從而可由此精確設定氫氣的量。同樣適用於含硫化合物。
該方法較佳與源自催化裂解器(FCC C4)或蒸汽裂解器(裂解C4)的含硫醇類的C4烴類的混合物一同使用。當然也可加工C4餾分。
用作饋料的C4烴類混合物首先較佳藉由蒸餾移除低沸物,特別是異丁烷。或者,在移除異丁烷之前採用該方法。
下文藉由實施例闡明本發明。然而,僅為了說明而選擇此等實施例,而不應視其為限制性的。
實施例1(非本發明):管狀反應器中填充有540ml的催化劑,其中在Al2O3上含有0.5重量%的Pd。C4混合物在90℃及20bar下以連續4kg/h的速度通過反應器。C4混合物具有以下組成:0.5重量%的1,3-丁二烯、13.8重量%的丁烷、40.3重量%的2-丁烯類、20.3重量%的1-丁烯、22.0重量%的異丁烯類及3.1重量%的C5烴類,以及120重量ppm的異戊二烯類、來自乙硫醇的2.8重量ppm的硫及來自二甲基二硫化物的
6.0重量ppm的硫。
在反應器上游將4.4Nl/h的氫氣計量加入。來自反應器排放的組成如下:0.4重量%的1,3-丁二烯、14.1重量%的丁烷、40.3重量%的2-丁烯類、20.3重量%的1-丁烯、21.8重量%的異丁烯類及3.1重量%的C5烴類,以及100重量ppm的異戊二烯類、來自乙硫醇的0.7重量ppm的硫及來自二甲基二硫化物的2.2重量ppm的硫。亦檢測出來自甲硫醇類的1.5重量ppm的硫,以及來自高沸點化合物的4.4重量ppm的硫。
這對應於乙硫醇75%的轉化,以及二甲基二硫化物38.3%轉化為高沸點硫化合物,與二甲基二硫化物25%轉化為甲硫醇。
乙硫醇類的完全轉化並無實現,此外,由二甲基二硫化物形成額外的硫醇(甲硫醇)。
實施例2(本發明):管狀反應器中填充有540ml的催化劑,其中在Al2O3上含有0.5重量%的Pd及0.2重量%的Pt。C4混合物在90℃及20bar下以連續4kg/h的速度通過反應器。C4混合物具有以下組成:0.6重量%的1,3-丁二烯、12.3重量%的丁烷、40.5重量%的2-丁烯類、19.5重量%的1-丁烯、23.8重量%的異丁烯類及3.3重量%的C5烴類,以及95重量ppm的異戊二烯類、來自乙硫醇的3.4重量ppm的硫及來自二甲基二硫化物的3.2重量ppm的硫。
在反應器上游將4.4Nl/h的氫氣計量加入。來自反應器排放的組成如下:0.5重量%的1,3-丁二烯、12.6重量%的丁烷、39.5重量%的2-丁烯類、19.5重量%的1-丁烯、24.6重量%的異丁烯類及3.3重量%的C5烴類,以及80
重量ppm的異戊二烯類、來自乙硫醇的0.0重量ppm的硫及來自二甲基二硫化物的1.2重量ppm的硫,以及來自高沸點化合物的5.4重量ppm的硫。
未檢測到甲硫醇。這對應於乙硫醇100%的轉化,以及二甲基二硫化物62.5%轉化為高沸點硫化合物。
藉由使用根據本發明的催化劑,與非本發明的催化劑相比,硫醇類的轉化率顯著提高。
實施例3(非本發明):管狀反應器中填充有540ml的催化劑,其中在Al2O3上含有0.5重量%的Pd及0.2重量%的Pt。該催化劑具有根據AN SOP 1954(version 1)藉由CO脈衝化學吸附法測定的以下特性。
C4混合物在90℃及20bar下以連續4kg/h的速度通過反應器。C4混合物具有以下組成:0.7重量%的1,3-丁二烯、13.6重量%的丁烷、40.4重量%的2-丁烯類、20.3重量%的1-丁烯、22.2重量%的異丁烯類及2.9重量%的C5烴類,以及87重量ppm的異戊二烯類、來自乙硫醇的5.1重量ppm的硫及來自二甲基二硫化物的5.1重量ppm的硫。
在反應器上游將5.3Nl/h的氫氣計量加入。來自反應器排放的組成如下:0.4重量%的1,3-丁二烯、13.7重量%的丁烷、39.1重量%的2-丁烯
類、20.8重量%的1-丁烯、23.2重量%的異丁烯類及2.9重量%的C5烴類,以及72重量ppm的異戊二烯類、來自乙硫醇的1.4重量ppm的硫及來自二甲基二硫化物的1.7重量ppm的硫。另外檢測出來自甲硫醇類的0.9重量ppm的硫,以及來自高沸點化合物的6.2重量ppm的硫。
這對應於乙硫醇72.5%的轉化,以及二甲基二硫化物35.3%轉化為高沸點硫化合物,與二甲基二硫化物17.6%轉化為甲硫醇。乙硫醇類的完全轉化並無實現,此外,甲硫醇的存在表示二甲基二硫化物形成了額外的硫醇。
實施例4(本發明):管狀反應器中填充有540ml的催化劑,其中在Al2O3上含有0.5重量%的Pd及0.2重量%的Pt。該催化劑具有根據AN SOP 1954(version 1)藉由CO脈衝化學吸附法測定的以下特性。
C4混合物在90℃及20bar下以連續4kg/h的速度通過反應器。C4混合物具有以下組成:0.7重量%的1,3-丁二烯、13.0重量%的丁烷、39.8重量%的2-丁烯類、19.2重量%的1-丁烯、23.9重量%的異丁烯類及3.4重量%的C5烴類,以及112重量ppm的異戊二烯類、來自乙硫醇的5.7重量ppm的硫及來自二甲基二硫化物的5.4重量ppm的硫。
在反應器上游將5.6Nl/h的氫氣計量加入。來自反應器排放的組成如下:
0.4重量%的1,3-丁二烯、13.0重量%的丁烷、40.4重量%的2-丁烯類、18.9重量%的1-丁烯、23.8重量%的異丁烯類及3.4重量%的C5烴類,以及96重量ppm的異戊二烯類、來自乙硫醇的0.0重量ppm的硫及來自二甲基二硫化物的0.7重量ppm的硫。
未檢測到甲硫醇。這對應於乙硫醇100%的轉化,以及二甲基二硫化物87%轉化為高沸點硫化合物。
實施例5(本發明):管狀反應器中填充有540ml的催化劑,其中在Al2O3上含有0.5重量%的Pd及0.2重量%的Pt。該催化劑具有根據AN SOP 1954(version 1)藉由CO脈衝化學吸附法測定的以下特性。
C4混合物在90℃及20bar下以連續4kg/h的速度通過反應器。C4混合物具有以下組成:0.6重量%的1,3-丁二烯、12.4重量%的丁烷、39.8重量%的2-丁烯類、19.9重量%的1-丁烯、23.9重量%的異丁烯類及3.8重量%的C5烴類,以及124重量ppm的異戊二烯類、來自乙硫醇的3.3重量ppm的硫及來自二甲基二硫化物的2.2重量ppm的硫。
在反應器上游將4.4Nl/h的氫氣計量加入。來自反應器排放的組成如下:0.4重量%的1,3-丁二烯、12.6重量%的丁烷、39.8重量%的2-丁烯
類、19.7重量%的1-丁烯、23.4重量%的異丁烯類及3.8重量%的C5烴類,以及104重量ppm的異戊二烯類、來自乙硫醇的0.0重量ppm的硫及來自二甲基二硫化物的0.6重量ppm的硫。
未檢測到甲硫醇。這對應於乙硫醇100%的轉化,以及二甲基二硫化物72.7%轉化為高沸點硫化合物。
在實施例3至5的比較中,顯示了當使用金屬總分散度小於70%的催化劑時,硫醇類不能完全轉化。當催化劑上的金屬總分散度高於70%時,僅在實施例4及5中實現完全轉化。
Claims (15)
- 一種非均相催化劑,用於在高級二烯類存在下從烴類流中移除硫醇類及任選的二硫化物類,其中該催化劑為核殼催化劑,其特徵在於該催化劑包含氧化鋁、矽膠或活性碳作為載體材料以及鈀和鉑作為催化活性金屬,其中該催化劑的鈀濃度至高為2.0重量%,鉑濃度至高為1.0重量%,且該催化劑的金屬總分散度至少為70%,其中該催化劑的金屬總分散度係根據AN-SOP 1954 version 1藉由CO脈衝化學吸附法測定,其中該催化劑的內表面積(根據DIN ISO 9277藉氣體吸附測定)為50至400m2/g。
- 如請求項1之非均相催化劑,其特徵在於,該催化劑的鈀濃度至高為1.0重量%。
- 如請求項1或2之非均相催化劑,其特徵在於,該催化劑的鉑濃度至高為0.5重量%。
- 如請求項1或2之非均相催化劑,其特徵在於,該催化劑的總金屬表面積為至少0.5m2/g。
- 如請求項1或2之非均相催化劑,其特徵在於,該催化劑的金屬總分散度為至少80%,其中該催化劑的金屬總分散度係根據AN-SOP 1954 version 1藉由CO脈衝化學吸附法測定。
- 一種在至少一種高級二烯類存在下藉由硫醇類與多不飽和烴類的硫醚化反應從烴類流中移除硫醇類及任選的二硫化物類的方法,其中該方法在添加氫氣的反應器中進行,其中氫與多不飽和烴類的莫耳比不大於1,其特徵在於,該方法中使用的非均相催化劑包含鈀和鉑作為催化活性金屬,其中該催化劑的鈀濃度至高為2.0重量%,鉑濃度至高為1.0重量%,且該催化劑的金屬總分散度至少為70%, 其中該催化劑的金屬總分散度係根據AN-SOP 1954 version 1藉由CO脈衝化學吸附法測定,其中該催化劑的內表面積(根據DIN ISO 9277藉氣體吸附測定)為50至400m2/g。
- 如請求項6之方法,其特徵在於,該高級二烯類為C5二烯類。
- 如請求項6或7之方法,其特徵在於,該等硫醇類以多不飽和烴類硫醚化,其中該等多不飽和烴類選自1,3-丁二烯、3-丁烯-1-炔及1,2-丁二烯所組成之群。
- 如請求項6或7之方法,其特徵在於,至少乙硫醇及/或甲硫醇作為硫醇類存在。
- 如請求項6或7之方法,其特徵在於,氫與多不飽和烴類的莫耳比介於0.01與0.8之間。
- 如請求項6或7之方法,其特徵在於,該方法在一氧化碳存在下進行,其中以饋料的質量計,該反應器饋料中一氧化碳的含量小於20ppm。
- 如請求項6或7之方法,其特徵在於,該反應器饋料的入口溫度介於0℃與180℃之間。
- 如請求項6或7之方法,其特徵在於,該方法作為液相方法操作,且氫氣完全溶解在液相中。
- 如請求項6或7之方法,其特徵在於,C4烴流用作該反應器的進料。
- 如請求項6或7之方法,其特徵在於,若該烴類流中1-丁烯的濃度高於1-丁烯雙鍵異構化為2-丁烯的熱力學平衡時的濃度,則藉由異構化及/或氫化成正丁烷而將1-丁烯轉化為2-丁烯類的比例小於5%。
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- 2020-01-07 KR KR1020200001837A patent/KR20200086228A/ko unknown
- 2020-01-07 TW TW109100451A patent/TWI835968B/zh active
- 2020-01-07 EP EP20150484.2A patent/EP3680014A1/de active Pending
- 2020-01-08 CN CN202010016947.7A patent/CN111408367A/zh active Pending
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EP3680014A1 (de) | 2020-07-15 |
US11186782B2 (en) | 2021-11-30 |
TW202026407A (zh) | 2020-07-16 |
US20200216763A1 (en) | 2020-07-09 |
CN111408367A (zh) | 2020-07-14 |
KR20200086228A (ko) | 2020-07-16 |
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