CN106881147A - 金属通道内改性zsm-5分子筛催化剂膜的制备及催化剂膜和应用 - Google Patents
金属通道内改性zsm-5分子筛催化剂膜的制备及催化剂膜和应用 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 claims abstract description 27
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims 2
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- 229910052789 astatine Inorganic materials 0.000 claims 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
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- 238000010306 acid treatment Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
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- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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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
- B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
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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
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/46—Iron group metals or copper
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Abstract
本发明提供一种金属通道内改性ZSM-5分子筛催化剂膜的制备及催化剂膜和应用。该分子筛催化剂膜以含有氢氧化铝、硅溶胶、氢氧化钠、水和有机胺模板剂的溶胶液为分子筛膜生长液,通过静动态水热合成原位生长在细长金属通道内表面上形成NaZSM-5分子筛膜,并焙烧除去模板剂;通过铵盐溶液交换及热处理形成HZSM-5膜;通过浸渍及热处理过程对HZSM-5膜进行表面改性。本发明制备的金属通道内改性ZSM-5分子筛催化剂膜具有较薄的厚度、高均匀性和结合强度,没有大孔缺陷;而且本发明方法不需要对金属载体进行表面预处理和表面再构,显著简化制备过程和膜生长的重复性。本发明制备的分子筛催化剂膜用于碳氢燃料催化裂解过程,具有较高的催化裂解活性和烯烃选择性。
Description
技术领域
本发明涉及一种碳氢燃料催化裂解用金属通道内改性ZSM-5分子筛催化剂膜的制备及催化剂膜和应用,具体地,本发明涉及一种将碳氢燃料催化裂解为小分子烯烃和烷烃的细长金属通道内表面改性ZSM-5催化剂膜的制备方法及应用。
背景技术
碳氢燃料催化裂解为小分子烯烃和烷烃是提高燃料吸热能力和燃烧性能的有效方法。与热裂解相比,催化裂解能提高碳氢燃料的裂解率、烯烃选择性和吸热性能。
金属或陶瓷规整载体(蜂窝状及多/微通道等)催化反应器在石油和精细化工等催化领域得到了广泛研究和应用。分子筛膜作为一种重要的新型无机膜材料,具有机械强度高、耐高温、耐侵蚀、化学和水热稳定及孔径分布均一可调的特点。其微孔孔径一般在0.3-1nm之间,通常被用于有机物的分离过程。同时,分子筛膜规整催化剂因其机械强度高、压降低、传质传热效率高,而在催化裂解等反应过程具有明显优势和广阔的应用前景。目前,在蜂窝陶瓷和蜂窝金属(FeCrAl)、管式多孔α-Al2O3和多孔不锈钢载体上的分子筛膜已经被广泛研究,并取得了较大进展。这些载体的共同特点是载体中具有丰富的微米级孔道和粗糙表面,使得分子筛膜能深入微米级孔道中生长,从而与载体牢固结合。而在不具有微米级孔道和粗糙表面的金属上壁载分子筛膜具有较大难度,因而正被深入研究。
金属载体上分子筛膜制备的主要方法是原位生长法和浸涂法。浸涂法是通过含粘结剂的分子筛悬浮液在表面再构(高温氧化或酸处理等)的金属载体上的涂覆及后续的干燥和焙烧来制备分子筛涂层的方法。原位生长法是在一定温度和自生压力下,用含组分前驱体的分子筛合成液在金属表面原位水热合成出分子筛膜的方法。Eleta等比较了900℃氧化的FeCrAl载体上浸涂法和原位生长法制备的ZSM-5分子筛涂层(A.Eleta,P.Navarro,L.costa,M.Montes,Microporous and Mesoporous Materials,123(2009)113-122)。浸涂法分子筛涂层的不足之处是由于含有30%以上的粘结剂,导致涂层中分子筛催化剂含量降低,从而影响催化剂涂层催化活性,并且在未经表面再构处理和未预涂过渡层的金属表面难以用粘结剂制备出高牢固度浸涂分子筛涂层。而原位生长法分子筛涂层无粘结剂成分,能显著提高分子筛含量,并且能直接在金属表面制备分子筛膜层。
ZSM-5、HY、SAPO-34等分子筛是常用的碳氢燃料裂解催化剂,能明显提高碳氢燃料的吸热能力和燃烧性能,并抑制结焦的生成(H.Huang,D.R.Sobel,L.J.Spadaccini,AIAA 2002-3871)。中国专利CN1069554C公开了一种ZSM-5沸石与多孔金属复合材料及其制备方法。其在多孔金属载体上原位合成ZSM-5涂层。Zamaro等在900℃预氧化处理的FeCrAl合金上原位生长了ZSM-5涂层(J.M.Zamoro,M.A.Ulla,E.E.Miro,Microporous and Mesoporous Materials,115(2008)113-122)。Louis等在316不锈钢丝网表面一步法原位水热合成了ZSM-5涂层(B.Louis,L.Kiwi-Minsker,P.Reuse,and A.Renken,Ind.Eng.Chem.Res.40(2001)1454-1459)。其通过酸处理和超声振荡处理在不锈钢表面创建缺陷位,以增强水热合成分子筛涂层的结合力。Yuranov等在烧结金属(Inconel 601镍基高温合金)纤维上原位合成了MFI型分子筛涂层(I.Yuranov,A.Renken,L.Kiwi-Minsker,Applied Catalysis A:General,281(2005)55-60)。上述原位生长法分子筛涂层的制备需要通过高温预氧化或酸处理等进行金属表面再构,以利于分子筛涂层与金属之间的结合。未经表面再构的金属载体,因表面缺少缺陷位及孔道,难以与分子筛膜层牢固结合。本发明的方法是在未经表面再构的金属通道内表面制备高结合强度的分子筛催化剂膜。
在本发明中,通过对ZSM-5催化剂膜进行改性修饰,来进一步提高其对碳氢燃料的催化裂解转化率和烯烃选择性。
发明内容
本发明的目的在于提供一种碳氢燃料催化裂解用金属通道内改性ZSM-5催化剂膜的制备及催化剂膜和应用,该制备方法简单,容易实施,在细长金属通道内表面壁载的分子筛催化剂膜均匀牢固,具有较好的燃料裂解活性和烯烃选择性。
为实现上述目的,本发明采用的技术方法如下:
一种金属通道内改性ZSM-5分子筛催化剂膜的制备方法,其特征在于,它包括以下步骤:
(1)将氢氧化铝、硅溶胶、氢氧化钠、去离子水和有机胺模板剂按照摩尔组成1Al2O3:aSiO2:bNa2O:cH2O:dRNH2的比例配制成溶胶液,作为分子筛膜生长液,其中a=25~1000,b=10~100,c=1000~10000,d=0.01~30;所述有机胺为四丙基氢氧化铵(TPAOH)、四丙基溴化铵(TPABr)或正丁胺(NBA)中的至少一种或两种以上;
(2)将分子筛膜生长液移入金属通道中,金属通道两端封好后移入烘箱中并与竖直方向呈0~45°角放置,在100~200℃温度下静动态生长5~240小时;生长完成后,将金属通道冷却至室温,用去离子水充分清洗分子筛膜,干燥后在500~650℃下焙烧1~10小时以除去模板剂,获得金属通道内表面NaZSM-5膜;重复上述合成过程0~5次,以获得要求的分子筛膜厚度;所述静动态为每静态生长10~180分钟后将金属通道方向调转180°;
(3)将0.4~1mol/L浓度的硝酸铵或氯化铵溶液中的一种在40~90℃下通入步骤(2)制备的具有NaZSM-5膜的金属通道中交换1~10小时,以除去NaZSM-5分子筛膜的钠离子,交换后用去离子水洗涤至中性并干燥,然后在500~650℃下焙烧1~10小时,获得金属通道内表面HZSM-5膜;
(4)用浓度为0.2~2mol/L改性剂溶液浸渍步骤(3)制备的金属通道内HZSM-5膜0.1~3小时,然后用0.1~1MPa高压气体吹出多余的浸渍液,经80~150℃干燥后在500~650℃下焙烧1~10小时,获得金属通道内表面改性ZSM-5分子筛膜;所述的改性剂为硅溶胶或有机硅烷、磷酸、可溶性的镧盐、铈盐、镨盐、钕盐、钾盐、锌盐和镁盐的至少一种;所述的有机硅烷为直链烷基、支链烷基、环烷基或芳基的三甲氧基硅烷或其三乙氧基硅烷的至少一种。
上述的金属通道为镍基高温合金、钴基高温合金、铁基高温合金或不锈钢通道中的一种;金属通道的截面形状为圆形、椭圆形、三角形、方形、梯形、多边形或多角形中的一种;金属通道的当量直径为0.2~5毫米。
上述的ZSM-5分子筛膜的厚度为0.1~30微米。
上述分子筛膜生长液于金属通道中装填量为金属通道容积的50-90%。
上述制备方法制备获得的金属通道内改性ZSM-5分子筛催化剂膜。
所述催化剂膜的应用,其特征在于:用于碳氢燃料催化裂解反应中。
所述催化剂膜的应用,其特征在于:所述碳氢燃料为C8~C15的正构烷烃、异构烷烃、环烷烃、烯烃和芳烃中的至少一种或两种以上。
本发明的优点在于ZSM-5分子筛催化剂膜合成工艺和设备简单,容易实施,解决了目前制备技术存在的需要金属表面再构、膜强度差及难以在细长通道中实施的不足,使分子筛催化剂膜的碳氢燃料催化裂解活性和烯烃选择性得到明显提高。
附图说明
图1为实施例1中镍基高温合金表面ZSM-5膜的表面微观形貌。
图2为实施例1中ZSM-5膜的XRD结果。
具体实施方式
为了更好地说明本发明的制备方法,下面举出一些实施例,但本发明不限于这些实施例。
实施例1
(1)称取0.20g氢氧化铝、30.00g硅溶胶(25wt.%SiO2)、4.00g氢氧化钠、3.00g模板剂溶液(25wt.%TPAOH)和15.70g去离子水,首先将氢氧化钠溶于5.00g水中配成氢氧化钠溶液,在100℃下将氢氧化铝溶于氢氧化钠溶液中,然后在50℃下恒温搅拌,将余量水、硅溶胶和模板剂加入其中,配成透明溶胶液,陈化24小时,作为分子筛膜生长液;
(2)将分子筛膜生长液移入经去油处理和酸洗过的镍基高温合金(GH3128)管(外径3mm,内径2mm,长800mm)中,分子筛膜生长液装填量为金属管容积的80%;金属管两端封好后移入烘箱中,呈45°角倾斜放置,在180℃温度下生长24小时,生长过程中每隔1小时将金属管方向调转180°;生长完成后,将金属管冷却至室温,用去离子水充分清洗分子筛膜,干燥后在550℃下焙烧4小时以除去模板剂,获得镍基高温合金管内表面NaZSM-5膜;
(3)将0.7mol/L浓度的氯化铵溶液在70℃下通入步骤(2)制备的具有NaZSM-5膜的镍基高温合金管中交换6小时,以除去NaZSM-5分子筛膜的钠离子,交换后用去离子水洗涤至中性并干燥,然后在550℃下焙烧4小时,获得内表面壁载HZSM-5膜的镍基高温合金催化剂管;
(4)对制备的HZSM-5分子筛膜镍基高温合金管进行理化性能和燃料裂解性能测试。
实施例2
按照实施例1步骤(1)配制分子筛合成液,然后按照实施例1步骤(2)相同的步骤进行2次NaZSM-5膜的生长;然后按照实施例1步骤(3)相同的步骤进行NaZSM-5膜的铵交换,获得2次生长HZSM-5膜镍基高温合金管;对2次生长的HZSM-5膜镍基高温合金管进行理化性能和燃料裂解性能测试。
实施例3
按照实施例1步骤(1)配制分子筛合成液,然后按照实施例1步骤(2)相同的步骤进行3次NaZSM-5膜的生长;然后按照实施例1步骤(3)相同的步骤进行NaZSM-5膜的铵交换,获得3次生长HZSM-5膜镍基高温合金管;对3次生长的HZSM-5膜镍基高温合金管进行理化性能和燃料裂解性能测试。
实施例4
按照实施例1步骤(1)配制分子筛合成液,然后按照实施例1步骤(2)相同的步骤进行4次NaZSM-5膜的生长;然后按照实施例1步骤(3)相同的步骤进行NaZSM-5膜的铵交换,获得4次生长HZSM-5膜镍基高温合金管;对4次生长的HZSM-5膜镍基高温合金管进行理化性能和燃料裂解性能测试。
实施例5
用0.30mol/L浓度H3PO4溶液浸渍实施例4中制备的镍基高温合金管内HZSM-5分子筛膜1小时,干燥后在550℃下焙烧4小时,获得P改性ZSM-5分子筛膜镍基高温合金管样品;对制备的P改性HZSM-5分子筛膜镍基高温合金管进行理化性能和燃料裂解性能测试。
实施例6
用0.30mol/L浓度H3PO4和0.14mol/L浓度La(NO3)3的混合液浸渍实施例4中制备的镍基高温合金管内HZSM-5分子筛膜1小时,干燥后在550℃下焙烧4小时,获得P-La改性ZSM-5分子筛膜镍基高温合金管样品;对制备的P-La改性HZSM-5分子筛膜镍基高温合金管进行理化性能和燃料裂解性能测试。
对比例1
用含无机粘结剂的30%纳米α-Al2O3粉体(D50:75nm)浆液涂覆镍基高温合金管(外径3mm,内径2mm,长800mm),经干燥和600℃焙烧后获得纳米α-Al2O3涂层镍基高温合金管。对其进行裂解性能测试。
实施例7
膜样品的厚度和微观形貌用FEI公司的Quanta 200FEG型场发射扫描电镜(SEM)获得,测试电压为20kV。膜样品的表面物相结构用帕纳科(PANalytical)公司的X’Pert Pro型X射线衍射仪(XRD)表征,测试电压40kV,电流40mA。膜样品的牢固度用超声振荡试验测试。超声振荡试验步骤为:将样品完全浸入超声波清洗器(工作频率53kHz,消耗功率250W)清洗槽的去离子水中,超声振荡60分钟,然后将样品干燥后称重。计算膜失重率((超声前样品质量-超声后样品质量)/超声前膜质量×100%)。分子筛催化剂膜样品管的碳氢燃料裂解性能试验在直接电加热式碳氢燃料裂解性能测试***上进行,采用两点式电加热***将碳氢燃料从常温加热到设定工况下的出口流体温度,试验工况:燃料8220,出口流体温度700℃,试验压力3.5MPa,质量流量1g/s,测试时间10min,样品管长度800mm,内径2mm。
分子筛催化剂膜样品管的测试结果如表1所述。实施例1-6中制备的膜样品表现出了较好的膜与金属之间的结合强度,涂层形貌在超声后保持完好。实施例1中镍基高温合金表面ZSM-5膜的表面微观形貌如图1所示。分子筛晶粒间紧密生长,没有明显的裂缝。SEM结果表明,本发明制备的ZSM-5膜微观结构较好。图2为实施例1中ZSM-5膜的XRD结果。结果表明,镍基高温合金表面ZSM-5膜具有典型的ZSM-5分子筛特征峰,说明形成的分子筛膜保持了ZSM-5分子筛的特性。如表1所示,ZSM-5分子筛催化剂膜管比氧化铝涂层管的碳氢燃料裂解转化率和烯烃选择性高,这是由于分子筛催化剂的选择催化裂解性能所致,因而比氧化铝涂层管的热沉高,从而提高了吸热能力。
表1.分子筛膜样品管性能测试结果
本发明制备的金属通道内改性ZSM-5分子筛催化剂膜具有较薄的厚度、高均匀性和结合强度,没有大孔缺陷;而且本发明方法不需要对金属载体进行表面预处理和表面再构,显著简化制备过程和膜生长的重复性。本发明制备的分子筛催化剂膜用于碳氢燃料催化裂解过程,具有较高的催化裂解活性和烯烃选择性。
Claims (10)
1.金属通道内改性ZSM-5分子筛催化剂膜的制备方法,其特征在于,它包括以下步骤:
(1)将氢氧化铝、硅溶胶、氢氧化钠、去离子水和有机胺模板剂按照摩尔组成1Al2O3:aSiO2:bNa2O:cH2O:dRNH2的比例配制成溶胶液,作为分子筛膜生长液,其中a=25~1000,b=10~100,c=1000~10000,d=0.01~30;所述有机胺为四丙基氢氧化铵(TPAOH)、四丙基溴化铵(TPABr)或正丁胺(NBA)中的至少一种或两种以上;
(2)将分子筛膜生长液移入金属通道中,金属通道两端封好后移入烘箱中并与竖直方向呈0~45°角放置,在100~200℃温度下静动态生长5~240小时;生长完成后,将金属通道冷却至室温,用去离子水充分清洗分子筛膜,干燥后在500~650℃下焙烧1~10小时以除去模板剂,获得金属通道内表面NaZSM-5膜;
重复上述合成过程0~5次,以获得要求的分子筛膜厚度;所述静动态为每静态生长10~180分钟后将金属通道方向调转180°;
(3)将0.4~1mol/L浓度的硝酸铵或氯化铵溶液中的一种在40~90℃下通入步骤(2)制备的具有NaZSM-5膜的金属通道中交换1~10小时,以除去NaZSM-5分子筛膜的钠离子,交换后用去离子水洗涤至中性并干燥,然后在500~650℃下焙烧1~10小时,获得金属通道内表面HZSM-5膜;
(4)用浓度为0.2~2mol/L改性剂溶液浸渍步骤(3)制备的金属通道内HZSM-5膜0.1~3小时,然后用0.1~1MPa高压气体吹出多余的浸渍液,经80~150℃干燥后在500~650℃下焙烧1~10小时,获得金属通道内表面改性ZSM-5分子筛膜;
所述的改性剂为硅溶胶或有机硅烷、磷酸、可溶性的镧盐、铈盐、镨盐、钕盐、钾盐、锌盐和镁盐的至少一种;所述的有机硅烷为直链烷基、支链烷基、环烷基或芳基的三甲氧基硅烷或其三乙氧基硅烷的至少一种。
2.按照权利要求1所述的制备方法,其特征在于:所述的金属通道为镍基高温合金、钴基高温合金、铁基高温合金或不锈钢通道中的一种。
3.按照权利要求1或2所述的制备方法,其特征在于:所述的金属通道的截面形状为圆形、椭圆形、三角形、方形、梯形、多边形或多角形中的一种;所述的金属通道的当量直径为0.2~5毫米。
4.按照权利要求1所述的制备方法,其特征在于:所述的ZSM-5分子筛膜的厚度为0.1~30微米。
5.按照权利要求1所述的制备方法,其特征在于:所述分子筛膜生长液于金属通道中装填量为金属通道容积的50-90%。
6.按照权利要求1所述的制备方法,其特征在于:所述改性剂的改性元素为Si、P、La、Ce、Pr、Nd、K、Zn和Mg中的至少一种。
7.一种权利要求1~6任一所述制备方法制备获得的金属通道内改性ZSM-5分子筛催化剂膜。
8.一种权利要求7所述催化剂膜的应用,其特征在于:用于碳氢燃料催化裂解反应中。
9.按照权利要求8所述催化剂膜的应用,其特征在于:所述碳氢燃料为C8~C15的正构烷烃、异构烷烃、环烷烃、烯烃和芳烃中的至少一种或两种以上。
10.按照权利要求8所述催化剂膜的应用,其特征在于:反应包括的以下条件:
以正癸烷为模型碳氢燃料,内壁具有改性分子筛催化剂膜的高温合金管为反应器,在600℃、3.5MPa压力和1g/s流速下进行裂解反应。
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