CN112125867B - 一种赖氨酸催化合成哌啶的方法 - Google Patents
一种赖氨酸催化合成哌啶的方法 Download PDFInfo
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000004472 Lysine Substances 0.000 title claims abstract description 54
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 229960003646 lysine Drugs 0.000 claims abstract description 53
- 235000018977 lysine Nutrition 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011949 solid catalyst Substances 0.000 claims abstract description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 8
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- XAHQYEAIJGTPET-JEDNCBNOSA-N [(1s)-5-amino-1-carboxypentyl]azanium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.NCCCC[C@H]([NH3+])C(O)=O XAHQYEAIJGTPET-JEDNCBNOSA-N 0.000 claims description 2
- RRNJROHIFSLGRA-JEDNCBNOSA-N acetic acid;(2s)-2,6-diaminohexanoic acid Chemical compound CC(O)=O.NCCCC[C@H](N)C(O)=O RRNJROHIFSLGRA-JEDNCBNOSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 229960005357 lysine acetate Drugs 0.000 claims description 2
- 229960005337 lysine hydrochloride Drugs 0.000 claims description 2
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical group CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 230000032683 aging Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 46
- 230000003197 catalytic effect Effects 0.000 description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 235000019766 L-Lysine Nutrition 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 3
- 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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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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
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Abstract
本发明提供了一种赖氨酸催化合成哌啶的方法,将赖氨酸或赖氨酸盐、水、固体催化剂和液体酸置于高压反应釜中进行反应,得到哌啶水溶液。所述固体催化剂以Al2O3、活性炭、ZrO2或SBA‑15为载体,活性组分为Fe、Co、Ni、Ru或Pt中的至少一种。本发明采用L‑赖氨酸盐酸盐为原料,水为溶剂,在高效催化剂的催化作用下,一步生产目标产物哌啶。该方法即节约了原料设备成本,也保证哌啶的收率在92%以上,减小了后续分离的成本。
Description
技术领域
本发明涉及化学合成领域,具体涉及一种赖氨酸催化合成哌啶的方法。
背景技术
哌啶(化学式C5H11N),又名六氢吡啶,无色液体,能与水互溶,水溶液呈碱性,具有腐蚀作用。哌啶主要用在橡胶硫化剂和植物生长调节剂领域,其次可以用于合成医药中间体,环氧树脂固化剂,杀菌剂、润湿剂等;此外,哌啶还可以合成多种高附加值的新型精细化工中间体,随着市场对于药物的需求和重视,目前,在许多精细化学中引入哌啶已经成为开发新品的重要手段,因此,开发一种廉价高效制备哌啶的方法具有重要的现实意义。
在现有制备哌啶的方法中,多为吡啶加氢催化合成哌啶工艺。国外专利使用Ru/C、Pd/C贵金属催化剂下,于160℃及8MPa压力下吡啶催化加成制得哌啶,吡啶转化率接近100%,贵金属催化剂价格昂贵,且未报道催化剂的寿命。国内工厂采用雷尼镍或二硫化钼(MoS2)作催化剂,哌啶收率为88%,但催化剂的稳定性差,容易自燃和失活,保管和使用均不方便。考察具备工业化前景制备哌啶的方法且具有良好催化活性的催化剂是制备哌啶的关键问题。
中国专利(申请号:CN 101723877A)公开了一种由吡啶经氢化制备哌啶的方法。该方法使用氧化铝-二氧化硅作为载体,负载镍基活性组分,反应压力为4.0~10.0MPa,哌啶的收率在95%以上,高压条件对设备要求较高,存在一定的安全隐患,工业化较为困难的缺点。
中国专利(申请号:CN 104844539A)公开了一种由分子筛催化剂催化戊二胺与气体释放剂制备哌啶的方法。该方法使用改性分子筛作为催化剂,反应温度为320~380℃,哌啶的收率在98%以上。该方法使用戊二胺为原料,成本较高,且国内生产戊二胺为卡脖子技术,且本方法反应温度高,能耗较大。
发明内容
本发明提出了一种赖氨酸催化合成哌啶的方法,采用L-赖氨酸盐酸盐为原料,水为溶剂,在高效催化剂的催化作用下,一步生产目标产物哌啶。该方法即节约了原料设备成本,也保证哌啶的收率在92%以上,减小了后续分离的成本。
实现本发明的技术方案是:
一种赖氨酸催化合成哌啶的方法,将赖氨酸或赖氨酸盐、水、固体催化剂和液体酸置于高压反应釜中进行反应,得到哌啶水溶液。
所述赖氨酸为L-赖氨酸,赖氨酸盐为赖氨酸盐酸盐、赖氨酸硫酸盐、赖氨酸醋酸盐、赖氨酸磷酸盐中的任意一种。
所述液体酸为磷酸,硫酸,醋酸,硝酸或柠檬酸的一种。
所述固体催化剂以Al2O3、活性炭、ZrO2或SBA-15为载体,活性组分为Fe、Co、Ni、Ru或Pt中的至少一种。含有上述组分的催化剂可以采用本领域所熟悉的常规催化剂制备方法如:溶胶凝胶法、沉淀法、浸渍法、水热合成法或上述方法结合使用。
高压反应釜中赖氨酸或赖氨酸盐溶解后溶液的浓度为0.001mol/L~3mol/L,赖氨酸或赖氨酸盐与固体催化剂的摩尔比为1:(0.005~0.1)。
所述高压反应釜中反应温度为150~300℃,压力为0.1~8MPa,反应时间为0.5h~8h,反应溶液的pH值为1.80~7.00。
所述高压反应釜中反应在氮气、氢气、氩气、或氦气一种或几种气氛下进行。
所述固体催化剂重复使用50次后,哌啶的收率可达75.0%。
所述固体催化剂中活性组分的负载量为催化剂重量的0.5~15%。
所述载体的比表面积为300~800m2·g-1。
本发明赖氨酸催化合成哌啶的反应是在高压釜式反应器中进行的,并配有100mL聚四氟乙烯内衬和不锈钢搅拌桨。催化剂占反应底物的5%mmol。将高压反应釜完全封闭后,先用N2置换釜内空气6次,再用H2置换釜内N2 6次,后用H2加压至特定的反应压力,反应釜开始升温同时并搅拌。保持特定反应温度1~8h,停止加热采用冰水猝冷,冷却至室温后产物离心取样进行分析。
本发明的有益效果是:赖氨酸制备哌啶是一个复杂的平行串联反应,目的产物哌啶是该平行串联反应中一个比较稳定的产物,采用自制的高效催化剂可控制该反应朝着合成哌啶的方向进行,可避免合成过程中吸附在催化剂上的过渡态提前脱附,从而可减少副产物的形成,且随着反应时间的延长,形成的副产物可在催化剂的进一步作用下合成哌啶,从而获得较高收率的哌啶。
自制的高效催化剂具有高比表面积的特点,活性组分可负载到催化剂表面和孔道内,从而暴露出更多促进生成哌啶的活性位点,进而获得高收率的哌啶,且自制的负载型催化剂寿命较高。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1、图2为本发明实施例1产物的液相色谱图。
图3为本发明实施例1产物的质谱图。
图4为本发明实施例1催化剂的吸附脱附曲线。
具体实施方式
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种L-赖氨酸化学法制备哌啶的方法,步骤如下:
(1)催化剂制备
1.1 载体制备
将16.1gAl(NO3)3•9H2O与100mL无水乙醇在室温下搅拌半小时,充分水合后加入2.3mL去离子水。H3PO4作为模板剂,按照P/Al摩尔比为1,向上述溶液加入2.94mLH3PO4,继续搅拌20min;环氧丙烷作为凝胶剂,加入33mL,20min内得到白色不透明胶体。胶体在室温下老化两天,将老化后的胶体于80℃下干燥两天。最后升至700℃焙烧5h(升温速率为1℃/min)除去模板剂,得到Al2O3载体。经BET表征后,载体比表面积为378.35m2·g-1。
1.2 活性组分负载
采用浸渍法制备负载量为5%的Ni/Al2O3催化剂,具体制备步骤为:称取1.2387g Ni(NO3)2•6H2O,溶于去离子水中,得浅绿色澄清溶液,往该溶液中加入5gAl2O3载体,充分搅拌后静置过夜,用旋转蒸发仪将溶液蒸干后,放置干燥箱中,在105℃干燥12h,干燥研磨后的催化剂在马弗炉中进行程序升温到550℃,恒温焙烧4h(升温速率为1℃/min),得到浅绿色粉末。在H2/Ar氛围下400 ℃还原得到Ni/ Al2O3催化剂。
(2)催化合成反应
取5 mmol赖氨酸、50 mL水置于容积为100 mL的反应釜中,搅拌至赖氨酸原料完全溶解,加入5mol%的Ni/Al2O3催化剂,搅拌5min后用磷酸调节pH至3.0。密封反应釜后,用氢气置换釜中的空气,随后加压至2MPa,升温至150℃,搅拌速度为500 r/min,6h后停止反应。采用高效液相色谱检测手段分析反应产物中的哌啶,赖氨酸转化率为86.0%,哌啶选择性为64.5%,收率为55.5%。
实施例2
与实施例1的不同在与,磷酸调节pH=2.0。催化性能评价,赖氨酸转化率为88.1%,哌啶选择性为75.3%,收率66.3%。
实施例3
与实施例2的不同在与,反应体系H2压力为4MPa。催化性能评价,赖氨酸转化率为86.8%,哌啶选择性为70.6%,收率61.3%。
实施例4
与实施例2的不同在与,反应体系温度为200℃。催化性能评价,赖氨酸转化率为98.8%,哌啶选择性为85.1%,收率84.1%。
实施例5
与实施例4的不同在与,催化剂活性组分负载量为10%。催化性能评价,赖氨酸转化率为100%,哌啶选择性为80.7%,收率80.7%。
实施例6
与实施例4的不同在与,反应时间为8h。催化性能评价,赖氨酸转化率为100%,哌啶选择性为75.5%,收率75.5%。
实施例7
一种L-赖氨酸化学法制备哌啶的方法,步骤如下:
(1)催化剂制备
1.1 载体制备
在35℃的条件下,将三嵌段表面活性剂P123溶于适量去离子水,向其中加入正硅酸乙酯(TEOS)、盐酸(HCl),持续剧烈地搅拌24h以上,装入聚四氟乙烯瓶内100℃晶化24h,过滤、洗涤并干燥,最后在550℃煅烧5h以上除去模板剂得到的白色粉末即为SBA-15。实验所用各原料的摩尔比约为1TEOS:0.017P123:5.88HCl:136H2O。
经BET表征后,载体比表面积为786.68m2·g-1。
1.2 活性组分负载
采用浸渍法制备负载量为5%的Fe/SBA-15催化剂,具体制备步骤为:称取1.8086 g硝酸铁,溶于去离子水中,得淡黄色澄清溶液,往该溶液中加入5g SBA-15载体,充分搅拌后静置过夜,用旋转蒸发仪将溶液蒸干后,放置干燥箱中,在105℃干燥12h,干燥研磨后的催化剂在马弗炉中进行程序升温到550℃,恒温焙烧4h(升温速率为1℃/min)。在H2/Ar氛围下400 ℃还原得到Fe/SBA-15催化剂。
(2)催化合成反应
取5mmol赖氨酸、50mL水置于容积为100mL的反应釜中,搅拌至赖氨酸原料完全溶解,加入5mol%的Fe/SBA-15催化剂,搅拌5min后用磷酸调节pH至3.0。密封反应釜后,用氢气置换釜中的空气,随后加压至2 MPa,升温至200 ℃,搅拌速度为500 r/min,6h后停止反应。采用高效液相色谱检测手段分析反应产物中的哌啶,赖氨酸转化率为99.2%,哌啶选择性为86.2%,收率为85.5%。
实施例8
与实施例7的不同在与,磷酸调节pH=2.0。催化性能评价,赖氨酸转化率为100%,哌啶选择性为88.7%,收率88.7%。
实施例9
与实施例7的不同在与,负载型催化剂载体为实例1中溶胶-凝胶法制备的介孔Al2O3载体。催化性能评价,赖氨酸转化率为100%,哌啶选择性为92.3%,收率92.3%。
实施例10
与实施例9的不同在与,反应体系温度为220℃。催化性能评价,赖氨酸转化率为100%,哌啶选择性为90.9%,收率90.9%。
实施例11
与实施例9的不同在与,反应体系H2压力为4MPa。催化性能评价,赖氨酸转化率为100%,哌啶选择性为91.0%,收率91.0%。
实施例12
与实施例9的不同在与,反应体系原料L-赖氨酸投入量为10mmol。催化性能评价,赖氨酸转化率为99%,哌啶选择性为86.0%,收率85.1%。
实施例13
一种L-赖氨酸化学法制备哌啶的方法,步骤如下:
(1)催化剂制备
采用共沉淀法制备质量分数5mol% Pt/ZrO2催化剂,用去离子水配制氧氯化锆溶液、氯铂酸溶液以及尿素溶液,氧氯化锆溶液为0.4mol/L,与尿素溶液混合,尿素的物质的量为氧氯化锆和氯铂酸总量的10倍,控制总的反应体积为300mL,充分搅拌,并从室温升温到85℃持续搅拌8h后静置过夜,将反应得到的产物进行离心分离,去离子水洗涤至中性同时无氯离子(硝酸银溶液检测无沉淀产生),并在105℃下干燥12h,研磨后在马弗炉中以2℃/min的升温速率从室温升温至650℃焙烧5h。后在H2/Ar气氛中,400℃活化2 h,得到Pt/ZrO2催化剂。
(2)催化合成反应
取5mmol赖氨酸、50mL水置于容积为100mL的反应釜中,搅拌至赖氨酸原料完全溶解,加入5mol%的Pt/ZrO2催化剂,搅拌5 min后用磷酸调节pH至3.0。密封反应釜后,用H2置换釜中的空气,随后加压至2MPa,升温至200℃,搅拌速度为500 r/min,6h后停止反应。采用高效液相色谱检测手段分析反应产物中的哌啶,赖氨酸转化率为95.0%,哌啶选择性为80.3%,收率为76.3%。
实施例14
与实施例13的不同在与,催化剂活性组分Pt负载量为1%。催化性能评价,赖氨酸转化率为76.0%,哌啶选择性为78.1%,收率59.4%。
实施例15
与实施例13的不同在与,反应体系温度为250℃;催化性能评价,赖氨酸转化率为98.7%,哌啶选择性为78.9%,收率77.9%。
实施例16
与实施例13的不同在与,反应体系pH=2.0。催化性能评价,赖氨酸转化率为95.3%,哌啶选择性为85.6%,收率81.6%。
实施例17
与实施例13的不同在与,反应体系调节pH的酸为浓硫酸。催化性能评价,赖氨酸转化率为59.0%,哌啶选择性为30.5%,收率18.0%。
实施例18
与实施例13的不同在与,反应体系气体组分为N2。催化性能评价,赖氨酸转化率为10.0%,哌啶选择性为20.2%,收率2%。
催化剂循环使用次数
实施例9中的Fe/Al2O3催化剂,反应后经离心后去离子水洗至中性,于105℃下干燥12h,研磨后在管式炉H2气氛中,400℃活化2 h,得到新生催化剂Fe/Al2O3重复使用。重复使用50次后,仍具有较高催化活性,哌啶的收率可达75.0%。
以上所述仅为本发明的较佳实施例而已,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 (9)
1.一种赖氨酸催化合成哌啶的方法,其特征在于:将赖氨酸或赖氨酸盐溶液、固体催化剂和液体酸置于高压反应釜中进行反应,得到哌啶水溶液;
所述固体催化剂的制备方法如下:
(1)载体制备:将16.1gAl(NO3)3•9H2O与100mL无水乙醇在室温下搅拌半小时,充分水合后加入2.3mL去离子水;H3PO4作为模板剂,按照P/Al摩尔比为1,向上述溶液加入2.94mLH3PO4,继续搅拌20min;环氧丙烷作为凝胶剂,加入33mL,20min内得到白色不透明胶体;胶体在室温下老化两天,将老化后的胶体于80℃下干燥两天;最后升至700℃焙烧5h除去模板剂,得到Al2O3载体;
(2)活性组分负载:称取1.2387g Ni(NO3)2•6H2O,溶于去离子水中,得浅绿色澄清溶液,往该溶液中加入5gAl2O3载体,充分搅拌后静置过夜,用旋转蒸发仪将溶液蒸干后,放置干燥箱中,在105℃干燥12h,干燥研磨后的催化剂在马弗炉中进行程序升温到550℃,恒温焙烧4h(升温速率为1℃/min),得到浅绿色粉末,在H2/Ar氛围下400 ℃还原得到Ni/ Al2O3催化剂。
2.根据权利要求1所述的赖氨酸催化合成哌啶的方法,其特征在于:所述赖氨酸为L-赖氨酸,赖氨酸盐为赖氨酸盐酸盐、赖氨酸硫酸盐、赖氨酸醋酸盐、赖氨酸磷酸盐中的任意一种。
3.根据权利要求1所述的赖氨酸催化合成哌啶的方法,其特征在于:所述液体酸为磷酸。
4.根据权利要求1所述的赖氨酸催化合成哌啶的方法,其特征在于:赖氨酸或赖氨酸盐溶液的浓度为0.001mol/L~3mol/L,赖氨酸或赖氨酸盐与固体催化剂的摩尔比为1:(0.005~0.1)。
5.根据权利要求1所述的赖氨酸催化合成哌啶的方法,其特征在于:所述高压反应釜中反应温度为150~300℃,压力为0.1~8MPa,反应时间为0.5h~8h,反应溶液的pH值为1.80~7.00。
6.根据权利要求4或5所述的赖氨酸催化合成哌啶的方法,其特征在于:所述高压反应釜中反应在氢气气氛下进行。
7.根据权利要求1所述的赖氨酸催化合成哌啶的方法,其特征在于:所述固体催化剂重复使用50次后,哌啶的收率可达75.0%。
8.根据权利要求1所述的赖氨酸催化合成哌啶的方法,其特征在于:所述固体催化剂中活性组分的负载量为催化剂重量的0.5~15%。
9.根据权利要求1所述的赖氨酸催化合成哌啶的方法,其特征在于:所述载体的比表面积为300~800m2·g-1。
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