CN114920687B - 一种4,4′-联吡啶的制备方法 - Google Patents
一种4,4′-联吡啶的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 65
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 37
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- 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 21
- 238000005859 coupling reaction Methods 0.000 claims abstract description 14
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000004508 fractional distillation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 238000011068 loading method Methods 0.000 description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- 229910001948 sodium oxide Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PVMNPAUTCMBOMO-UHFFFAOYSA-N 4-chloropyridine Chemical compound ClC1=CC=NC=C1 PVMNPAUTCMBOMO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RMHQDKYZXJVCME-UHFFFAOYSA-N 2-pyridin-4-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=NC=C1 RMHQDKYZXJVCME-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- OEHTZLHLYQKGGH-UHFFFAOYSA-N formaldehyde pyridine Chemical compound C=O.C1=CC=NC=C1.C1=CC=NC=C1 OEHTZLHLYQKGGH-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- -1 nickel-phosphine compound Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
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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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种4,4'‑联吡啶的制备方法，包括：以吡啶为原料，吡啶经过预热气化后，在负载型Ni/HY催化剂催化作用下，经脱氢偶联反应生成4,4'‑联吡啶；所述的负载型Ni/HY催化剂的镍负载量为5％～30％，负载型Ni/HY催化剂的载体为HY分子筛。本发明以廉价的吡啶为原料，生产成本低；本发明采用负载型Ni/HY催化剂，经一步催化偶联脱氢反应得到4,4'‑联吡啶，目标产物选择性高，反应流程简单，易于操作，且产生的三废量少，对环境友好，适合连续化、工业化生产4,4'‑联吡啶。
Description
技术领域
本发明属于精细化工和有机合成领域，涉及一种4,4′-联吡啶的制备方法，具体涉及一种吡啶气相催化脱氢偶联制备4,4′-联吡啶的方法。
背景技术
4,4′-联吡啶可用于合成除草剂百草枯，是化工和医药合成的重要中间体，由于具有独特的螯合作用，可以作为金属催化剂的配体、光敏剂、检测金属离子的指示剂等。
4,4′-联吡啶主要合成方法包括：
①热钠法或低温钠法：热钠法即吡啶与钠在加热回流条件下反应，然后通入一定量的空气进行氧化得到4,4′-联吡啶，收率低于50％，且产品纯度不高。低温钠法由ICI公司首创，吡啶与钠的液氨溶液在-20℃～-30℃下反应得中间体，然后再经空气氧化得到4,4′-联吡啶，该法产品纯度高，吡啶利用率高。由于钠法工艺用到钠，存在着火和爆炸的危险，制约工业化生产。
②4-氯吡啶法：以4-氯吡啶为原料，用含镍-膦化合物为催化剂制备4,4′-联吡啶。该方法反应容易进行，且收率较高，但原料4-氯吡啶价格较高，成本高，不适合工业化生产。
③对甲醛基吡啶法：以铝酸盐或磷酸盐为催化剂，在反应温度300～450℃下，对甲醛基吡啶与乙醛和氨在氮气流中进行气相反应。该方法所用原料对甲醛基吡啶不易得，成本高，没有工业化价值。
发明内容
本发明的目的在于克服了现有技术的不足，提供一种4,4′-联吡啶的制备方法，以廉价的吡啶为原料，经一步催化脱氢偶联反应得到4,4′-联吡啶，该方法具有原子利用率高、成本低、操作简单方便、安全性高、适合工业化的优点。
本发明的目的是通过以下技术方案实现的：
一种4,4′-联吡啶的制备方法，包括：以吡啶为原料，吡啶经过预热气化后，在负载型Ni/HY催化剂催化作用下，经脱氢偶联反应生成4,4′-联吡啶。
具体的，所述的4,4′-联吡啶的制备方法包括：以吡啶为原料，吡啶进入预热器，经过预热气化后，通过装填有负载型Ni/HY催化剂的固定床反应器，在负载型Ni/HY催化剂催化作用下，经脱氢偶联反应生成4,4′-联吡啶。
作为本发明所述的4,4′-联吡啶的制备方法的进一步优选方案，还包括：4,4′-联吡啶溶于未反应的吡啶中，通过精馏分离将4,4′-联吡啶和吡啶分离，吡啶循环套用。
吡啶气化前的液体空速为0.5～6g吡啶/(g催化剂·h)，优选为0.5～2g吡啶/(g催化剂·h)，更优选为2g吡啶/(g催化剂·h)。
脱氢偶联反应的温度为250～450℃，优选为280～400℃，进一步优选为300～350℃，最优选为320℃；脱氢偶联反应的压力为常压。
所述的负载型Ni/HY催化剂的镍负载量为5％～30％，优选为10％～30％，进一步优选为10％；所述的负载型Ni/HY催化剂的载体为HY分子筛(即氢型Y分子筛)，HY分子筛的硅铝比为5～100，HY分子筛的硅铝比对反应结果影响较为显著，若硅铝比过低，催化剂易失活，若硅铝比过高，会生成2,4′-联吡啶、2,2′-联吡啶副产物，造成目标产物选择性下降。因此，HY分子筛的硅铝比优选为40～60。
本发明的另一个目的是提供一种所述的负载型Ni/HY催化剂的制备方法，包括：将六水硝酸镍溶于蒸馏水，搅拌下加入HY分子筛，浸渍过夜，然后在120℃下烘干，在温度400～500℃下焙烧，压片成型，再在温度450～550℃下、氢气还原，即得负载型Ni/HY催化剂。
本发明的另一个目的是提供一种4,4′-联吡啶的制备装置，包括预热器、固定床反应器、冷凝器；固定床反应器包括筒体，筒体外设有夹套，所述的夹套的下部、上部分别设有导热物质进口、导热物质出口；所述的预热器的进料口分别与液体进料管、进气管相连，预热器的出料口与固定床反应器顶部的进料口相连；所述的固定床反应器内装有负载型Ni/HY催化剂，固定床反应器分别设有温度测量器、压力测量器，用于测量固定床反应器内温度、压力；固定床反应器底部出料口设有出料管，在出料管上设有所述的冷凝器用于降温收集反应产物。
优选的，所述的固定床反应器为不锈钢筒体。
优选的，在预热器和固定床反应器的连接管路上设有气体流量计。
优选的，所述的温度测量器为工业常用温度测量器均可，如热电偶；所述的压力测量器可以为任何工业常用压力测量器，如压力表；反应器内压力控制可选用现有技术中任何的工业常用方式，如由背压阀控制。
和现有技术相比，本发明具有以下有益效果：
(1)、本发明以廉价的吡啶为原料，避免昂贵原材料的使用，生产成本低。
(2)、本发明避免使用易燃易爆的金属钠，且反应为连续反应，反应安全可控。
(3)、本发明采用负载型Ni/HY催化剂，经一步催化偶联脱氢反应得到4,4′-联吡啶，目标产物选择性高，反应流程简单，易于操作，且产生的三废量少，对环境友好，适合连续化、工业化生产4,4′-联吡啶。
(4)、本发明负载型Ni/HY催化剂催化寿命更长，在本发明工艺条件下，即使连续反应1000小时，也能维持较高的吡啶转化率和较高的目标产物选择性。
附图说明
图1为制备4,4’-联吡啶的装置的结构示意图。
图中，E-预热器，R-固定床反应器，C-冷凝器；1-液体进料管；2-进气管，3-气体流量计，4-压力表，5-背压阀，6-导热油进料管，7-导热油出料管，8-热电偶，9-出料管，10-夹套。
具体实施方式
下面结合实施例对本发明的技术方案做进一步说明，应当说明的是，实施例仅是提供了一种具体的实施方案，并不是对本发明所述方法的限定，能够实现本发明所述条件的设备均可以用来实现本发明。
实施例1
负载型Ni/HY催化剂(以下简称负载镍)的制备方法如下：20g六水硝酸镍溶于200mL蒸馏水中，将40g HY分子筛粉末(硅铝比40，孔径4nm，比表面积750g/m2，氧化钠0.03％)浸入到硝酸镍水溶液中，常温搅拌过夜，120℃干燥12h，450℃焙烧16h，压片机压片，筛分，取10～20目催化剂前体，催化剂前体于500℃氢气流(18L/h)中还原12h，即得镍负载量10％的负载型Ni/HY催化剂(记为催化剂1)。
实施例2
采用HY分子筛粉末(硅铝比5，孔径4nm，比表面积750g/m2，氧化钠0.2％)替换实施例1HY分子筛粉末，其余均与实施例1相同，制得镍负载量10％的负载型Ni/HY催化剂(记为催化剂2)。
实施例3
采用HY分子筛粉末(硅铝比20，孔径4nm，比表面积750g/m2，氧化钠0.2％)替换实施例1HY分子筛粉末，其余均与实施例1相同，制得镍负载量10％的负载型Ni/HY催化剂(记为催化剂3)。
实施例4
采用HY分子筛粉末(硅铝比80，孔径4nm，比表面积750g/m2，氧化钠0.03％)替换实施例1HY分子筛粉末，其余均与实施例1相同，制得镍负载量10％的负载型Ni/HY催化剂(记为催化剂4)。
实施例5
10g六水硝酸镍溶于100mL蒸馏水中，将40g HY分子筛粉末(硅铝比40，孔径4nm，比表面积750g/m2，氧化钠0.03％)浸入到硝酸镍水溶液中，常温搅拌过夜。其余均与实施例1相同，制得镍负载量5％的负载型Ni/HY催化剂(记为催化剂5)。
实施例6
60g六水硝酸镍溶于600mL蒸馏水中，将40g HY分子筛粉末(硅铝比40，孔径4nm，比表面积750g/m2，氧化钠0.03％)浸入到硝酸镍水溶液中，常温搅拌过夜。其余均与实施例1相同，制得镍负载量30％的负载型Ni/HY催化剂(记为催化剂6)。
表1.实施例1-实施例6制得的负载型Ni/HY催化剂
| 催化剂编号 | 镍负载量％ | HY分子筛硅铝比 |
| 催化剂1 | 10 | 40 |
| 催化剂2 | 10 | 5 |
| 催化剂3 | 10 | 20 |
| 催化剂4 | 10 | 80 |
| 催化剂5 | 5 | 40 |
| 催化剂6 | 30 | 40 |
实施例7
如图1所示，一种制备4,4’-联吡啶的装置，包括固定床反应器R、预热器E、冷凝器C，固定床反应器R为内径2cm不锈钢反应管，筒体外设有夹套10，所述的夹套10的下部、上部分别设有导热油进口6、导热油出口7；所述的预热器E的进料口分别与液体进料管1、进气管2相连，预热器E的出料口与固定床反应器R顶部的进料口相连，在预热器E和固定床反应器R的连接管路上设有气体流量计3；固定床反应器R内装有负载型Ni/HY催化剂，固定床反应器R内温度由热电偶8测量，压力由压力表4测量，固定床反应器R内压力由背压阀5控制，固定床反应器R底部出料口设有出料管9，在出料管9上设有冷凝器C用于降温收集反应产物。
在反应管下端装入适量的惰性石英沙作为支撑，取30g催化剂前体(10～20目)装入反应管，在反应管上端装入适量的惰性石英沙作为缓冲；往固定床反应器中通入氢气(流量18L/h)，于500℃氢气流中还原12h，即得负载型Ni/HY催化剂，然后降温至200℃；见表2参数，通入原料吡啶，吡啶经预热器115℃预热气化后进入固定床反应器，从上往下通过催化剂床层，在常压下，经一步催化脱氢偶联反应得到4,4′-联吡啶，反应产物自固定床反应器底部排出，经冷凝器降温后收集反应液，取反应液进行分析，结果如表2所示。
表2.不同条件下的反应结果
注：空速为吡啶气化前的液体空速；
4,4′：4,4′-联吡啶；2,4′：2,4′-联吡啶；2,2′：2,2′-联吡啶。
Claims (8)
1.一种4,4'-联吡啶的制备方法，其特征在于：包括：以吡啶为原料，吡啶经过预热气化后，在负载型Ni/HY催化剂催化作用下，经脱氢偶联反应生成4,4'-联吡啶；
吡啶气化前的液体空速为0.5～6g吡啶/(g催化剂·h)；
所述的负载型Ni/HY催化剂的镍负载量为5%～30%；所述的负载型Ni/HY催化剂的载体为HY分子筛，HY分子筛的硅铝比为5～100；
脱氢偶联反应的温度为250～450℃。
2.根据权利要求1所述的4,4'-联吡啶的制备方法，其特征在于：吡啶气化前的液体空速为0.5～2g吡啶/(g催化剂·h)。
3.根据权利要求2所述的4,4'-联吡啶的制备方法，其特征在于：吡啶气化前的液体空速为2 g吡啶/(g催化剂·h)。
4.根据权利要求1所述的4,4'-联吡啶的制备方法，其特征在于：脱氢偶联反应的温度为280～400℃。
5.根据权利要求4所述的4,4'-联吡啶的制备方法，其特征在于：脱氢偶联反应的温度为300～350℃。
6.根据权利要求1所述的4,4'-联吡啶的制备方法，其特征在于：所述的负载型Ni/HY催化剂的镍负载量为10%～30%；所述的HY分子筛的硅铝比为40～60。
7.根据权利要求1所述的4,4'-联吡啶的制备方法，其特征在于：还包括：通过精馏分离将4,4'-联吡啶和吡啶分离。
8.根据权利要求1所述的4,4'-联吡啶的制备方法，其特征在于：负载型Ni/HY催化剂的制备方法包括：将六水硝酸镍溶于蒸馏水，搅拌下加入HY分子筛，浸渍过夜，然后在120℃下烘干，在温度400～500℃下焙烧，压片成型，再在温度450～550℃下、氢气还原，即得负载型Ni/HY催化剂。
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