CN114425415A - 一种改性分子筛及其制备方法和生产燃料油组分的方法 - Google Patents
一种改性分子筛及其制备方法和生产燃料油组分的方法 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000000295 fuel oil Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims abstract description 54
- 150000001336 alkenes Chemical class 0.000 claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 21
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 18
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 11
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 2
- JIUFYGIESXPUPL-UHFFFAOYSA-N 5-methylhex-1-ene Chemical compound CC(C)CCC=C JIUFYGIESXPUPL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 17
- 238000011069 regeneration method Methods 0.000 abstract description 8
- 230000008929 regeneration Effects 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 4
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- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 239000000376 reactant Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- -1 ZSM-5 Chemical compound 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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- B01J2229/38—Base treatment
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
本发明涉及一种改性分子筛及其制备方法和生产燃料油组分的方法,包括:以ZSM‑22分子筛为基础分子筛,经过扩孔剂改性,使其具有更大的孔径和更小的晶体粒径,随后将其用于烯烃叠合反应制备燃料油组分。ZSM‑22分子筛经过改性后具有活性高、副反应少、寿命长且易再生重复使用的特点,具有工业应用前景。
Description
技术领域
本发明涉及一种分子筛及其制备方法,还涉及通过烯烃叠合反应制备燃料油组分的方法。
背景技术
分子筛是一类具有有序而均匀的孔道结构的晶体材料,具有优异的催化活性,已广泛应用于石油化工等领域。对于分子筛催化剂,催化剂的孔结构、酸量和晶体粒径等都会显著地影响催化剂的活性、选择性及寿命。相比于三维分子筛如ZSM-5,beta等和二维分子筛如丝光沸石等,一维分子筛如ZSM-22的孔道基本为直筒型,由于其独特的孔道结构,使其具有更好的择形选择性。但是ZSM-22为典型的微孔分子筛,其较小的孔径和较长的孔道限制了反应物和产物的扩散,导致催化剂孔道内易结焦失活,影响催化剂寿命,因此对其进行改性处理以获得更大的孔径、更多的介孔体积以及较小的晶粒尺寸将有助于调节催化剂的活性并延长催化剂寿命。
烯烃叠合技术是一种烯烃综合利用制备高经济性产品的主流技术,其主要的应用方向是制备清洁液体燃料和高附加值化学品。叠合反应工艺灵活、应用广泛,可作为各种加工工艺的中间手段,是增加碳数的主要途径,其发展的核心主要为开发高活性、长寿命、低成本、低污染的催化剂。叠合催化剂包扩固体磷酸催化剂、酸性树脂催化剂、分子筛、离子液体等。其中,固体磷酸催化剂容易泥化、寿命短、酸性易流失并对设备造成腐蚀、且不可再生;酸性树脂催化剂不耐高温、热稳定性差、不可再生、有溶胀性;离子液体不易制备、不易分离、价格昂贵,难以用于工业化。专利CN102633587A公布了一种复合催化剂:由30~80%HZSM-5,20~70%的粘结剂组成,用于C4烯烃转化制备高碳烯烃,C4烯烃转化率为84.9%,C9+选择性为81.7%。文章“ZSM-5分子筛催化1-己烯叠合反应的研究”(石油炼制与化工,9,7-11,2015)中介绍了ZSM-5催化1-己烯叠合反应制备喷气燃料组分的方法,其中在最优催化剂作用下,己烯转化率为77%,产物选择性为80%。文章“1-hexene oligomerization inliquid,vapor,and supercritical phases over beidellite and ultrastable Yzeolite catalysts”(Journal of Catalysis,179,477-482,1998)介绍了利用Y分子筛叠合1-己烯的方法,在200℃,5MPa下,以十二烷为溶剂,1-己烯转化率最高可达86%,但催化剂出现了快速的失活。目前分子筛催化剂用于烯烃叠合存在的主要问题是副反应较多,催化剂易结焦失活,寿命短,不易再生。
发明内容
针对现有技术存在的缺陷,本发明提供一种改性ZSM-22分子筛及其制备方法。本发明针对ZSM-22分子筛具有独特的一维孔结构但又基本为微孔结构的特点,提供一种改性ZSM-22分子筛的方法,改性后的ZSM-22分子筛孔体积和孔径显著增大,晶粒尺寸减小,具有活性高、副反应少、寿命长且易再生重复使用的特点,具有工业应用前景。
本发明还提供一种改性ZSM-22分子筛的应用,即通过烯烃叠合制备燃料油组分的方法。
第一方面,本发明提供一种改性ZSM-22分子筛的制备方法,包扩:将ZSM-22分子筛与扩孔剂水溶液在反应器中混合,在130~210℃下动态处理4~20h,洗涤、过滤、烘干、煅烧,即得到改性后的ZSM-22分子筛。
本发明所述的ZSM-22分子筛的Si/Al比为20~100,优选25~70;Na2O含量小于0.5wt%,优选小于0.1wt%;ZSM-22的酸中心数为0.1~1.5mmol/g,优选0.2~1.0mmol/g。通常所述的ZSM-22分子筛的孔径范围2~10nm,介孔体积0.10~0.35cm3/g,粒径200~600nm。
所述扩孔剂可以选自己二胺、四乙基氢氧化铵,优选四乙基氢氧化铵。
所述扩孔剂与分子筛中SiO2摩尔比为0.05~0.20,优选0.08~0.15。
所述扩孔剂水溶液的浓度为10~45wt%,优选20~35wt%。
所述动态处理是让浆液持续流动或者搅拌、翻转。所述动态处理温度可以为130~210℃,优选150~180℃;所述反应压力可以为0.1~1MPa,优选0.1~0.5MPa。动态处理时间为4~20h,优选6~15h。
所述反应器可以为搅拌釜,高压反应釜,优选高压反应釜。
所述洗涤、过滤、烘干为本领域常规操作。
所述煅烧条件为常规操作,可以在500~600℃下煅烧1~3h。
第二方面,本发明提供一种改性ZSM-22分子筛,该分子筛由上述改性方法得到。所述改性分子筛具有以下特征:孔径2~10nm,优选4~8nm;介孔体积0.10~0.35cm3/g,优选0.20~0.30cm3/g;粒径200~600nm,优选300~500nm。
所述改性的ZSM-22分子筛的Si/Al比为20~100,优选25~70;Na2O含量小于0.5wt%,优选小于0.1wt%;ZSM-22的酸中心数为0.1~1.5mmol/g,优选0.2~1.0mmol/g。
第三方面,本发明提供一种通过烯烃叠合生产燃料油组分的方法,包扩:使C5~C7烯烃原料从固定床反应器上部进入,通过装有改性ZSM-22分子筛的催化剂床层,在分子筛的催化作用下发生烯烃叠合反应,产物从下部采出,得到燃料油组分。
所述的C5~C7烯烃原料可以来源于但不限于FCC汽油、费托合成烯烃等原料,可以选自戊烯、2-甲基-丁烯、己烯、异己烯、庚烯、异庚烯中的一种或者几种的混合物。
所述的叠合反应温度为140~260℃,优选180~240℃;反应压力为1.0~8.0MPa,优选3.0~5.0MPa。质量空速为0.5~10.0h-1,优选3.0~7.0h-1。本发明所述的反应后的催化剂经过煅烧即可实现再生。反应后的催化剂置于反应管中间,在O2或者空气氛围下,在100~300mL/min的气体流速,300~600℃下,焙烧2~8h即可重复使用。
根据本发明方法,反应原料储存于耐压原料罐中,随后可选择性地经过预处理反应器,脱除其中的二烯烃及含硫化合物等杂质,再将预处理流出物经过80~100℃切割去除重组分后,以轻组分作为叠合原料。
所述的预处理反应器为固定床反应器,其中装有活性白土,预处理反应温度保持为50~110℃,优选70~90℃;压力为1.0~7.0MPa,优选3.0~5.0MPa;质量空速为0.5~10.0h-1,优选3.0~7.0h-1。
根据本发明方法,可将产物选择性地经过80~100℃切割后,轻组分部分循环至反应原料管线,重组分作为燃料油馏分采出,可进一步生产航煤和柴油。
本发明对ZSM-22分子筛进行改性后,相比于未改性的分子筛孔体积增大,孔径增大,介孔体积增加,晶体粒径变小。分子筛的催化活性中心主要位于孔道内,孔体积和孔径增大有利于反应物和产物在孔道内的扩散,使得反应物和产物分子不易在孔径内堵塞停留,从而抑制了其进一步深度反应生成结焦前驱体或结焦物,进而提高催化剂稳定性;晶粒尺寸减小有利于缩短反应物和产物在催化剂晶粒孔道中的扩散路程,同样使得其在孔道内不会过长时间停留而生成结焦前驱体或结焦物,从而延长分子筛催化剂寿命。而且本发明改性分子筛的再生方法简便,再生后的分子筛仍然具有很高的活性。
本发明以改性ZSM-22分子筛作为催化剂进行烯烃叠合反应,可有效控制烯烃聚合程度主产喷气燃料和柴油馏分油,原料转化率高,目标产物选择性高,同时催化剂稳定性好,寿命高,具有良好的工业应用前景。
具体实施方式
以下结合实施例,进一步说明本发明的技术方案和效果。
实施例中,催化剂孔径、介孔体积采用氮气物理吸脱附(BET)方法测定,晶粒粒径采用透射电镜(TEM)方法测定。
改性前的ZSM-22分子筛购自中国石化长岭催化剂厂。
催化剂制备例1~5(四乙基氢氧化铵改性对分子筛的影响)
将ZSM-22-A(Na2O=0.08wt%,Si/Al=36)进行四乙基氢氧化铵改性,改性条件为:TEAOH浓度为27.5%,加入的TEAOH与分子筛中SiO2摩尔比为0.1即n(TEAOH)/n(SiO2)=0.1;将物料按上述配比混合均匀后,加入高压反应釜中,在140~200℃下,动态处理4~18h,随后经过洗涤、过滤、烘干在550℃下煅烧2h得到TEAOH改性后的ZSM-22分子筛。改性后的催化剂孔径、介孔体积及晶粒粒径列于表1中。
催化剂制备例6(四乙基氢氧化铵与SiO2摩尔比对分子筛改性的影响)
将ZSM-22-B(Na2O=0.03%,Si/Al=70)按照催化剂制备例1中的条件对ZSM-22-B分子筛进行改性,但调整TEAOH与分子筛中SiO2摩尔比为0.15,得到改性催化剂ZSM-22-6,改性后的催化剂孔径、介孔体积及晶粒粒径列于表1中。
催化剂制备例7(四乙基氢氧化铵浓度对分子筛改性的影响)
按照催化剂制备例1中的条件对ZSM-22-A分子筛进行改性,但调整TEAOH的浓度为40.0%,得到改性催化剂ZSM-22-7,改性后的催化剂孔径、介孔体积及晶粒粒径列于表1中。
催化剂制备例8(己二胺对分子筛改性的影响)
按照催化剂制备例1中的条件对ZSM-22-A分子筛进行改性,但用己二胺代替四乙基氢氧化铵进行,己二胺浓度为10%,加入的己二胺与分子筛中SiO2摩尔比为0.05即n(己二胺)/n(SiO2)=0.05,在170℃下进行6h,其他改性条件不变,得到改性催化剂ZSM-22-8,改性后的催化剂孔径、介孔体积及晶粒粒径列于表1中。
表1
实施例1
采用表1中所列催化剂进行烯烃叠合反应。反应条件:固定床中反应温度为200℃,己烯进料质量空速为3h-1,固定床中反应压力保持为5MPa,系统稳定反应10h,100h后,在出口处开始取样进行气相色谱分析,考察其对己烯转化率以及对二聚和三聚燃料油馏分产物收率的影响以及催化剂的稳定性,其结果如表2所示:
表2
从表2可以看出,本发明改性后的分子筛催化剂反应100小时后仍然具有很高的活性,其中尤其以2号、4号和6号效果显著。1号催化剂改性温度较低,导致四乙基氢氧化铵脱硅扩孔的作用不明显,影响了改性效果;3号催化剂由于扩孔温度过高,导致催化剂孔结构受到了一些破坏,不利于催化剂的稳定性;5号催化剂由于碱处理时间较长,导致催化剂被过度脱硅,催化剂骨架部分坍塌,介孔体积反而有所下降,因此稳定性下降;7号催化剂由于碱的浓度较高,导致催化剂脱硅程度较高,部分结构坍塌,催化剂稳定性没有达到最佳。8号催化剂为ZSM-22-A经过己二胺改性得来,稳定性相比于ZSM-22-A有了一定提升,但是未达到经过四乙基氢氧化铵改性后的水平。
实施例2(反应温度的考察)
按照实施例1中所述的试验方法,以实施例1中ZSM-22-2为催化剂,在己烯进料质量空速为3h-1,固定床中反应压力保持为5MPa条件下,经过10h反应后,在出口处开始取样进行气相色谱分析,考察不同反应温度的影响,其结果如下所示:
实施例3(反应压力的考察)
按照实施例1中所述的试验方法,以实施例1中ZSM-22-2为催化剂,在己烯进料质量空速为3h-1,反应温度为200℃条件下,经过10h反应后,在出口处开始取样进行气相色谱分析,考察不同反应压力的影响,其结果如下所示:
实施例4(质量空速的考察)
按照实施例1中所述的试验方法,以实施例1中ZSM-22-2为催化剂,在反应温度为200℃,反应压力为5MPa条件下,经过10h反应后,在出口处开始取样进行气相色谱分析,考察不同质量空速的影响,其结果如下所示:
实施例5(反应原料的考察)
按照实施例1中所述的试验方法,以实施例1中ZSM-22-2为催化剂,在反应温度为200℃,反应压力为5.0MPa,进料空速为3h-1的条件下,将原料己烯换为工业FCC轻汽油时,原料先通过预处理反应器去除杂质,其中装有活性白土,温度为80℃,压力为5MPa,质量空速为2.0h-1,反应后再经过80℃切割去除重组分,得到轻组分再进入叠合反应器。经过10h反应后,在出口处开始取样进行气相色谱分析,考察不同原料的烯烃转化率以及二聚和三聚产物燃料油馏分产物收率的影响,其结果如下所示:
实施例6(催化剂再生的考察)
将实施例1中的进一步使用100h后的ZSM-22-A催化剂和使用300h后的ZSM-22-2催化剂,在空气气氛下,450℃下煅烧5h,再在反应温度为200℃,反应压力为5.0MPa,进料空速为3h-1的条件下,按照实施例1中所述方案,考察催化剂的再生活性,其结果如下所示:
从表中结果可知,本发明改性后的催化剂稳定性好,寿命长,再生后仍然具有很高的活性。
Claims (12)
1.一种改性ZSM-22分子筛的制备方法,包括:将ZSM-22分子筛与扩孔剂水溶液在反应器中混合,在130~210℃下动态处理4~20h,洗涤、过滤、烘干、煅烧,即得到改性后的ZSM-22分子筛。
2.按照权利要求1所述的方法,其中,所述的ZSM-22分子筛的Si/Al比为20~100,优选25~70;Na2O含量小于0.5wt%,优选小于0.1wt%;ZSM-22的酸中心数为0.1~1.5mmol/g,优选0.2~1.0mmol/g。
3.按照权利要求1所述的方法,其中,所述扩孔剂选自己二胺、四乙基氢氧化铵,优选四乙基氢氧化铵。
4.按照权利要求1所述的方法,其中,所述扩孔剂与分子筛中SiO2摩尔比为0.05~0.20,优选0.08~0.15。
5.按照权利要求1所述的方法,其中,所述扩孔剂水溶液的浓度为10~45wt%,优选20~35wt%。
6.按照权利要求1所述的方法,其中,所述动态处理温度150~180℃,压力为0.1~1MPa,动态处理时间为6~15h。
7.权利要求1~6之一得到的改性ZSM-22分子筛。
8.一种烯烃叠合生产燃料油组分的方法,包括:使C5~C7烯烃原料从固定床反应器上部进入,通过装有权利要求7所述改性ZSM-22分子筛的催化剂床层,在分子筛的催化作用下发生烯烃叠合反应,产物从下部采出,得到燃料油组分。
9.按照权利要求8所述的方法,其中,所述的C5~C7烯烃原料来源于但不限于FCC汽油、费托合成烯烃,优选戊烯、2-甲基-丁烯、己烯、异己烯、庚烯、异庚烯中的一种或者几种的混合物。
10.按照权利要求8所述的方法,其中,所述的叠合反应温度为140~260℃,优选180~240℃;反应压力为1.0~8.0MPa,优选3.0~5.0MPa;质量空速为0.5~10.0h-1,优选3.0~7.0h-1。
11.按照权利要求8所述的方法,其中,所述反应原料选择性地经过预处理反应器,再将预处理流出物经过80~100℃切割去除重组分后,以轻组分作为叠合原料。
12.按照权利要求8所述的方法,其中,将产物选择性地经过80~100℃切割后,轻组分部分循环至反应原料管线,重组分作为燃料油馏分采出,进一步生产航煤和柴油。
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