CN105658314A - 分离用的交联橡胶聚氨酯-醚膜 - Google Patents
分离用的交联橡胶聚氨酯-醚膜 Download PDFInfo
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- CN105658314A CN105658314A CN201480058117.3A CN201480058117A CN105658314A CN 105658314 A CN105658314 A CN 105658314A CN 201480058117 A CN201480058117 A CN 201480058117A CN 105658314 A CN105658314 A CN 105658314A
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- ether
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- polyurethane
- crosslinking rubber
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 238000000926 separation method Methods 0.000 title description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims description 56
- 238000004132 cross linking Methods 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 27
- 239000003345 natural gas Substances 0.000 claims description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- 239000012456 homogeneous solution Substances 0.000 claims description 9
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- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 5
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- 229920002284 Cellulose triacetate Polymers 0.000 claims description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
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- 239000004721 Polyphenylene oxide Substances 0.000 abstract 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 2
- 239000012466 permeate Substances 0.000 abstract 1
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 13
- 229960004063 propylene glycol Drugs 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- 0 Cc1ccc(C)c(*=C)c1 Chemical compound Cc1ccc(C)c(*=C)c1 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
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- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 239000003949 liquefied natural gas Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- IFVGFQAONSKBCR-UHFFFAOYSA-N n-[bis(aziridin-1-yl)phosphoryl]pyrimidin-2-amine Chemical compound C1CN1P(N1CC1)(=O)NC1=NC=CC=N1 IFVGFQAONSKBCR-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
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- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
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- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000009329 sexual behaviour Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
由交联橡胶聚氨酯-醚聚合物制造交联橡胶聚氨酯-醚聚合膜,所述聚合物由二异氰酸酯封端聚醚和具有四个羟基官能团的四醇合成。该四醇上的羟基与该二异氰酸酯封端聚醚上的异氰酸酯基团反应以形成氨酯键。该交联橡胶聚氨酯-醚聚合膜选择性渗透可冷凝蒸气,如C3至C35烃、芳族化合物、水蒸气、二氧化碳和硫化氢并截留甲烷和乙烷。该交联橡胶聚氨酯-醚聚合膜具有对可冷凝蒸气的高渗透性、对可冷凝蒸气超过对甲烷和乙烷的高选择性和对液体化学品的高耐受性。
Description
优先权声明
本申请要求2013年10月29日提交的美国申请No.14/066248的优先权,其内容全文经此引用并入本文。
发明背景
在过去30-35年,聚合物膜基气体分离法的技术状况快速演化。与传统分离方法相比,膜基技术具有低资本成本和高能量效率的优点。膜气体分离对石油生产商和炼制商、化学公司和工业气体供应商特别有意义。一些应用已获得商业上的成功,包括从天然气和从生物气中除去二氧化碳和强化采油,以及在氨吹扫气流中从氮气、甲烷和氩气中脱氢。
但是,在实践中证实,如果不使用预处理系统,膜性能会极快退化。膜性能损失的主要原因是在膜表面上的重烃液体冷凝。可以通过基于膜产物气体的计算露点为操作提供足够的露点余地来防止冷凝。开发出UOP’sMemGuardTM系统(一种使用分子筛的预处理可再生吸附系统)以从天然气料流中除去水以及C6至C35的重烃并因此降低该料流的露点。通过预处理系统选择性除去重烃可显著改进该膜的性能。
尽管这些预处理系统可从天然气料流中有效除去重烃以控制天然气的露点,但成本极高。一些商业膜项目显示,根据进料组成,该预处理系统的成本高达总成本(预处理系统和膜系统)的10至40%。降低预处理系统成本或彻底消除预处理系统会显著降低用于天然气提质的膜系统成本。另一方面,近年来,越来越多的膜系统已用于大型海上天然气提质项目。对于海上项目,占地面积是一大限制。因此,占地面积的降低对海上项目非常重要。预处理系统的占地面积也非常高——整个膜系统的占地面积的大于10-50%。因此,从该膜系统中除去预处理系统明显降低该膜系统的成本和占地面积,尤其是对海上天然气用途,如浮式生产储油卸油船(FPSO)用途而言。
调质天然气已用作烃加工工业中的燃气发动机和涡轮机中的燃料气体,特别用于海上平台和边远地区,并将用于未来的浮式液化天然气(FLNG)和FPSO用途。为改进用于燃料气体调质的设备的可靠性和减少计划外停工期,需要简单的燃料气体调质技术。可选择性和有效渗透重烃和其它污染物,如CO2、H2S和水蒸汽的橡胶聚合膜能够实现燃料气体的调质。
可选择性渗透可冷凝重烃蒸气,如C3+烃并可截留不可冷凝气体,如甲烷的橡胶聚合膜也可用于天然气凝液(NGL)回收。
传统Grace橡胶聚脲/聚氨酯膜(S-Brane)已用于芳族化合物/非芳族化合物分离。但是,处理量(通量)对大多数芳族化合物分离用途而言不够高。
本发明描述了新型交联橡胶聚氨酯-醚聚合膜、制造该膜的方法和这种新型膜的用途。
发明概述
本发明涉及交联橡胶聚氨酯-醚聚合膜、制造该膜的方法和这种新型膜系统用于NGL回收、燃料气体调质、天然气预处理、从流化催化裂化(FCC)和其它石脑油料流中脱硫以及芳族化合物分离,如芳族化合物/正链烷烃分离和二甲苯分离的用途。
本发明中描述的交联橡胶聚氨酯-醚聚合膜包含由二异氰酸酯封端聚醚和包含四个或更多个羟基官能团的刚性交联剂合成的交联橡胶聚氨酯-醚聚合物。在本发明中使用包含四个或更多个羟基官能团的刚性交联剂合成交联橡胶聚氨酯-醚聚合物导致形成交联的聚合物结构。该刚性交联剂上的羟基与该二异氰酸酯封端聚醚上的异氰酸酯基团反应以形成氨酯键。
本发明中描述的交联橡胶聚氨酯-醚聚合膜选择性渗透可冷凝蒸气,如C3至C35烃、芳族化合物、水蒸气、二氧化碳和硫化氢并截留甲烷和乙烷。可以处理流体料流,包括气体和液体,以从天然气中分离高级烃。这些膜也可用于芳族化合物料流的分离。本发明中描述的交联橡胶聚氨酯-醚聚合膜具有对可冷凝蒸气的高渗透性、对可冷凝蒸气超过甲烷和乙烷的高选择性和对液体化学品的高耐受性。
发明详述
本发明涉及新型交联橡胶聚氨酯-醚聚合膜、制造该膜的方法和这种新型膜系统用于NGL回收、燃料气体调质、天然气预处理、从流化催化裂化(FCC)料流和其它石脑油料流中脱硫以及芳族化合物分离,如芳族化合物/正链烷烃分离和二甲苯分离的用途。
本发明中描述的交联橡胶聚氨酯-醚聚合膜包含由二异氰酸酯封端聚醚和包含四个或更多个羟基官能团的刚性交联剂合成的交联橡胶聚氨酯-醚聚合物。在本发明中使用包含四个或更多个羟基官能团的刚性交联剂合成交联橡胶聚氨酯-醚聚合物导致形成交联的聚合物结构。该刚性交联剂上的羟基与该二异氰酸酯封端聚醚上的异氰酸酯基团反应以形成氨酯键。
本发明中描述的交联橡胶聚氨酯-醚聚合膜选择性渗透可冷凝蒸气,如C3至C35烃、芳族化合物、水蒸气、二氧化碳和硫化氢并截留甲烷和乙烷。本发明中描述的交联橡胶聚氨酯-醚聚合膜具有对可冷凝蒸气的高渗透性、对可冷凝蒸气超过对甲烷和乙烷的高选择性和对液体化学品的高耐受性。
本发明中描述的交联橡胶聚氨酯-醚聚合膜包含具有多个式(I)的重复单元的交联橡胶聚氨酯-醚聚合物,其中所述式(I)是:
其中X1、X2、X3和X4分别选自
及其混合物;X1、X2、X3和X4彼此相同或不同;其中Y选自
及其混合物;其中Z1、Z2、Z3和Z4分别选自
及其混合物;Z1、Z2、Z3和Z4彼此相同或不同且t为0至4;其中n、m、p、q、r和s独立地为2至500的整数。式(I)的X1、X2、X3和X4优选相同并具有化学结构
式(I)的X1、X2、X3和X4的Z1优选是:
式(I)的Y优选是:
本发明中的交联橡胶聚氨酯-醚膜优选如下制备:1)将二异氰酸酯封端聚醚和包含四个或更多个羟基官能团的刚性交联剂溶解在溶剂中以形成均匀溶液;2)在30℃至100℃的温度下加热该溶液0.5至12小时以形成聚氨酯-醚预聚物;3)在相对多孔的膜载体(例如由无机陶瓷材料制成的载体或由聚合物制成的载体)上涂布该聚氨酯-醚预聚物溶液的层;4)将该涂膜在30℃至100℃的温度下加热0.5至12小时以在膜载体上提供包含该交联橡胶聚氨酯-醚材料的选择性薄层。在一些情况下,在步骤4)后通过重复步骤3)和4)添加该交联橡胶聚氨酯-醚的第二层。
用于合成本发明中的交联橡胶聚氨酯-醚聚合物的二异氰酸酯封端聚醚选自
及其混合物;其中Z1、Z2、Z3和Z4分别选自
及其混合物;Z1、Z2、Z3和Z4彼此相同或不同且t为0至4;其中m、p、q、r和s独立地为2至500的整数。
用于合成本发明中的交联橡胶聚氨酯-醚聚合物的包含四个或更多个羟基官能团的刚性交联剂选自
及其混合物。
用于溶解二异氰酸酯封端聚醚和包含四个或更多个羟基官能团的刚性交联剂的溶剂主要根据它们完全溶解二异氰酸酯封端聚醚和包含四个或更多个羟基官能团的刚性交联剂的能力和在膜形成步骤中溶剂易清除性选择。溶剂选择中的其它考量包括低毒性、低腐蚀活性、低环境危害潜力、可得性和成本。用于本发明的代表性溶剂包括,但不限于,N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAC)、二氯甲烷、四氢呋喃(THF)、丙酮、N,N-二甲基甲酰胺(DMF)、二甲亚砜(DMSO)、甲苯、二氧杂环己烷、1,3-二氧戊环、它们的混合物。也可以使用本领域技术人员已知的其它溶剂。
可以将本发明中的交联橡胶聚氨酯-醚膜制成任何方便的形式,如片、盘、管或中空纤维。也可以将这些交联橡胶聚氨酯-醚膜制成包含选择性薄交联橡胶聚氨酯-醚层和含聚合物材料或无机材料的多孔载体层的复合薄膜。
本发明涉及新型膜系统用于天然气提质的用途。这种膜系统包括本发明中描述的第一阶段交联橡胶聚氨酯-醚聚合膜以选择性除去C3至C35烃以控制天然气的露点,和第二阶段膜以从天然气中选择性除去CO2。本发明中描述的新型膜系统消除了高成本和高占地面积的膜预处理系统的使用。本发明中描述的膜系统不需要级间压缩机。这是因为具有受控露点的天然气在高压下离开第一交联橡胶聚氨酯-醚聚合膜的渗余侧并作为高压进料直接引入第二膜。因此,与包括非膜相关的预处理系统的当前市售膜系统相比,该膜系统显著降低用于天然气提质的膜系统的占地面积和成本。最常用于商业天然气提质用途的膜,如乙酸纤维素和聚酰亚胺是玻璃态聚合物。但是,这些膜不能用于控制天然气的露点,因为它们对CH4比对C3至C35烃更选择性可渗透。当使用这些商业玻璃态聚合物膜进行天然气提质时,预处理系统是必需的。用作本发明中描述的新型膜系统中的第二阶段膜的膜具有比本发明中描述的用于天然气提质的第一阶段交联橡胶聚氨酯-醚聚合膜高的CO2/CH4选择性。用于本发明中描述的新型膜系统中的第二阶段膜的膜材料在50℃下在6.89MPa(1000psig)进料气压力下和在进料气中10%CO2和90%CH4下优选具有10或更高的CO2/CH4选择性。用于本发明中描述的新型膜系统中的第二阶段膜的膜材料可选自,但不限于,聚丙烯腈、聚砜;磺化聚砜;聚醚酰亚胺,如Ultem;纤维素聚合物,如乙酸纤维素和三乙酸纤维素;聚酰胺;聚酰亚胺,如Matrimid和P84或P84HT;聚酰胺/酰亚胺;聚酮、聚醚酮;聚(氧亚芳基),如聚(苯醚)和聚(氧化二甲苯);聚(酯酰胺-二异氰酸酯);聚氨酯;聚酯(包括聚芳酯),如聚(对苯二甲酸乙二醇酯)、聚(甲基丙烯酸烷基酯)、聚(丙烯酸酯)和聚(对苯二甲酸苯二醇酯);多硫化物;除上列聚合物外,由具有α-烯烃不饱和的单体形成的聚合物,包括聚(乙烯)、聚(丙烯)、聚(丁烯-1)、聚(4-甲基戊烯-1)、聚乙烯化合物,例如聚(氯乙烯)、聚(氟乙烯)、聚(偏二氯乙烯)、聚(偏二氟乙烯)、聚(乙烯醇)、聚(乙烯酯),如聚(乙酸乙烯酯)和聚(丙酸乙烯酯)、聚(乙烯基吡啶)、聚(乙烯基吡咯烷酮)、聚(乙烯醚)、聚(乙烯基酮)、聚(乙烯基醛),如聚(乙烯醇缩甲醛)和聚(乙烯醇缩丁醛)、聚(乙烯基酰胺)、聚(乙烯胺)、聚(乙烯基氨酯)、聚(乙烯基脲)、聚(磷酸乙烯酯)和聚(硫酸乙烯酯);聚烯丙基;聚(苯并苯并咪唑);聚酰肼;聚噁二唑;聚三唑;聚(苯并咪唑);聚碳二亚胺;聚膦嗪。
用于本发明中描述的新型膜系统中的第二阶段膜的制备的一些优选聚合物包括,但不限于,聚砜;磺化聚砜;聚醚酰亚胺,如Ultem;纤维素聚合物,如乙酸纤维素和三乙酸纤维素;聚酰胺;聚酰亚胺,如P84和聚(3,3’,4,4’-二苯甲酮四甲酸二酐-苯均四酸二酐-3,3’,5,5’-四甲基-4,4’-亚甲基二苯胺)(聚(BTDA-PMDA-TMMDA));聚酰胺/酰亚胺;聚酮;聚醚酮;和聚丙烯腈。
本发明中描述的交联橡胶聚氨酯-醚聚合膜也可用于从天然气中回收NGL。本发明中描述的交联橡胶聚氨酯-醚聚合膜选择性渗透可冷凝蒸气,如C3至C35烃和芳族化合物,因此其可以将C3+烃与甲烷和乙烷分离以回收NGL。
本发明中描述的交联橡胶聚氨酯-醚聚合膜也可用于燃料气体调质。调质天然气已用作烃加工工业中的燃气发动机和涡轮机中的燃料气体,特别用于海上平台和边远地区以及FLNG和FPSO用途。本发明中描述的交联橡胶聚氨酯-醚聚合膜已表现出对C3+烃超过对甲烷的高渗透性和高选择性,这能够实现燃料气体的调质。
实施例
提供下列实施例以例示本发明的一个或多个优选实施方案,但并不限于其实施方案。可以对下列实施例作出许多变动,它们落在本发明的范围内。
实施例1、交联聚氨酯-丙二醇膜的制备
将15.0克2,4-二异氰酸酯封端的聚(丙二醇)甲苯(poly(propyleneglycol)toluene)在搅拌下溶解在30克无水DMF溶剂中以形成均匀溶液。将1.1克3,3,3’,3’-四甲基-1,1”-螺环双茚满-5,5’,6,6’-四醇(3,3,3’,3’-tetramethyl-1,1”-spirobisindane-5,5’,6,6’-tetrol)在搅拌下添加到该溶液中。将该溶液在60℃下混合1小时以形成均匀溶液。将该溶液脱气1小时,然后浇注到干净玻璃板的表面上。在50℃下蒸发DMF溶剂12小时。从该玻璃板上剥离所得膜并在真空中在120℃下进一步干燥24小时以形成交联聚氨酯-丙二醇(polyurethane-propyleneglycerol)致密膜。
实施例2、交联聚氨酯-丙二醇膜的分离性能的评估
下表显示该交联聚氨酯-丙二醇膜的纯气体渗透率和选择性。通过纯气体测量法在50℃下测量该交联聚氨酯-丙二醇膜对CH4、CO2、丙烷(C3H8)和正丁烷(n-C4H10)的渗透率(PA)和选择性(αA/B)。从该表中可以看出,该交联聚氨酯-丙二醇膜具有>200Barrers的CO2渗透率,这比传统聚合物膜,如CA、Matrimid聚酰亚胺和Ultem聚醚酰亚胺膜高得多。不同于对小气体,如CH4比对大的可冷凝有机蒸气,如C3H8和n-C4H10更可渗透的这些传统聚合物膜,该表中的结果已表明,该交联聚氨酯-丙二醇膜对大的可冷凝有机蒸气,如C3H8和n-C4H10比对小的永久气体,如CH4可渗透得多。因此,该交联聚氨酯-丙二醇膜可用于选择性除去水和C3至C35烃以控制用于天然气加工的天然气的露点。来自该交联聚氨酯-丙二醇膜的高压渗余物主要包含CH4、CO2和痕量乙烷和丙烷和一些其它组分。
表、交联聚氨酯-丙二醇膜的纯气体渗透试验结果
气体 | 渗透率(Barrer) | 选择性(气体/CH4) |
CH4 a | 33.7 | --- |
CO2 a | 222.1 | 6.5 |
丙烷(C3H8)a | 205.5 | 6.1 |
正丁烷(n-C4H10)b | 343.3 | 10.2 |
a在50℃和791kPa(100psig)下测试;
b在50℃和170kPa(10psig)下测试;
1Barrer=10-10cm3(STP).cm/cm2.sec.cmHg.
实施例3、交联聚氨酯-丙二醇复合薄膜的制备
将6.0克2,4-二异氰酸酯封端的聚(丙二醇)甲苯在搅拌下溶解在155克1,3-二氧戊环溶剂中以形成均匀溶液。将0.44克3,3,3’,3’-四甲基-1,1”-螺环双茚满-5,5’,6,6’-四醇在搅拌下添加到该溶液中。将该溶液在60℃下混合1小时以形成均匀溶液。将该溶液脱气1小时。通过浸涂或刮刀流延(knifecasting)将所得溶液涂布到多孔聚丙烯腈(PAN)超滤膜基底的表面上。蒸发溶剂以形成连续膜。然后将该聚氨酯-丙二醇复合薄膜在烘箱中在100℃下加热1小时以形成交联聚氨酯-丙二醇/PAN复合薄膜。
具体实施方案
尽管下面联系具体实施方案进行描述,但要理解的是,该描述意在举例说明而非限制上述说明书和所附权利要求书的范围。
在第一实施方案中,本发明涉及一种交联橡胶聚氨酯-醚聚合膜,其包含具有多个式(I)的重复单元的交联橡胶聚氨酯-醚聚合物,其中式(I)由下列结构表示:
其中X1、X2、X3和X4分别选自
及其混合物;X1、X2、X3和X4彼此相同或不同;其中Y选自
及其混合物;其中Z1、Z2、Z3和Z4分别选自
及其混合物;Z1、Z2、Z3和Z4彼此相同或不同且t为0至4;且其中n、m、p、q、r和s独立地为2至500的整数。式(I)的X1、X2、X3和X4可以相同并具有包括以下的化学结构:
式(I)的X1、X2、X3和X4的Z1可以如下表示
式(I)的Y可以是
在第二实施方案中,本发明涉及一种制造交联橡胶聚氨酯-醚膜的方法,其包括将二异氰酸酯封端聚醚和包含四个或更多个羟基官能团的刚性交联剂溶解在溶剂中以形成均匀溶液;2)然后在30℃至100℃的温度下加热所述均匀溶液0.5至12小时以形成聚氨酯-醚预聚物溶液;3)在多孔膜载体上涂布所述聚氨酯-醚预聚物溶液的层;和4)将所述涂膜在30℃至100℃的温度下加热0.5至12小时以在所述多孔膜载体上提供包含交联橡胶聚氨酯-醚材料的选择性薄层。所述方法中制备的多孔膜载体可包含无机陶瓷材料或聚合物。可以在所述多孔膜载体上添加所述交联橡胶聚氨酯-醚材料的至少一个附加层。可以将所述交联橡胶聚氨酯-醚膜制成适当的构造,如片、盘、管或中空纤维。也可以将所述交联橡胶聚氨酯-醚膜制成包含选择性薄交联橡胶聚氨酯-醚层和含聚合物材料或无机材料的多孔载体层的复合薄膜。在所述方法中,所述交联橡胶聚氨酯-醚聚合膜包含具有多个式(I)的重复单元的交联橡胶聚氨酯-醚聚合物,其中所述式(I)由下列结构表示:
其中X1、X2、X3和X4分别选自
及其混合物;X1、X2、X3和X4彼此相同或不同;其中Y选自
及其混合物;其中Z1、Z2、Z3和Z4分别选自
及其混合物;Z1、Z2、Z3和Z4彼此相同或不同且t为0至4;且其中n、m、p、q、r和s独立地为2至500的整数。在所述方法的一个实施方案中,所述二异氰酸酯封端聚醚选自
及其混合物;其中Z1、Z2、Z3和Z4分别选自
及其混合物;Z1、Z2、Z3和Z4彼此相同或不同且t为0至4;其中m、p、q、r和s独立地为2至500的整数。在本发明的方法的一个实施方案中,所述包含四个或更多个羟基官能团的刚性交联剂选自
及其混合物。
在第三实施方案中,本发明包含一种处理流体料流的方法,其包括使所述流体料流与具有多个式(I)的重复单元的交联橡胶聚氨酯-醚聚合物膜接触,其中所述式(I)由下列结构表示:
其中X1、X2、X3和X4分别选自
及其混合物;X1、X2、X3和X4彼此相同或不同;其中Y选自
及其混合物;其中Z1、Z2、Z3和Z4分别选自
及其混合物;Z1、Z2、Z3和Z4彼此相同或不同且t为0至4;且其中n、m、p、q、r和s独立地为2至500的整数,以产生渗透料流和渗余料流。处理流体的方法包括从天然气中除去C3至C35烃的方法。在本发明的一个实施方案中,将天然气料流的露点控制在指定界限内。在本发明的一个实施方案中,从天然气料流中除去二氧化碳。在本发明的一个实施方案中,所述渗透料流包含丙烷、正丁烷和其它重烃,且所述渗余料流包含甲烷和乙烷。在本发明的一个实施方案中,所述流体料流包含芳族化合物的混合物。在本发明的一个实施方案中,使所述流体料流首先经过所述交联橡胶聚氨酯-醚聚合膜,然后经过第二膜。第二膜可包括选自聚砜、乙酸纤维素、三乙酸纤维素、聚酰胺、聚酰亚胺、聚酮、聚醚酮和聚丙烯腈的聚合物。在本发明的一些实施方案中,第二膜具有比所述交联橡胶聚氨酯-醚聚合膜高的CO2/CH4选择性。
Claims (10)
1.一种交联橡胶聚氨酯-醚聚合膜,其包含具有多个式(I)的重复单元的交联橡胶聚氨酯-醚聚合物,其中所述式(I)由下列结构表示:
其中X1、X2、X3和X4分别选自
及其混合物;X1、X2、X3和X4彼此相同或不同;其中Y选自
及其混合物;其中Z1、Z2、Z3和Z4分别选自
及其混合物;Z1、Z2、Z3和Z4彼此相同或不同且t为0至4;且其中n、m、p、q、r和s独立地为2至500的整数。
2.权利要求1的膜,其中式(I)的X1、X2、X3和X4相同并具有包括以下的化学结构:
其中式(I)的X1、X2、X3和X4的Z1是:
且其中式(I)的Y是:
3.制造权利要求1的交联橡胶聚氨酯-醚膜的方法,其包括将二异氰酸酯封端聚醚和包含四个或更多个羟基官能团的刚性交联剂溶解在溶剂中以形成均匀溶液;2)然后在30℃至100℃的温度下加热所述均匀溶液0.5至12小时以形成聚氨酯-醚预聚物溶液;3)在多孔膜载体上涂布所述聚氨酯-醚预聚物溶液的层;和4)将所述涂膜在30℃至100℃的温度下加热0.5至12小时以在所述多孔膜载体上提供包含交联橡胶聚氨酯-醚材料的选择性薄层。
4.权利要求3的方法,其进一步包括将所述交联橡胶聚氨酯-醚膜制成片、盘、管或中空纤维。
5.权利要求3的方法,其进一步包括将所述交联橡胶聚氨酯-醚膜制成包含选择性薄交联橡胶聚氨酯-醚层和含聚合物材料或无机材料的多孔载体层的复合薄膜。
6.一种处理流体料流的方法,其包括使所述流体料流与具有多个式(I)的重复单元的交联橡胶聚氨酯-醚聚合物膜接触,其中所述式(I)由下列结构表示:
其中X1、X2、X3和X4分别选自
及其混合物;X1、X2、X3和X4彼此相同或不同;其中Y选自
及其混合物;其中Z1、Z2、Z3和Z4分别选自
及其混合物;Z1、Z2、Z3和Z4彼此相同或不同且t为0至4;且其中n、m、p、q、r和s独立地为2至500的整数,以产生渗透料流和渗余料流。
7.权利要求6的方法,其中所述处理流体的方法包括从天然气中除去C3至C35烃和二氧化碳。
8.权利要求7的方法,其中将所述天然气料流的露点控制在指定界限内。
9.权利要求6的方法,其中所述渗透料流包含丙烷、正丁烷和其它重烃,且所述渗余料流包含甲烷和乙烷。
10.权利要求6的方法,其中使所述流体料流首先经过所述交联橡胶聚氨酯-醚聚合膜,然后经过第二膜,其中所述第二膜包含选自聚砜、乙酸纤维素、三乙酸纤维素、聚酰胺、聚酰亚胺、聚酮、聚醚酮和聚丙烯腈的聚合物。
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