CN111939925B - Catalyst for preparing n-octylamine and application thereof - Google Patents
Catalyst for preparing n-octylamine and application thereof Download PDFInfo
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- CN111939925B CN111939925B CN202010710504.8A CN202010710504A CN111939925B CN 111939925 B CN111939925 B CN 111939925B CN 202010710504 A CN202010710504 A CN 202010710504A CN 111939925 B CN111939925 B CN 111939925B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 98
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 23
- 239000011651 chromium Substances 0.000 claims abstract description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 22
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000005086 pumping Methods 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 2
- 239000002002 slurry Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000012071 phase Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing n-octylamine and application thereof, wherein the catalyst comprises the following components in percentage by weight: 1 to 30 percent of copper, 1 to 30 percent of nickel, 0.01 to 0.5 percent of platinum, 0.01 to 0.5 percent of chromium, 0.01 to 0.5 percent of zinc and the balance of aluminum oxide. The preparation method of n-octylamine comprises the following steps: evenly mixing n-octanol and a catalyst, pumping into a microchannel reactor, simultaneously introducing liquid ammonia and hydrogen, wherein the molar ratio of the n-octanol to the liquid ammonia is 1:1 to 3, controlling the reaction temperature at 100 to 150 ℃, the reaction pressure at 0.5 to 5.0Mpa, the reaction time at 30 to 40min, and then distilling to obtain the product.
Description
Technical Field
The invention relates to the field of synthesis of fine organic compounds, in particular to a catalyst for preparing n-octylamine and application thereof in preparing n-octylamine.
Background
N-octylamine (octylamine), alias 1-octylamine, 1-aminooctane, primary n-octylamine, aminooctane, octylamine. The product is an organic chemical product mainly used as a medical intermediate, a softening agent, a bactericide, an extracting agent and the like, and is mainly used as a bactericide intermediate for producing octyl isothiazolinone at home at present.
In the prior art, the production methods of n-octylamine mainly comprise the following three methods:
the first method is to produce n-octylnitrile by using n-octanoic acid and liquid ammonia as main raw materials under the conditions of high temperature and catalyst, and then the n-octylnitrile is hydrogenated under the action of catalyst to obtain n-octylamine. The method has higher requirement on equipment due to stronger acid corrosion under the condition of high temperature, and has less industrial application at present.
And secondly, taking n-octanol and liquid ammonia as main raw materials, preparing n-octylnitrile under a high-temperature condition, and then hydrogenating to obtain n-octylamine. The method has the advantages of long synthesis steps, low efficiency, low yield and high production cost.
The third method is to use Cu-Ni/Al under the conditions of 190-250 ℃ and 0.1-16.0 Mpa of high temperature and high pressure 2 O 3 The catalyst is obtained by ammoniating n-octyl alcohol and liquid ammonia which are used as raw materials in a reaction kettle, such as 200610154969.X (with the publication number of CN 1962604A), and the following information is disclosed: the larger the ammonia-alcohol molar ratio (1:9-12), the higher the conversion rate of n-octyl alcohol, the higher the temperature (190-250 ℃), the more the catalyst (3.8% of the n-octyl alcohol), the faster the reaction speed, but all the byproducts are generated, and the higher the content of nickel in the catalyst, the higher the reaction speed, the more the byproducts are increased.
Compared with the second method, the second method comprises two steps, and the third method comprises the steps of preparing n-octylamine from n-octanol and liquid ammonia, wherein although the structure is simple, the involved reaction principle is complex, firstly, n-octanol is oxidized into n-octylaldehyde under the action of a catalyst, and then, after addition of the n-octylaldehyde and the liquid ammonia, dehydration and hydrogenation are carried out under the action of the catalyst to generate the n-octylamine, so that aldol condensation products, di-n-octylamine, tri-n-octylamine and other byproducts are easily generated in the process, and therefore, the selectivity and the yield of the n-octylamine can be improved by increasing the using amount of the liquid ammonia in order to control the byproducts.
201110038964.1 (publication No. CN 102070460A) provides a fixed bed reactor of a diatomite-supported nickel catalyst, wherein nickel is 30-70%, diatomite is 30-70%, the mol ratio of ammonia to alcohol is 13-16, the temperature is 150-160 ℃, the pressure is 15-30 atm, and hydrogen is introduced.
201310734128.6 (publication No. CN 103664633A) is continuously fed by a high-pressure liquid-phase constant flow pump, and the catalyst comprises the following components: 1 to 30 percent of Cu, 1 to 30 percent of Cr, 0.1 to 5 percent of Fe0.1, 0.1 to 5 percent of Sn0.1, 0.1 to 5 percent of Zno, and the balance of alumina. In the document, the mol ratio of ammonia to alcohol is 4-10, the pressure is 0.5-2 MPa, the temperature is 120-250 ℃, and the space velocity is 20-40/h.
Although the method is improved to realize continuous production, the conversion efficiency is still low, and the required liquid ammonia amount is still high.
Disclosure of Invention
The invention is an improvement on the prior art.
The first purpose of the invention is to provide a catalyst for preparing n-octylamine, which consists of the following components in percentage by weight: 1 to 30 percent of copper, 1 to 30 percent of nickel, 0.01 to 0.5 percent of platinum, 0.01 to 0.5 percent of chromium, 0.01 to 0.5 percent of zinc and the balance of aluminum oxide.
Preferably, the catalyst consists of the following components in percentage by weight: 1 to 2 percent of copper, 0.1 to 1 percent of nickel, 0.01 to 0.1 percent of platinum, 0.01 to 0.1 percent of chromium, 0.01 to 0.1 percent of zinc and the balance of aluminum oxide.
Further preferably, the catalyst consists of the following components in percentage by weight: 1.5 to 2 percent of copper, 0.1 to 0.4 percent of nickel, 0.02 to 0.05 percent of platinum, 0.01 to 0.03 percent of chromium, 0.02 to 0.03 percent of zinc and the balance of aluminum oxide.
Still more preferably, the catalyst consists of the following components in percentage by weight: 1.5 to 1.8 percent of copper, 0.2 to 0.4 percent of nickel, 0.02 to 0.05 percent of platinum, 0.01 to 0.02 percent of chromium, 0.02 to 0.03 percent of zinc and the balance of aluminum oxide.
Most preferably, the catalyst consists of the following components in percentage by weight: 1.5 to 1.8 percent of copper, 0.2 to 0.3 percent of nickel, 0.02 to 0.05 percent of platinum, 0.01 to 0.02 percent of chromium, 0.02 to 0.03 percent of zinc and the balance of aluminum oxide.
The second purpose of the invention is to provide the application of the catalyst in preparing n-octylamine.
The third purpose of the invention is to provide a preparation method of n-octylamine, which comprises the following steps: mixing n-octanol and a catalyst, pumping into a reactor, and simultaneously introducing liquid ammonia and hydrogen, wherein the molar ratio of the n-octanol to the liquid ammonia is 1:1 to 3, controlling the reaction temperature at 100 to 150 ℃, the reaction pressure at 0.5 to 5.0Mpa, the reaction time at 30 to 40min, and then distilling to obtain the product.
The method comprises the following steps:
the catalyst consists of the following components in percentage by weight: 1 to 30 percent of copper, 1 to 30 percent of nickel, 0.01 to 0.5 percent of platinum, 0.01 to 0.5 percent of chromium, 0.01 to 0.5 percent of zinc and the balance of aluminum oxide.
Preferably, the catalyst consists of the following components in percentage by weight: 1 to 2 percent of copper, 0.1 to 1 percent of nickel, 0.01 to 0.1 percent of platinum, 0.01 to 0.1 percent of chromium, 0.01 to 0.1 percent of zinc and the balance of aluminum oxide.
Further preferably, the catalyst consists of the following components in percentage by weight: 1.5 to 2 percent of copper, 0.1 to 0.4 percent of nickel, 0.02 to 0.05 percent of platinum, 0.01 to 0.03 percent of chromium, 0.02 to 0.03 percent of zinc and the balance of aluminum oxide.
Still more preferably, the catalyst consists of the following components in percentage by weight: 1.5 to 1.8 percent of copper, 0.2 to 0.4 percent of nickel, 0.02 to 0.05 percent of platinum, 0.01 to 0.02 percent of chromium, 0.02 to 0.03 percent of zinc and the balance of aluminum oxide.
Most preferably, the catalyst consists of the following components in percentage by weight: 1.5 to 1.8 percent of copper, 0.2 to 0.3 percent of nickel, 0.02 to 0.05 percent of platinum, 0.01 to 0.02 percent of chromium, 0.02 to 0.03 percent of zinc and the balance of aluminum oxide.
The dosage of the catalyst is 0.1 to 2 percent of the mass of the n-octanol, and preferably 0.5 to 1 percent.
The reactor is a micro-channel continuous flow reactor.
Before reaction, the micro-channel continuous flow reactor is replaced by nitrogen for three times in advance, air in the reactor is removed, and the temperature is preheated to 50-70 ℃.
The flow rate of the mixture of n-octanol and catalyst entering the reactor is controlled between 15 and 25g/min.
The flow rate of introducing the n-octanol and the catalyst into the reactor is 15-25g/min.
The flow rate of liquid ammonia is 3.9 to 6.5g/min, preferably 5.2 to 6.5g/min, and more preferably 5.8 to 6.5g/min.
The flow rate of the hydrogen is 8-12 ml/min.
The molar ratio of n-octanol to liquid ammonia is 1:1.5 to 3, preferably 1:2 to 3, and more preferably 2.5 to 3.
The pressure is controlled to be 0.5 to 2MPa, preferably 0.5 to 1.0MPa.
The method provided by the invention has the following advantages:
1. as for the catalyst, metal ions of the catalyst are loaded on alumina, which plays a key role in the reaction process of n-octanol and liquid ammonia, but in order to increase the conversion rate of n-octanol, excessive liquid ammonia is generally added for reaction, but the large excessive liquid ammonia can generate excessive pressure under the condition of high temperature and is also pollution to the environment, the selectivity of the catalyst is improved by changing the composition of the catalyst, and the using amount of the liquid ammonia is reduced.
The invention also adopts the components, but the mixture ratio is different, the alcohol ammonia ratio is in the scope of the invention, the reaction device is the same, but the result is different, and the reason is that the mixture ratio relationship in the catalyst influences the quality of the final product.
2. By using the micro-channel continuous flow reactor, the mass transfer level is greatly improved, the reaction is quicker, the product purity is higher, the reaction temperature can be better controlled, the reaction is safer and more environment-friendly, and the continuous production is more facilitated.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The content of n-octylamine is analyzed by gas chromatography, and the specific conditions are shown in table 1:
table 1: detection conditions of gas chromatography
| Using instruments | GC-2014C gas chromatograph or equivalent |
| Specification of chromatographic column | HP-5;50 m.times.0.32 mm.times.0.52 μm or equivalent columns |
| Temperature programmed condition | 100℃(1min)→10℃/min→280℃(4min) |
| Pressure of carrier gas (He) | 0.1MPa |
| Air (Air) pressure | 0.04Mpa |
| Hydrogen (H) 2 ) Pressure of | 0.04Mpa |
| Detector type | FID |
| Split ratio | 50:1 |
| Detecting temperature | 300℃ |
| Vaporization temperature | 280℃ |
| Sample volume | 0.2 μ l (direct sample) |
| Calculation method | Area normalization method |
Example 1: preparation method of n-octylamine
Replacing a microchannel continuous flow reactor with nitrogen for three times, preheating to 50 ℃, uniformly mixing 650g of n-octanol and 4g of catalyst (the dosage of the catalyst is 0.62 percent of the mass of the n-octanol) to prepare slurry, pumping the slurry into the microchannel continuous flow reactor through a diaphragm pump to control the flow rate to be 20g/min, heating to 120 ℃, simultaneously introducing liquid ammonia to set the flow rate to be 5.2g/min and hydrogen to set the flow rate to be 10ml/min, and mixing the slurry with the liquid ammonia: liquid ammonia =1:2 (molar ratio), controlling the pressure of a unit module in the microchannel to be 0.5Mpa, fully contacting and continuously reacting gas-liquid-solid three-phase materials in a microchannel reactor, controlling the temperature to be 120 ℃ for reaction, reacting for 35 minutes, flowing the gas-liquid-solid three-phase materials into a material receiving kettle through a filter after the reaction is finished, distilling and removing liquid ammonia after all the reaction is finished to obtain a product, and analyzing by gas chromatography, wherein the content of n-octylamine is 98.7%, n-octanol is 0.6%, and di-n-octylamine is 0.5%.
The catalyst comprises the following components in percentage by weight: 1.5% of copper, 0.3% of nickel, 0.02% of platinum, 0.02% of chromium, 0.02% of zinc and the balance of aluminum oxide.
Example 2: preparation method of n-octylamine
Replacing a microchannel continuous flow reactor with nitrogen for three times, preheating to 60 ℃, uniformly mixing 520g of n-octanol and 5.2g of catalyst (the dosage of the catalyst is 1 percent of the mass of the n-octanol) to prepare slurry, pumping the slurry into the microchannel continuous flow reactor through a diaphragm pump, controlling the flow rate to be 15g/min, heating to 130 ℃, simultaneously introducing liquid ammonia, setting the flow rate to be 5.8g/min, setting the flow rate of hydrogen to be 12ml/min, and mixing the slurry with the liquid ammonia: liquid ammonia =1:3 (molar ratio), controlling the pressure of a unit module in the microchannel to be 1.0Mpa, fully contacting and continuously reacting gas-liquid-solid three-phase materials in a microchannel reactor, controlling the temperature to be 130 ℃ for reaction, reacting for 30 minutes, flowing the gas-liquid-solid three-phase materials into a material receiving kettle through a filter after the reaction is finished, distilling and removing water and liquid ammonia to obtain a product after all the reaction is finished, and performing gas chromatography analysis, wherein the content of n-octylamine is 99.1%, n-octanol is 0.6%, and di-n-octylamine is 0.1%.
The catalyst comprises the following components in percentage by weight: 1.5% of copper, 0.2% of nickel, 0.03% of platinum, 0.01% of chromium, 0.02% of zinc and the balance of aluminum oxide.
Example 3: preparation method of n-octylamine
Replacing a microchannel continuous flow reactor with nitrogen for three times, preheating to 70 ℃, uniformly mixing 780g of n-octanol and 4.8g of catalyst (the dosage of the catalyst is 0.62 percent of the mass of the n-octanol) to prepare slurry, pumping the slurry into the microchannel continuous flow reactor through a diaphragm pump, controlling the flow rate to be 25g/min, heating to 140 ℃, simultaneously introducing liquid ammonia, setting the flow rate to be 8.2g/min, setting the flow rate of hydrogen to be 8ml/min, and mixing the slurry with the liquid ammonia: liquid ammonia =1:2.5 (molar ratio), controlling the pressure of a unit module in the microchannel to be 0.8Mpa, fully contacting and continuously reacting gas-liquid-solid three-phase materials in a microchannel reactor, controlling the temperature to react at 140 ℃, reacting for 40 minutes, flowing into a material receiving kettle through a filter after the reaction is finished, distilling to remove water and liquid ammonia after all the reactions are finished to obtain a product, and analyzing by gas chromatography, wherein the content of n-octylamine is 98.8%, n-octanol is 0.5%, and di-n-octylamine is 0.4%.
The catalyst consists of the following components in percentage by weight: 1.8% of copper, 0.2% of nickel, 0.05% of platinum, 0.02% of chromium, 0.03% of zinc and the balance of aluminum oxide.
Example 4: preparation method of n-octylamine
Replacing a microchannel continuous flow reactor with nitrogen for three times, preheating to 50 ℃, uniformly mixing 520g of n-octanol and 5.2g of catalyst (the dosage of the catalyst is 1 percent of the mass of the n-octanol) to prepare slurry, pumping the slurry into the microchannel continuous flow reactor through a diaphragm pump, controlling the flow rate to be 20g/min, heating to 140 ℃, simultaneously introducing liquid ammonia, setting the flow rate to be 3.9g/min, setting the flow rate of hydrogen to be 8ml/min, and mixing the slurry with the liquid ammonia: liquid ammonia =1:1.5 (molar ratio), controlling the pressure of a unit module in the microchannel to be 0.5Mpa, fully contacting and continuously reacting gas-liquid-solid three-phase materials in a microchannel reactor, controlling the temperature to be 140 ℃ for reaction, reacting for 30 minutes, flowing into a material receiving kettle through a filter after the reaction is finished, distilling to remove water and liquid ammonia after all the reactions are finished to obtain a product, and analyzing by gas chromatography, wherein the content of n-octylamine is 94.1%, the content of n-octanol is 2.8%, and the content of di-n-octylamine is 2.7%.
The catalyst comprises the following components in percentage by weight: 2% of copper, 0.2% of nickel, 0.05% of platinum, 0.02% of chromium, 0.03% of zinc and the balance of aluminum oxide.
Example 5: preparation method of n-octylamine
Replacing a microchannel continuous flow reactor with nitrogen for three times, preheating to 50 ℃, uniformly mixing 650g of n-octanol and 5.5g of catalyst (the dosage of the catalyst is 0.85 percent of the mass of the n-octanol) to prepare slurry, pumping the slurry into the microchannel continuous flow reactor through a diaphragm pump, controlling the flow rate to be 20g/min, heating to 150 ℃, simultaneously introducing liquid ammonia, setting the flow rate to be 5.2g/min, setting the flow rate of hydrogen to be 12ml/min, and mixing the slurry with n-octanol: liquid ammonia =1:2 (molar ratio), controlling the pressure of a unit module in the microchannel to be 0.7Mpa, fully contacting and continuously reacting gas-liquid-solid three-phase materials in a microchannel reactor, controlling the temperature to be 150 ℃ for reaction, reacting for 30 minutes, flowing the gas-liquid-solid three-phase materials into a material receiving kettle through a filter after the reaction is finished, distilling and removing water and liquid ammonia to obtain a product after all the reaction is finished, and analyzing by gas chromatography, wherein the content of n-octylamine is 96.1%, n-octanol is 2.2%, and di-n-octylamine is 1.5%.
The catalyst comprises the following components in percentage by weight: 1.8% of copper, 0.4% of nickel, 0.02% of platinum, 0.03% of chromium, 0.02% of zinc and the balance of aluminum oxide.
Comparative example 1: existing catalyst 1
With reference to example 5 (highest conversion, 98.02% of which the molar ratio of ammonia to alcohol is 9:1) of 200610154969.X (publication No. CN 1962604A), the catalysts used in this scheme were Cu (copper) 3.5%, ni (nickel) 1.5%, ru (ruthenium) 0.05%, mg (magnesium) 0.5%, cr (chromium) 1.0%, and the remainder was Al 2 O 3 To prepare the powder catalyst. The amount of catalyst used was (5 ÷ 131= 3.82%).
Replacing a microchannel continuous flow reactor with nitrogen for three times, preheating to 60 ℃, uniformly mixing 600g of n-octanol and 22.8g of the catalyst (the dosage of the catalyst is 3.82% of the mass of the n-octanol) to prepare slurry, pumping the slurry into the microchannel continuous flow reactor through a diaphragm pump, controlling the flow rate to be 20g/min, heating to 140 ℃, simultaneously introducing liquid ammonia, setting the flow rate to be 6.5g/min, setting the flow rate of hydrogen to be 8ml/min, and mixing the slurry with the liquid ammonia: liquid ammonia =1:2.5 (molar ratio), controlling the pressure of a unit module in a microchannel to be 0.8Mpa, fully contacting and continuously reacting gas-liquid-solid three-phase materials in a microchannel reactor, controlling the temperature to be 140 ℃ for reaction, reacting for 30 minutes, flowing into a material receiving kettle through a filter after the reaction is finished, distilling to remove water and liquid ammonia after all the reactions are finished to obtain a product, and analyzing by gas chromatography, wherein the content of n-octylamine is 85.1%, n-octanol is 1.2%, di-n-octylamine is 9.1%, and tri-n-octylamine is 3.5%.
The explanation shows that the catalyst of the invention adopts the catalyst and the dosage of the prior literature, but at lower ammonia-alcohol ratio, even if the reaction is carried out by using a microchannel reactor, the content of the n-octylamine is still not high.
Comparative example 2: existing catalyst 2
Referring to example 1 of 200610012310.0 (publication No. CN100357024 a), the catalyst used in this scheme was copper oxide 30%, chromium oxide 40%, nickel oxide 20%, and the balance diatomaceous earth, and was made into a powder catalyst.
Replacing a microchannel continuous flow reactor with nitrogen for three times, preheating to 60 ℃, uniformly mixing 520g of n-octanol and 8.0g of the catalyst (the dosage of the catalyst is 1.54 percent of the mass of the n-octanol) to prepare slurry, pumping the slurry into the microchannel continuous flow reactor through a diaphragm pump, controlling the flow rate to be 25g/min, heating to 130 ℃, simultaneously introducing liquid ammonia, setting the flow rate to be 6.5g/min, setting the flow rate of hydrogen to be 10ml/min, and mixing the slurry with the liquid ammonia: liquid ammonia =1:2 (molar ratio), controlling the pressure of a unit module in the microchannel to be 0.9Mpa, enabling gas-liquid-solid three-phase materials to fully contact and continuously react in a microchannel reactor, controlling the temperature to react at 130 ℃, enabling the reaction time to be 30 minutes, enabling the gas-liquid-solid three-phase materials to flow into a material receiving kettle through a filter after the reaction is finished, distilling and removing water and liquid ammonia to obtain a product after all the reactions are finished, and analyzing by gas chromatography, wherein the content of n-octylamine is 45.1%, the content of n-octanol is 1.1%, the content of di-n-octylamine is 28.5%, and the content of tri-n-octylamine is 24.0%.
It is explained that the catalyst of the invention is prepared by using the catalyst and the amount of the catalyst in the prior literature, the preparation method is referred to the method of the invention, and the molar ratio of alcohol to ammonia and the reaction device are also the same as the invention.
Comparative example 3: existing catalyst 3
In combination with the prior art 200610154969.X (publication number CN 1962604A), ruthenium and magnesium are replaced by zinc and platinum, the dosage is the same as the highest dosage of the corresponding elements of the invention, and 3.5% of copper, 1.5% of nickel, 1% of chromium, 0.03% of zinc, 0.05% of platinum and the balance of alumina are adopted to prepare the powder catalyst.
Replacing a microchannel continuous flow reactor with nitrogen for three times, preheating to 60 ℃, uniformly mixing 650g of n-octanol and 5g of catalyst (the amount of the catalyst is 0.77 percent of the mass of the n-octanol) to prepare slurry, pumping the slurry into the microchannel continuous flow reactor through a diaphragm pump to control the flow rate to be 20g/min, heating to 120 ℃, simultaneously introducing liquid ammonia to set the flow rate to be 5.2g/min and hydrogen to set the flow rate to be 10ml/min, and mixing the slurry with the liquid ammonia: liquid ammonia =1:2 (molar ratio), controlling the pressure of a unit module in the microchannel to be 0.5Mpa, enabling gas-liquid-solid three-phase materials to fully contact and continuously react in a microchannel reactor, controlling the temperature to be 120 ℃ for reaction, enabling the reaction time to be 35 minutes, enabling the gas-liquid-solid three-phase materials to flow into a material receiving kettle through a filter after the reaction is finished, distilling and removing liquid ammonia after all the reactions are finished to obtain a product, and analyzing by gas chromatography, wherein the content of n-octylamine is 90.7%, the content of n-octanol is 0.3%, the content of di-n-octylamine is 7.5%, and the content of tri-n-octylamine is 1.2%.
Experimental example 1: examples 1 to 5 and comparative examples 1 to 3 were combined
A summary of examples 1-5 and comparative examples 1-3 is shown in Table 2
Table 2: compatibility of catalysts of examples 1 to 5 and comparative examples 1 to 3
Table 2 the results show: different catalysts are adopted, the same relation between the reaction device and the alcohol ammonia ratio is fixed, the content of the n-octylamine is different, and other byproducts are different, such as:
the main reason why the effect is not as good as that of examples 1-5 is found by increasing the content of copper and nickel in comparative example 3 is that the rate of formation of n-octanal, which is an intermediate, is increased due to the increased content of copper and nickel, so that n-octanal is locally excessive relative to liquid ammonia, and more di-n-octanal and tri-n-octanal are generated.
In a word, the catalyst provided by the invention can reduce the proportion of ammonia alcohol, and has high product purity and few byproducts.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (10)
1. The preparation method of n-octylamine is characterized in that raw materials comprise n-octanol and liquid ammonia, and a catalyst used in the method comprises the following components in percentage by weight: copper 1~2%, nickel 0.1-1%, platinum 0.01-0.1%, chromium 0.01-0.1%, zinc 0.01-0.1%, and the balance of aluminum oxide.
2. The preparation method according to claim 1, wherein the catalyst consists of the following components in percentage by weight: 1.5 to 2 percent of copper, 0.1 to 0.4 percent of nickel, 0.02 to 0.05 percent of platinum, 0.01 to 0.03 percent of chromium, 0.02 to 0.03 percent of zinc and the balance of aluminum oxide.
3. The preparation method according to claim 1, wherein the catalyst consists of the following components in percentage by weight: 1.5 to 1.8 percent of copper, 0.2 to 0.4 percent of nickel, 0.02 to 0.05 percent of platinum, 0.01 to 0.02 percent of chromium, 0.02 to 0.03 percent of zinc and the balance of aluminum oxide.
4. The preparation method according to claim 1, wherein the catalyst consists of the following components in percentage by weight: 1.5 to 1.8 percent of copper, 0.2 to 0.3 percent of nickel, 0.02 to 0.05 percent of platinum, 0.01 to 0.02 percent of chromium, 0.02 to 0.03 percent of zinc and the balance of aluminum oxide.
5. The production process according to any one of claims 1 to 4, wherein the molar ratio of n-octanol to liquid ammonia is 1:1~3, the dosage of the catalyst is 0.1 to 2 percent of the mass of n-octanol.
6. The method of claim 5, comprising the steps of:
mixing n-octanol and a catalyst, pumping into a reactor, and simultaneously introducing liquid ammonia and hydrogen, wherein the molar ratio of the n-octanol to the liquid ammonia is 1:1.5 to 3, controlling the reaction temperature to be 100 to 150 ℃, the reaction pressure to be 0.5 to 5.0MPa, the reaction time to be 30 to 40min, and then distilling to obtain the catalyst.
7. The production method according to claim 6, wherein the reactor is a microchannel continuous flow reactor.
8. The method according to claim 6, wherein the molar ratio of n-octanol to liquid ammonia is 1:2~3.
9. The method according to claim 8, wherein the molar ratio of n-octanol to liquid ammonia is 1:2.5 to 3.
10. The process according to claim 7, wherein the catalyst is used in an amount of 0.5 to 1% by mass based on n-octanol.
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