CN116947582A - 一种氟化工艺制备硝基化合物的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 150000002828 nitro derivatives Chemical class 0.000 title claims abstract description 37
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 238000006396 nitration reaction Methods 0.000 claims abstract description 58
- 239000007789 gas Substances 0.000 claims abstract description 49
- -1 nitrogen heterocyclic compounds Chemical class 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000007791 liquid phase Substances 0.000 claims abstract description 31
- 239000012071 phase Substances 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002608 ionic liquid Substances 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 25
- 230000001546 nitrifying effect Effects 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011964 heteropoly acid Substances 0.000 claims description 13
- WUSYAIQLOOSERH-UHFFFAOYSA-N N=O.F Chemical compound N=O.F WUSYAIQLOOSERH-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000713 high-energy ball milling Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- YPDSOAPSWYHANB-UHFFFAOYSA-N [N].[F] Chemical compound [N].[F] YPDSOAPSWYHANB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- VRLOMVGLFOVCKX-UHFFFAOYSA-N n-ethoxy-2-methoxyethanamine Chemical compound CCONCCOC VRLOMVGLFOVCKX-UHFFFAOYSA-N 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims 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 claims description 2
- 229910004039 HBF4 Inorganic materials 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 230000000802 nitrating effect Effects 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 150000002221 fluorine Chemical class 0.000 description 3
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004030 azacyclic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/02—Formation or introduction of functional groups containing nitrogen of nitro or nitroso groups
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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Abstract
本发明一种氟化工艺制备硝基化合物的方法,其特征在于:采用NO2F及所述NO2F与催化剂反应制得的NO2 +BF4 ‑作为硝化剂,与芳烃、氮杂环化合物、胺类、醇类或低碳烷烃硝化反应,在催化剂催化下生成所述芳烃、氮杂环化合物、胺类、醇类或低碳烷烃的硝基化合物;所述催化剂为气相硝化催化剂或液相硝化离子液体催化剂。具体步骤为:制备NO2F、制备气相硝化催化剂或液相硝化离子液体催化剂、NO2F与催化剂中HBF4反应生成强硝化能力的NO2 +BF4 ‑、催化剂催化下生成硝基化合物。该工艺可制得高转化率的硝基化合物。
Description
技术领域
本发明涉及有机合成技术领域,具体地,涉及一种氟化工艺制备硝基化合物的方法。
背景技术
硝基化合物是硝基(硝酸分子中去掉一个羟基后剩下的基团)与其他元素结合形成的物质,如碳硝基化合物、氮硝基化合物及各类芳香族硝基化合物等,可广泛用做医药、染料、香料、***等工业的化工原料及有机合成试剂。
现今,硝基化合物主要通过使用混酸(硝酸/硫酸)硝化工艺制备而成,这类工艺存在许多问题。硝化能力受硝酰正离子浓度影响大,较高浓度的硝酸电离出硝酰正离子少,特别是纯硝酸中仅约3.5%以离子形态存在,绝大部分是分子态,加入强质子酸(如硫酸)虽可提高离其离子态占比,但会降低硝酰根总数,当硝酸浓度较低时,与低碳烷基发生取代时易导致侧链氧化,发生副反应。因此,硝酸的硝化能力较弱、羟基吸电子能力较小,使得反应速率及效率较低。
发明内容
为解决现有技术中光刻胶曝光显影中出现的技术问题,本发明提供一种氟化工艺制备硝基化合物的方法,采用NO2F及NO2F与催化剂反应制得的NO2 +BF4 -作为硝化剂,与芳烃、氮杂环化合物、胺类、醇类或低碳烷烃硝化反应,在气相硝化催化剂或液相硝化离子液体催化剂催化下生成相应的所述硝基化合物;
所述芳烃为苯、硝基苯、萘、氯苯、甲苯、苯酚、邻二甲苯、间二甲苯、对二甲苯中的至少一种;所述氮杂环化合物为含氮杂环的吡咯类、噻唑类、咪唑类化合物;所述胺类为氨气、三辛胺、二乙胺、三乙胺、二-正丙胺、三-2-(2-甲氧基(乙氧基)乙基胺)中的至少一种;所述醇类为脂肪醇;所述低碳烷烃的碳原子数为1-5的直链烷烃;
所述气相硝化催化剂为掺杂有杂多酸氟盐催化剂,所述杂多酸负载在二氧化硅载体上,所述杂多酸为H3PW12O40/HBF4、H4SiW12O40/HBF4中的至少一种,其中HBF4在所述杂多酸的质量占比为25-45%;
将H3PW12O40/HBF4、H4SiW12O40/HBF4与二氧化硅高能球磨,球磨时长为3-8H,球料比10:1,制得粒径为150-550nm级别高效催化的H3PW12O40/HBF4/SiO2、H4SiW12O40/HBF4/SiO2;
所述液相硝化离子液体催化剂采用N-己内酰胺类四氟硼酸盐、N-甲基咪唑四氟硼酸盐中的至少一种四氟硼酸盐;
步骤如下:
S100:制备NO2F
a.在常温下以氟气和氮气的摩尔比为1:(5-8),通入氟氮混合气对反应釜预处理,然后通入纯氟气对反应釜钝化处理;
b.在常温下以纯氟气和NO2的摩尔比为1:(5-8),通入纯氟气和NO2,制得粗硝酰氟,在常温下以粗硝酰氟与氮气的摩尔比为1:(5-8),在反应釜通入制得的所述粗硝酰氟-氮气;
c.将NO2F粗气体经过-30~-50℃冷阱去除HF杂质后送入NO2F精馏***;
d.将气体NO2F通过特制的氟化钠分子筛后升温至30℃,进一步去除HF杂质;
e.将粗纯化后的NO2F通入精馏***中,精馏控制参数为:塔压控制在0.1~0.3Mpa,第二塔板控制温度在-40~-50℃,倒二塔板控制温度30~40℃,以去除F2、NOF杂质,制得所述NO2F;
S200:制备气相硝化催化剂
在200-300℃高温焙烤杂多酸及SiO2,提供HBF4,HBF4在气相硝化催化剂的质量占比为25-45%,称取HBF4、杂多酸及SiO2,高能球磨,球磨时长为3-8H,球料比10:1,将制得的H3PW12O40/HBF4/SiO2、H4SiW12O40/HBF4/SiO2,将其分别与氟化钠或氟化钙共混,制得所述气相硝化催化剂;
S300:制备液相硝化离子液体催化剂
将0.3mol-1.2mol的N-己内酰胺类四氟硼酸盐、N-甲基咪唑四氟硼酸盐中的至少一种,超声波分散溶解在500mL的CCl4或CH2Cl2有机溶剂中,浓度为0.6-2.4mol/L,制得所述液相硝化离子液体催化剂;
S400:气相硝化制备硝基化合物
按所述气相硝化催化剂与芳烃、氮杂环化合物、胺类、醇类或低碳烷烃的摩尔比值(0.05-0.25):1,取所述气相硝化催化剂和芳烃、氮杂环化合物、胺类、醇类或低碳烷烃;
在连续管式固定床反应器放置所述气相硝化催化剂,加温65-80℃预热,先通入所述NO2F气体,30-60min后,NO2F气体与所述气相硝化催化剂中HBF4反应,生成强硝化能力的NO2 +BF4 -;
通入氮气或氦气,再将已气化的芳烃、氮杂环化合物、胺类、醇类或低碳烷烃与所述NO2F气体通入连续管式固定床反应器,充分反应2-5小时,制得相应的所述硝基化合物;
S500:液相硝化制备硝基化合物
提供高压反应釜,按所述液相硝化离子液体催化剂与芳烃、氮杂环化合物、胺类、醇类或低碳烷烃的摩尔比值(0.05-0.25):1,取所述液相硝化离子液体催化剂和所述芳烃、氮杂环化合物、胺类、醇类或低碳烷烃;
将芳烃、氮杂环化合物、胺类、醇类或低碳烷烃放置或通入高压反应釜,通入所述NO2F气体,加压1~1.3Mpa,NO2F气体与所述液相硝化离子液体催化剂水解电离产生的BF4 -离子反应,生成强硝化能力的NO2 +BF4 -,然后超声波硝化反应2-5小时,碱液水洗,制得所述相应的所述硝基化合物。
本发明取得的有益效果有:
1)采用NO2F气体氟化苯分子,硝酰氟以离子的形态存在,极大提高了硝酰根离子浓度,极大的提高了硝化能力;
2)同时硝酰氟与气相硝化催化剂中的HBF4或者液相硝化离子液体催化剂水解电离产生的BF4 -离子反应,生成强硝化能力的NO2 +BF4 -,催化剂既起到催化硝化的作用,同时可生成硝化能力强的NO2 +BF4 -,进一步提高硝基化合物的转化率,可调控BF4 -的含量,进而调整硝基化合物的转化率;
3)通过调整催化剂投料的摩尔比,催化剂提供更多的HBF4或者水解电离产生的BF4 -离子参与反应,硝基化合物的转化率也随之提高。
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为一种氟化工艺制备硝基化合物的方法的流程图。
具体实施方式
为了能够更清楚地理解本发明的上述目的、特征和优点,下面结合附图和实施例对本发明做进一步说明。需要说明的是,在不冲突的情况下,本申请的实施例及实施例中的特征可以相互组合。
下面结合附图和具体实施例对本发明作进一步说明。
如图1,为实施例一种氟化工艺制备硝基化合物的方法的流程图。
实施例1:气相硝化制备苯硝基化合物
S100:制备气相硝化催化剂
在200-300℃高温焙烤杂多酸及S iO2,按HBF4在气相硝化催化剂的质量占比为35%称取HBF4,按SiO2的质量占比为12%称取SiO2,其余为杂多酸H3PW12O40或H4SiW12O40;
高能球磨,球磨时长为3-8H,球料比10:1,制得的H3PW12O40/HBF4/S iO2、H4SiW12O40/HBF4/SiO2;
按与氟盐的摩尔比为1.2:1取氟盐,与氟盐(氟化钠或氟化钙)共混,制得气相硝化催化剂;
S200:制备气相硝化制备苯硝基化合物
在连续管式固定床反应器放置S100制得的气相硝化催化剂,加温65-80℃预热,先通入NO2F气体,30min后,NO2F气体与气相硝化催化剂中HBF4反应,生成强硝化能力的NO2 +BF4 -1;
通入氮气,再将已气化的苯分子与NO2F气体通入连续管式固定床反应器,硝化反应5小时,以NO2F的强氟化及NO2 +BF4 -1的强硝化能力,制得苯硝基化合物。
实施例2:液相硝化制备苯硝基化合物
S100:制备液相硝化离子液体催化剂
将0.5molN-甲基咪唑四氟硼酸盐超声波分散溶解在500mLCCl4有机溶剂中,制得液相硝化离子液体催化剂;
S200:液相硝化制备苯硝基化合物
提供高压反应釜,加入步骤S100制得的液相硝化离子液体催化剂,将苯放置在高压反应釜,通入NO2F气体,加压1.3Mpa,NO2F气体与液相硝化离子液体催化剂水解电离产生的BF4 -1离子反应,生成强硝化能力的NO2 +BF4 -1,然后超声波硝化反应5小时,碳酸氢钠水洗三次,制得苯硝基化合物。
实施例3:
将硝化剂调整为浓硝酸+浓硫酸体系,形成对照组;
液相硝化离子液体催化剂及气相硝化催化剂与苯的摩尔比值为0.05:1、0.1:1、0.15:1、0.2:1、0.25:1,设置为实验组,硝化反应5小时,测试形成的苯硝基化合物的转化率,如表1:
表1
由表1可知,由于对照组中浓硝酸的硝化能力受硝酰正离子浓度影响大,较高浓度的硝酸电离出硝酰正离子少,特别是纯硝酸中仅约3.5%以离子形态存在,绝大部分是分子态,在催化剂等量条件下,苯硝基化合物的转化率保持在较低水平;
实验组采用NO2F气体氟化苯分子,硝酰氟以离子的形态存在,极大提高了硝酰根离子浓度,极大的提高了硝化能力,同时硝酰氟与催化剂中的HBF4或者水解电离产生的BF4 -1离子反应,生成强硝化能力的NO2 +BF4 -1,进一步提高了苯硝基化合物的转化率;随着催化剂摩尔比提高,催化剂提供更多的HBF4或者水解电离产生的BF4 -11离子参与反应,苯硝基化合物的转化率也随之提高;
同时,液相硝化采用了超声波微波硝化,超声波在溶液中会产生空化现象,液体中的微小气泡核在超声波作用下被激化,泡核的会震荡、生长、收缩及崩溃,在空化泡崩溃的极短时间内空化泡及其周围极小空间范围内出现热点产生极大的能量在这些极端条件下进入空化核内的物质在高温和高压下发生超临界反应,液相硝化的速率得到极大提升,液相硝化苯硝基化合物的转化率仅略低于气相硝化苯硝基化合物的转化率。
通过上面具体实施方式,技术领域的技术人员可容易的实现本发明。但是应当理解,本发明并不限于上述的具体实施方式。在公开的实施方式的基础上,技术领域的技术人员可任意组合不同的技术特征,从而实现不同的技术方案。
Claims (10)
1.一种氟化工艺制备硝基化合物的方法,其特征在于:采用NO2F及所述NO2F与催化剂反应制得的NO2 +BF4 -作为硝化剂,与芳烃、氮杂环化合物、胺类、醇类或低碳烷烃硝化反应,在所述催化剂催化下生成所述芳烃、氮杂环化合物、胺类、醇类或低碳烷烃的硝基化合物;
所述催化剂为气相硝化催化剂或液相硝化离子液体催化剂;
具体步骤为:
S100:制备所述NO2F:
1)在常温下通入氟氮混合气对反应釜预处理,然后通入纯氟气对反应釜钝化处理;
2)在常温下以纯氟气和NO2的摩尔比为1:(5-8),通入纯氟气和NO2,制得粗硝酰氟;
3)所述粗硝酰氟经过冷阱去除HF杂质后送入NO2F精馏***;
4)将所述粗硝酰氟通过氟化钠分子筛后升温,进一步去除HF杂质;
5)将粗纯化后的所述粗硝酰氟通入精馏***中,制得所述NO2F;
S200:制备所述气相硝化催化剂:
高温焙烤杂多酸及SiO2,称取HBF4、杂多酸及SiO2,高能球磨,将制得产物与氟化钠或氟化钙共混,制得所述气相硝化催化剂;
S300:制备所述液相硝化离子液体催化剂:
将四氟硼酸盐超声波分散溶解在有机溶剂中,制得所述液相硝化离子液体催化剂;
S400:气相硝化制备所述硝基化合物:
取所述气相硝化催化剂和所述芳烃、氮杂环化合物、胺类、醇类或低碳烷烃;在连续管式固定床反应器放置所述气相硝化催化剂,加温预热,先通入所述NO2F气体,所述NO2F气体与所述气相硝化催化剂中的所述HBF4反应,生成NO2 +BF4 -;
通入氮气或氦气,再将已气化的所述芳烃、氮杂环化合物、胺类、醇类或低碳烷烃与所述NO2F气体通入连续管式固定床反应器,充分反应2-5小时,制得所述硝基化合物;
S500:液相硝化制备所述硝基化合物:
提供高压反应釜,取所述液相硝化离子液体催化剂和所述芳烃、氮杂环化合物、胺类、醇类或低碳烷烃;
将所述芳烃、氮杂环化合物、胺类、醇类或低碳烷烃放置或通入高压反应釜,通入所述NO2F气体,加压,所述NO2F气体与所述液相硝化离子液体催化剂水解电离产生的BF4 -离子反应,生成NO2 +BF4 -,然后超声波硝化反应2-5小时,碱液水洗,制得所述硝基化合物。
2.如权利要求1所述一种氟化工艺制备硝基化合物的方法,其特征在于:所述芳烃为苯、硝基苯、萘、氯苯、甲苯、苯酚、邻二甲苯、间二甲苯、对二甲苯中的至少一种;所述氮杂环化合物为含氮杂环的吡咯类、噻唑类、咪唑类化合物;所述胺类为氨气、三辛胺、二乙胺、三乙胺、二-正丙胺、三-2-(2-甲氧基(乙氧基)乙基胺)中的至少一种;所述醇类为脂肪醇;所述低碳烷烃的碳原子数为1-5的直链烷烃。
3.如权利要求1所述一种氟化工艺制备硝基化合物的方法,其特征在于:通过将所述杂多酸、所述HBF4与所述二氧化硅高能球磨,将所述杂多酸、所述HBF4负载在所述二氧化硅载体上,球磨时长为3-8小时,球料比10:1。
4.如权利要求3所述一种氟化工艺制备硝基化合物的方法,其特征在于:所述杂多酸为H3PW12O4、H4SiW12O40中的至少一种,与所述HBF4及所述二氧化硅高能球磨,制得粒径在150-550nm级别的H3PW12O40/HBF4/SiO2、H4SiW12O40/HBF4/SiO2中的至少一种。
5.如权利要求1所述一种氟化工艺制备硝基化合物的方法,其特征在于:所述气相硝化催化剂中所述HBF4的质量占比为25-45%。
6.如权利要求1所述一种氟化工艺制备硝基化合物的方法,其特征在于:所述液相硝化离子液体催化剂通过采用N-己内酰胺类四氟硼酸盐、N-甲基咪唑四氟硼酸盐中的至少一种所述四氟硼酸盐制得。
7.如权利要求1所述一种氟化工艺制备硝基化合物的方法,其特征在于:所述液相硝化离子液体催化剂中所述四氟硼酸盐的浓度为0.6-2.4mol/L。
8.如权利要求1所述一种氟化工艺制备硝基化合物的方法,其特征在于:所述液相硝化离子液体催化剂中所述有机溶剂为CCl 4、CH2Cl 2中的至少一种。
9.如权利要求1所述一种氟化工艺制备硝基化合物的方法,其特征在于:按摩尔比值(0.05-0.25):1称取所述气相硝化催化剂与所述芳烃、氮杂环化合物、胺类、醇类或低碳烷烃,制备所述硝基化合物。
10.如权利要求1所述一种氟化工艺制备硝基化合物的方法,其特征在于:按摩尔比值(0.05-0.25):1称取所述液相硝化离子液体催化剂与所述芳烃、氮杂环化合物、胺类、醇类或低碳烷烃,制备硝基化合物。
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