CN112316974B - 一种双功能催化剂及其制备方法和应用 - Google Patents
一种双功能催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 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 41
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 33
- 239000011265 semifinished product Substances 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 13
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 230000029936 alkylation Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- CDNBBXKOCUDMCC-UHFFFAOYSA-N but-1-ene;2-methylpropane Chemical compound CCC=C.CC(C)C CDNBBXKOCUDMCC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004898 kneading Methods 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 13
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 11
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 239000000047 product Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- -1 tert-butyl carbonium ions Chemical class 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000005626 carbonium group Chemical group 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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- 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
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Abstract
本发明涉及一种双功能催化剂及其制备方法和应用，属于催化剂技术领域。本发明公开了一种双功能催化剂的制备方法，包括以下步骤：将分子筛A加入水中得到均匀浆液；将金属盐溶液M1加入浆液中；将制得的浆液过滤、洗涤，干燥，焙烧得到催化剂半成品I；将分子筛B加入水中得到均匀浆液；将金属盐溶液M2加入浆液中；将制得的浆液过滤、洗涤，干燥，焙烧得到催化剂半成品II；催化剂半成品I和催化剂半成品II加入水中，过滤、干燥，再捏合后成型得到双功能催化剂。本发明还公开了一种由上述制备方法所制得双功能催化剂以及其用于同时催化丁烯齐聚和异丁烷‑丁烯烷基化制备汽油调和组分的应用。本发明的制备过程简单易操作，简化了工艺流程。
Description
技术领域
本发明涉及一种双功能催化剂及其制备方法和应用，属于催化剂技术领域。
背景技术
混合碳四中丁烯齐聚和异丁烷-丁烯烷基化生产高辛烷值汽油调和组分一直以来是碳四轻烃高值化利用的重要途径。
丁烯齐聚的反应机理如下：
Step 1：催化剂上的氢质子在丁烯双键上加成，生成叔丁基正碳离子
Step 2：叔丁基正碳离子在另一个丁烯双键上加成，生成碳八正碳离子
C4H9 ++C4H8→C8H17 +
Step 3：碳八正碳离子失去氢质子给质子受体，生成齐聚产物
异丁烷-丁烯烷基化的反应机理如下：
Step 1：催化剂上的氢质子在丁烯双键上加成，生成叔丁基正碳离子
Step 2：叔丁基正碳离子在另一个丁烯双键上加成，生成碳八正碳离子
C4H9 ++C4H8→C8H17 +
Step 3：碳八正碳离子从异丁烷叔碳原子上得到氢负离子，生成烷基化产物
H-C4H9+C8H17 +→C8H18+C4H9 +
对上述丁烯齐聚和异丁烷-丁烯烷基化两个反应机理深入分析，可以获悉两反应具有下述共同特点：(1)丁烯齐聚和异丁烷-丁烯烷基化目的产物基本一致，丁烯齐聚的产物辛烯和异丁烷-丁烯烷基化的产物辛烷均是汽油中高辛烷值调和组分，还可以对辛烯进一步加氢得到辛烷；(2)两者均是酸催化反应，且对催化剂酸性的要求基本相当，即中等强度的酸，若酸性过高易发生裂化反应；(3)反应机理均遵循正碳离子理论，即链引发反应相同，均首先生成了叔丁基正碳离子，随后正碳离子在丁烯双键上加成生成了碳八正碳离子这一中间产物；(4)两者所需反应条件基本一致(若均采用分子筛催化剂，反应温度均可控制在80-100℃，压力1.5-2.5MPa)。两者的不同主要在于反应的最后一步，即在丁烯齐聚反应中，碳八正碳离子上的氢质子转移至催化剂或另一个烯烃双键上，从而生成辛烯；而异丁烷-丁烯烷基化反应中，碳八正碳离子可以从异丁烷叔碳原子上得到一个氢负离子便生成了辛烷。由此看来，通过合理设计和优化催化剂配方，可达到调控齐聚与烷基化两反应同步进行的目的，从而实现简化工艺流程，降低操作复杂程度与能耗。
发明内容
本发明针对现有技术的上述问题，提供一种双功能催化剂及其制备方法和应用，用于催化混合碳四中丁烯齐聚和异丁烷-丁烯烷基化反应，生产高辛烷值汽油调和组分。
本发明解决上述技术问题的技术方案如下：一种双功能催化剂的制备方法，包括以下步骤：
步骤一、将分子筛A加入水中，搅拌，制得均匀浆液；
步骤二、将金属盐溶液M1加入到步骤一得到的浆液中，搅拌均匀；
步骤三、将步骤二制得的浆液过滤、洗涤后，恒温干燥，再经过焙烧得到催化剂半成品I；
步骤四、将分子筛B加入水中，搅拌，制得均匀浆液；
步骤五、将金属盐溶液M2加入到步骤四得到的浆液中，搅拌均匀；
步骤六、将步骤五制得的浆液过滤、洗涤后，恒温干燥，再经过焙烧得到催化剂半成品II；
步骤七、将步骤三制得的催化剂半成品I和步骤六制得的催化剂半成品II加入水中，搅拌，制得均匀浆液；
步骤八、将步骤七制得的浆液过滤、干燥，再捏合后成型得到双功能催化剂。
在上述技术方案的基础上，本发明为了达到使用的方便以及装备的稳定性，还可以对上述的技术方案作出如下的改进：
进一步，所述分子筛A为β型分子筛、ZSM-5型分子筛、ZSM-11型分子筛、SAPO-34型分子筛中的任意一种。
进一步，所述分子筛B为X型分子筛或者Y型分子筛。
进一步，所述金属盐溶液M1为铁、镍、铬、锌中的任意一种的硫酸盐或硝酸盐溶液。
进一步，所述金属盐溶液M2为镧或者铈的硫酸盐或硝酸盐溶液。
进一步，所述分子筛A与金属盐溶液M1的质量比为1:5-1:15。
进一步，所述分子筛B与金属盐溶液M2的质量比为1:5-1:15。
进一步，所述步骤三中的焙烧温度为400℃-500℃，焙烧时间为3-6小时；所述步骤六三中的焙烧温度为400℃-500℃，焙烧时间为3-6小时。
本发明还公开了一种由上述制备方法所制得双功能催化剂以及所述双功能催化剂的应用，其用于同时催化丁烯齐聚和异丁烷-丁烯烷基化制备汽油调和组分。
本发明的优点在于：
一、本发明的双功能催化剂的有效成份为金属改性的分子筛A和金属改性的分子筛B，经过不同金属改性的分子筛A和分子筛B可以起到同时催化烯烃齐聚和烷基化的目的，而且前述两个反应的目标产物基本是一致的，均为汽油高辛烷值组分。因此，本发明起到“合二为一”的功效，极大地缩短工艺流程，降低装置操作复杂程度和能耗。
二、制得的双功能催化剂可同时实现混合碳四馏分中丁烯齐聚和异丁烷-丁烯烷基化反应的同步进行，提高汽油中的高辛烷值调和组分，在石油烃类加工领域具有非常重要的应用价值。
具体实施方式
以下将对本发明提供的方法予以进一步的说明，所举实例只用于解释本发明，并非用于限定本发明的范围。以下所举实施例中所有使用的试剂均为市售的化学纯试剂。
实施例1
(1)在200ml去离子水中加入20gβ型分子筛，搅拌均匀；
(2)向步骤(1)的浆液中加入100g 0.2mol/L硫酸铁溶液，80℃恒温水浴下搅拌2h；
(3)重复操作步骤(2)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，得到催化剂半成品I；
(4)在200ml去离子水中加入20g X型分子筛，搅拌均匀；
(5)向步骤(4)的浆液中加入100g 0.2mol/L硫酸镧溶液，80℃恒温水浴下搅拌2h；
(6)重复操作步骤(5)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，得到催化剂半成品II；
(7)取5g催化剂半成品I和5g催化剂半成品II加入到200ml去离子水中，室温下搅拌均匀；
(8)将步骤(7)制得的浆液经过过滤、干燥，得到固体粉末，在粉末中加入2g氧化铝充当粘合剂，经充分混合和捏合后，经过带有多孔模板的挤出机中挤条成型，得到催化剂成品。
实施例2
(1)在200ml去离子水中加入20g ZSM-5型分子筛，搅拌均匀；
(2)向步骤(1)的浆液中加入100g 0.2mol/L硫酸镍溶液，80℃恒温水浴下搅拌2h；
(3)重复操作步骤(2)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，得到催化剂半成品I；
(4)在200ml去离子水中加入20g Y型分子筛，搅拌均匀；
(5)向步骤(4)的浆液中加入100g 0.2mol/L硫酸铈溶液，在80℃恒温水浴下搅拌2h；
(6)重复操作步骤(5)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，得到催化剂半成品II；
(7)取5g催化剂半成品I和5g催化剂半成品II加入到200ml去离子水中，室温下搅拌均匀；
(8)将步骤(7)制得的浆液经过过滤、干燥，得到固体粉末，在粉末中加入2g氧化铝充当粘合剂，经充分混合和捏合后，压片成型，得到催化剂成品。
实施例3
(1)在200ml去离子水中加入20g ZSM-11型分子筛，搅拌均匀；
(2)向步骤(1)的浆液中加入100g 0.2mol/L硫酸铬溶液，在80℃恒温水浴下搅拌2h；
(3)重复操作步骤(2)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，得到催化剂半成品I；
(4)在200ml去离子水中加入20g X型分子筛，搅拌均匀；
(5)向步骤(4)的浆液中加入100g 0.2mol/L硫酸镧溶液，在80℃恒温水浴下搅拌2h；
(6)重复操作步骤(5)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，得到催化剂半成品II；
(7)取5g催化剂半成品I和5g催化剂半成品II加入到200ml去离子水中，室温下搅拌均匀；
(8)将步骤(7)制得的浆液经过过滤、干燥，得到固体粉末，在粉末中加入2g氧化铝充当粘合剂，经充分混合和捏合后，经过带有多孔模板的挤出机中挤条成型，得到催化剂成品。
实施例4
(1)在200ml去离子水中加入20g SAPO-34型分子筛，搅拌均匀；
(2)向步骤(1)的浆液中加入100g 0.2mol/L硫酸锌溶液，在80℃恒温水浴下搅拌2h；
(3)重复操作步骤(2)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，得到催化剂半成品I；
(4)在200ml去离子水中加入20g Y型分子筛，搅拌均匀；
(5)向步骤(4)的浆液中加入100g 0.2mol/L硫酸铈溶液，在80℃恒温水浴下搅拌2h；
(6)重复操作步骤(5)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，得到催化剂半成品II；
(7)取5g催化剂半成品I和5g催化剂半成品II加入到200ml去离子水中，室温下搅拌均匀；
(8)将步骤(7)制得的浆液经过过滤、干燥，得到固体粉末，在粉末中加入2g氧化铝充当粘合剂，经充分混合和捏合后，压片成型，得到催化剂成品。
对比例1
(1)在200ml去离子水中加入20gβ型分子筛，搅拌均匀；
(2)向步骤(1)的浆液中加入100g 0.2mol/L硫酸铁溶液，在80℃恒温水浴下搅拌2h；
(3)重复操作步骤(2)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，压片成型，得到催化剂成品。
对比例2
(1)在200ml去离子水中加入20g X型分子筛，搅拌均匀；
(2)向步骤(1)的浆液中加入100g 0.2mol/L硫酸镧溶液，在80℃恒温水浴下搅拌2h；
(3)重复操作步骤(2)2次；然后将得到的浆液经过过滤后用去离子水洗涤，在100℃温度下在恒温干燥箱中干燥12h，然后在马弗炉中，在空气气氛下，以3℃/min速率升温至450℃焙烧5h，压片成型，得到催化剂成品。
对以上实施例和对比例所制得的催化剂性能进行评价，以上实施例和对比例所得的样品用固定床反应器评价催化剂性能：
将催化剂粉碎成20-40目的颗粒，称取2g装入反应器中，在氮气吹扫下升温至170℃，原位活化10h，自然降温至80℃，随后通入混合碳四原料(组成为80％异丁烷、20％丁烯)，在压力1.5MPa和质量空速1h-1条件下，测得各催化剂样品活性数据，结果如表1所示；
表1催化剂反应性能评价结果
| 催化剂 | 丁烯转化率/％ | C8选择性/％ |
| 实施例1 | 98.6 | 87.8 |
| 实施例2 | 97.1 | 86.5 |
| 实施例3 | 97.7 | 88.4 |
| 实施例4 | 96.9 | 87.9 |
| 对比实施例1 | 85.5 | 67.1 |
| 对比实施例2 | 84.4 | 78.9 |
以上数据说明，本发明的催化剂的活性较高，产物转化率得到显著的提高，并且产物的选择性明显好于对比例所得的催化剂。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (6)
1.一种双功能催化剂的制备方法，其特征在于，包括以下步骤：
步骤一、将分子筛A加入水中，搅拌，制得均匀浆液，所述分子筛A为β型分子筛、ZSM-5型分子筛、ZSM-11型分子筛、SAPO-34型分子筛中的任意一种；
步骤二、将金属盐溶液M1加入到步骤一得到的浆液中，搅拌均匀，所述金属盐溶液M1为铁、镍、铬、锌中的任意一种的硫酸盐或硝酸盐溶液；
步骤三、将步骤二制得的浆液过滤、洗涤后，恒温干燥，再经过焙烧得到催化剂半成品I；
步骤四、将分子筛B加入水中，搅拌，制得均匀浆液，所述分子筛B为X型分子筛或者Y型分子筛；
步骤五、将金属盐溶液M2加入到步骤四得到的浆液中，搅拌均匀，所述金属盐溶液M2为镧或者铈的硫酸盐或硝酸盐溶液；
步骤六、将步骤五制得的浆液过滤、洗涤后，恒温干燥，再经过焙烧得到催化剂半成品II；
步骤七、将步骤三制得的催化剂半成品I和步骤六制得的催化剂半成品II加入水中，搅拌，制得均匀浆液；
步骤八、将步骤七制得的浆液过滤、干燥，再捏合后成型得到双功能催化剂。
2.根据权利要求1所述的双功能催化剂的制备方法，其特征在于，所述分子筛A与金属盐溶液M1的质量比为1:5-1:15。
3.根据权利要求1所述的双功能催化剂的制备方法，其特征在于，所述分子筛B与金属盐溶液M2的质量比为1:5-1:15。
4.根据权利要求1所述的双功能催化剂的制备方法，其特征在于，所述步骤三中的焙烧温度为400℃-500℃，焙烧时间为3-6小时；所述步骤六中的焙烧温度为400℃-500℃，焙烧时间为3-6小时。
5.一种双功能催化剂，其特征在于，由权利要求1-4任一项所述的双功能催化剂的制备方法所制得。
6.根据权利要求5所述的双功能催化剂在同时催化丁烯齐聚和异丁烷-丁烯烷基化制备汽油调和组分中的应用。
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