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CN117551056B - Method for preparing bio-based amine compound by converting marine biomass - Google Patents

Method for preparing bio-based amine compound by converting marine biomass Download PDF

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CN117551056B
CN117551056B CN202311525872.5A CN202311525872A CN117551056B CN 117551056 B CN117551056 B CN 117551056B CN 202311525872 A CN202311525872 A CN 202311525872A CN 117551056 B CN117551056 B CN 117551056B
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melamine
hno
rucl
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ruo
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CN117551056A (en
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谢绍朐
黄灏
郭栩聪
刘胜耀
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Jieyang Branch Center Of Guangdong Provincial Laboratory Of Chemistry And Fine Chemicals
Guangdong University of Technology
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Jieyang Branch Center Of Guangdong Provincial Laboratory Of Chemistry And Fine Chemicals
Guangdong University of Technology
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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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/12—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with only hydrogen atoms attached to the ring nitrogen atom
    • 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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Abstract

The invention relates to a method for preparing bio-based amine compounds by converting marine biomass; the method removes oxygen elements of chitin through a supported ruthenium catalyst and a phosphoric acid catalyst promoter, and simultaneously retains amino in the chitin to convert the chitin into biogenic amine; through optimization of the catalyst, amino groups are retained by the cocatalyst, so that the conversion rate of chitin is improved and the selective production of amine is realized. The method can realize high-value utilization of the crustacean marine product waste and reduce the use of high-energy consumption synthetic ammonia.

Description

Method for preparing bio-based amine compound by converting marine biomass
Technical Field
The invention belongs to the technical field of chemical engineering, relates to a catalytic conversion technology of biomass, and in particular relates to a method for preparing a bio-based amine compound by catalytic conversion of marine biomass chitin.
Background
Chitin is the raw material for pharmaceutical, cosmetic, textile, water treatment, household cleaners, soaps and carbon dioxide sequestering nitrogen-rich chemicals. Compared with cellulose, chitin is mainly distinguished by having biologically immobilized nitrogen in its side chains. Thus, N-containing chemicals are directly available from chitin, and industry typically begins with high energy-consuming ammonia synthesis to produce these chemicals.
Chitin is a suitable starting material for the preparation of nitrogen-containing chemicals. Although the use of chitin as a starting material for renewable organic nitrogen-containing compounds has been proposed since 2015, high yields of amine-based compounds have not been achieved yet. The key challenge is that the amide groups are easily detached from the backbone. However, selective deoxygenation of chitin or its monomeric NAG is of interest for the synthesis of commodity chemicals such as amines. To our knowledge, there is very limited research on the selective deoxygenation of chitin or NAG to amine. For example, NAG is partially deoxygenated by pyrolysis to produce chemicals such as 3-acetamido furan, 3-acetamido-5-acetylfuran (3A 5 AF), acetamido acetaldehyde, pyrazines, pyridines, etc., but with relatively low yields (J.Anal. Appl. Pyrolysis 1984,7,91-100;J.Agric.Food Chem.1998,46,3207-3209). On the other hand, the gold nanoparticles dispersed on the alkaline carrier can partially oxidize NAG in water to generate N-acetylglucosamine acid, and the yield is up to 95% (ChemSusChem 2013,6,2259-2262). In recent years, the pharmaceutical industry has developed new processes for converting NAG into platform chemical building block units, such as 3-acetamido-5-acetylfuran (3A 5 AF) for the synthesis of anticancer drug alkaloids ProximicinA (ChemSusChem 2018,11,532-535;ChemSusChem 2012,5,1767-1772). Under the condition of microwaves (220 ℃ C., 15 min), the yield of 3A5AF is improved from 2% (J.Anal. Appl. Pyrolysis 1984,7,91-100) to 58% (ChemSusChem 2012,5,1767-1772) by taking dimethylacetamide as a solvent. If the reaction occurs in an imidazole ionic liquid, the yield of 3A5AF can reach 60% (RSCAdv.2012, 2, 4642-4644). However, the market for special chemicals like 3A5AF is small and only very limited chitin raw materials are consumed.
In recent years, low yields of pyrrole were found during the conversion of chitin to acetic acid, with yields of only 12mol% (ACS sustein. Chem. Eng.2016,4, 3912-3920). The amide/amino substituted sugar alcohols, C2-C4 polyols and N-acetylmonoethanolamine (NMEA) produced by the hydrogenation of NAG over noble metal catalysts are less selective due to lack of protection of the NAG amino group (Green chem.2015,17, 1024-1031). As a result, deamination predominates, leading to the production of polyols. Therefore, in the conversion of chitin to amine over noble metal catalysts, effective catalytic strategies must be adopted to protect the amino groups.
Disclosure of Invention
The present invention provides a method for obtaining nitrogen-containing chemicals directly from chitin, aiming at the fact that the chitin side chain contains biologically immobilized nitrogen and that the industry generally begins with high energy-consuming ammonia synthesis to produce nitrogen-containing chemicals.
The present invention provides a novel method for directly obtaining nitrogen-containing chemicals from chitin, aiming at the fact that the chitin side chain contains biologically immobilized nitrogen, which avoids the problem of producing nitrogen-containing chemicals from high-energy ammonia synthesis in industry, and simultaneously retains the hydrocarbon component of the chitin skeleton.
In order to achieve the above purpose, the present invention adopts the following two technical schemes:
a method for preparing bio-based amine compounds by converting marine biomass through a two-step method comprises the following steps:
1) Mixing 5% -68% nitric acid aqueous solution with active carbon which is equivalent to 0.05-0.5 times of the amount of the nitric acid aqueous solution, namely Ac, and stirring for 0.5-48h at the temperature of 20-100 ℃ at the speed of 10-1000 pm to obtain Ac-HNO 3; mixing Ac-HNO 3 and melamine, namely melamine according to the mass ratio of 1:10-10:1, grinding, placing in a tube furnace, heating from 30 ℃ to 600 ℃ at the flow rate of nitrogen of 0.1-200 mL/min, maintaining for 120-480 minutes, and cooling to obtain a catalyst carrier Ac-HNO 3 -melamine; mixing Ac and melamine (melamine) according to a ratio of 10:1-1:10, grinding, placing in a tube furnace, heating from 30 ℃ to 400-800 ℃ at a nitrogen flow rate of 0.1-200 mL/min, maintaining for 120-480 minutes, and cooling to obtain a catalyst carrier Ac-melamine; dissolving RuCl 3 in acetone, respectively mixing with catalyst carriers Ac, ac-HNO 3、Ac-melamine、Ac-HNO3 -melamine, stirring until the liquid is dried, drying to obtain RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine; respectively, and hydrolyzing RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine by sodium hydroxide to obtain RuOx/Ac、RuOx/Ac-HNO3、RuOx/Ac-melamine、RuOx/Ac-HNO3-melamine, respectively or reducing RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine by sodium borohydride which is 1-10 times of Ru mass to obtain Ru/Ac, ru/Ac-HNO 3、Ru/Ac-melamine、Ru/Ac-HNO3 -melamine respectively;
2) 45-95% of water, 1-60% of phosphoric acid (H 3PO4) and 0.5-30% of chitin are placed in a reaction kettle to react for 1-12 hours under the nitrogen condition of 0.1-10 MPa at 80-150 ℃;
3) After the reaction liquid is cooled, adding 0.1-30% of one or more of the catalysts, putting the mixture into a reaction kettle again, and reacting for 1-12 hours under the hydrogen condition of 1.0-3.0 MPa at the temperature of 200-250 ℃ to obtain phosphorylated organic amine, wherein the yield of the organic amine is 1-99%.
2, A method for preparing bio-based amine compounds by converting marine biomass through a one-step method, which comprises the following steps:
1) Mixing 5% -68% nitric acid aqueous solution with active carbon which is equivalent to 0.05-0.5 times of the amount of the nitric acid aqueous solution, namely Ac, and stirring for 0.5-48h at the temperature of 20-100 ℃ at the speed of 10-1000 pm to obtain Ac-HNO 3; mixing Ac-HNO 3 and melamine (melamine) according to a mass ratio of 1:10-10:1, grinding, placing in a tube furnace, heating from 25 ℃ to 600 ℃ at a nitrogen flow rate of 0.1-200 mL/min, maintaining for 120-480 minutes, and cooling to obtain a catalyst carrier Ac-HNO 3 -melamine; mixing Ac and melamine (melamine) according to a ratio of 10:1-1:10, grinding, placing in a tube furnace, heating from 25 ℃ to 400-800 ℃ at a nitrogen flow rate of 0.1-200 mL/min, maintaining for 120-480 minutes, and cooling to obtain a catalyst carrier Ac-melamine; dissolving RuCl 3 in acetone, respectively mixing with catalyst carriers Ac, ac-HNO 3、Ac-melamine、Ac-HNO3 -melamine, stirring until the liquid is dried, drying to obtain RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine; respectively, and hydrolyzing RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine by sodium hydroxide to obtain RuOx/Ac、RuOx/Ac-HNO3、RuOx/Ac-melamine、RuOx/Ac-HNO3-melamine, respectively or reducing RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine by sodium borohydride which is 1-10 times of Ru mass to obtain Ru/Ac, ru/Ac-HNO 3、Ru/Ac-melamine、Ru/Ac-HNO3 -melamine respectively;
2) 45 to 95 percent of water, 1 to 60 percent of phosphoric acid (H 3PO4), 0.5 to 30 percent of chitin and 0.1 to 30 percent of one or more of the catalysts are placed in a reaction kettle to react for 1 to 12 hours under the hydrogen condition of 1.0 to 3.0MPa at the temperature of 200 to 250 ℃ to obtain the phosphorylated organic amine, and the yield of the organic amine is 1 to 99 percent.
Preferably, the mass fraction of the chitin in the reaction system is 1.5% -20%, the mass fraction of the phosphoric acid is 1% -20%, and the mass fraction of the catalyst is 0.1% -5%.
The catalyst may be one or more of RuOx/Ac、RuOx/Ac-HNO3、RuOx/Ac-melamine、RuOx/Ac-HNO3-melamine、Ru/Ac、Ru/Ac-HNO3、Ru/Ac-melamine、Ru/Ac-HNO3-melamine.
The catalyst can be reused after filtration, the organic amine can be neutralized by conventional alkali to be in a free state, and the mixture of the organic amine can be obtained by simple distillation.
Due to the adoption of the technical scheme, the invention has the following advantages:
(1) Aiming at the problem of high energy consumption of synthesizing organic amine by ammonia in industry, green production of organic amine by utilizing nitrogen element fixed by chitin in ocean is proposed. We have developed a novel catalytic process for converting NAG to biogenic amines by hydrolyzing chitin to monomeric NAG with an acidic promoter, selectively removing the oxygen-containing groups of NAG over a supported noble metal catalyst while retaining the amino groups in NAG.
(2) Through the optimization of the catalytic reaction system, amino groups are reserved through a cocatalyst, so that the conversion rate of chitin is improved, and the selective production of amine is realized. By developing a plurality of reaction paths for generating different amines by chitin, the high-value utilization of chitin is realized. These findings allow for high value utilization of crustacean seafood waste, opening up the nitrogen cycle on earth.
Drawings
Fig. 1: eight different catalysts catalyze the amine yield of chitin (two-step process).
Fig. 2: eight different catalysts catalyze the amine yield of chitin (one-step process).
Detailed Description
The present invention will be described in detail by way of examples.
Example 1
The preparation of 2.5wt% RuO x/Ac catalyst requires three steps:
In the first step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
In the second step, 0.78g of catalyst carrier Ac and ruthenium trichloride (RuCl 3) acetone solution are taken and mixed, stirring is continued in a fume hood until the liquid is stirred to dryness, and then 2.5wt% of RuCl 3/Ac is obtained after drying.
In a third step, 2.5wt% RuO x/Ac was obtained by hydrolyzing 2.5wt% RuCl 3/Ac with sodium hydroxide (NaOH). First 0.325g 2.5wt%RuCl 3/Ac was added to 40mL of water and stirred. Then 0.014g NaOH was mixed with 20mL water. The aqueous sodium hydroxide solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac suspension over 10 min. The obtained liquid was suction filtered, and the obtained solid was dried to obtain 2.5wt% ruo x/Ac catalyst.
Reaction part we used a two-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added and placed in a reaction vessel and reacted at 100℃under 0.5MPa of nitrogen for 2 hours.
After waiting for cooling, 0.1g of 2.5wt% RuO x/Ac catalyst is added, and the mixture is put into a reaction kettle again to react for 2 hours under the hydrogen condition of 3.0MPa at the temperature of 250 ℃ to obtain the organic amine.
Example 2
Four steps are required to prepare 2.5wt% ruox/Ac-HNO 3 catalyst:
In the first step, ac-HNO 3 is first prepared. 33.38mL of concentrated nitric acid was first mixed with 66mL of water to give an 8mol/L nitric acid solution. Then, 100mL of 8mol/L nitric acid solution was mixed with 10g of 400 mesh activated carbon, and stirred at 300rpm at 80℃for 8 hours. And (3) carrying out suction filtration on the liquid after stirring, and drying to obtain the Ac-HNO 3.
In the second step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And thirdly, mixing 0.78g of catalyst carrier Ac-HNO 3 with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac-HNO3.
Fourth, 2.5wt% RuCl 3/Ac-HNO3 was hydrolyzed by sodium hydroxide (NaOH) to give 2.5wt% RuO x/Ac-HNO3. First 0.325g 2.5wt%RuCl 3/Ac-HNO3 was added to 40mL of water and stirred. Then 0.014g NaOH was mixed with 20mL water. The aqueous sodium hydroxide solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-HNO3 -melamine suspension over 10 min. The obtained liquid was suction-filtered, and the obtained solid was dried to obtain 2.5wt% ruo x/Ac-HNO3 catalyst.
Reaction part we used a two-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added and placed in a reaction vessel and reacted at 100℃under 0.5MPa of nitrogen for 2 hours.
After cooling, 0.1g of 2.5wt% RuO x/Ac-HNO3 -melamine catalyst is added, and the mixture is put into a reaction kettle again to react for 2 hours under the hydrogen condition of 3.0MPa at the temperature of 250 ℃ to obtain the organic amine.
Example 3
Four steps are required to prepare 2.5wt% RuO x/Ac-melamine catalyst:
firstly, 1.5g of Ac and 1.5g of melamine (melamine) are mixed and ground and then put into a porcelain boat, the porcelain boat with the mixture is put into a tube furnace, nitrogen is firstly introduced for 10 minutes, then the temperature is increased from 25 ℃ to 600 ℃ for 190 minutes, and then the temperature is kept at 600 ℃ for 120 minutes. The catalyst carrier Ac-melamine can be obtained after cooling.
In the second step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And thirdly, mixing 0.78g of catalyst carrier Ac-melamine with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac-melamine.
In the fourth step, 2.5wt% RuCl 3/Ac-melamine was hydrolyzed by sodium hydroxide (NaOH) to give 2.5wt% RuO x/Ac-melamine. First 0.325g 2.5wt%RuCl 3/Ac-melamine was added to 40mL of water and stirred. Then 0.014g NaOH was mixed with 20mL water. The aqueous sodium hydroxide solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-melamine suspension over 10 min. The resulting liquid was suction filtered and the resulting solid was dried to give 2.5wt% ruo x/Ac-melamine catalyst.
Reaction part we used a two-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added and placed in a reaction vessel and reacted at 100℃under 0.5MPa of nitrogen for 2 hours.
After waiting for cooling, 0.1g of 2.5wt% RuO x/Ac-melamine catalyst is added, and the mixture is put into a reaction kettle again to react for 2 hours under the condition of hydrogen at 250 ℃ and 3.0MPa to obtain the organic amine.
Example 4
Five steps are required to prepare 2.5wt% ruo x/Ac-HNO3 -melamine catalyst:
In the first step, ac-HNO 3 is first prepared. 33.38mL of concentrated nitric acid was first mixed with 66mL of water to give an 8mol/L nitric acid solution. Then, 100mL of 8mol/L nitric acid solution was mixed with 10g of 400 mesh activated carbon, and stirred at 300rpm at 80℃for 8 hours. And (3) carrying out suction filtration on the liquid after stirring, and drying to obtain the Ac-HNO 3.
Secondly, 1.5g of Ac-HNO 3 and 1.5g of melamine (melamine) are mixed and ground and then put into a porcelain boat, the porcelain boat with the mixture is put into a tube furnace, nitrogen is firstly introduced for 10 minutes, then the temperature is increased from 25 ℃ to 600 ℃ for 190 minutes, and then the temperature is continuously maintained at 600 ℃ for 120 minutes. The catalyst carrier Ac-HNO 3 -melamine can be obtained after cooling.
Third, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
Fourth, 0.78g of catalyst carrier Ac-HNO 3 -melamine is taken and mixed with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, stirring is continued in a fume hood until the liquid is stirred to dryness, and then 2.5wt% RuCl 3/Ac-HNO3 -melamine is obtained after drying.
Fifth, 2.5wt% RuCl 3/Ac-HNO3 -melamine was hydrolyzed by sodium hydroxide (NaOH) to give 2.5wt% RuO x/Ac-HNO3 -melamine. First 0.325g 2.5wt%RuCl 3/Ac-HNO3 -melamine was added to 40mL of water and stirred. Then 0.014g NaOH was mixed with 20mL water. The aqueous sodium hydroxide solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-HNO3 -melamine suspension over 10min. The obtained liquid was suction-filtered, and the obtained solid was dried to obtain 2.5wt% ruo x/Ac-HNO3 -melamine catalyst.
Reaction part we used a two-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added and placed in a reaction vessel and reacted at 100℃under 0.5MPa of nitrogen for 2 hours.
After cooling, 0.1g of 2.5wt% RuO x/Ac-HNO3 -melamine catalyst is added, and the mixture is put into a reaction kettle again to react for 2 hours under the hydrogen condition of 3.0MPa at the temperature of 250 ℃ to obtain the organic amine.
Example 5
The preparation of 2.5wt% Ru/Ac catalyst requires three steps:
In the first step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
In the second step, 0.78g of catalyst carrier Ac and ruthenium trichloride (RuCl 3) acetone solution are taken and mixed, stirring is continued in a fume hood until the liquid is stirred to dryness, and then 2.5wt% of RuCl 3/Ac is obtained after drying.
In a third step, 2.5wt% RuCl 3/Ac was reduced by sodium borohydride to give 2.5wt% Ru/Ac. First 0.325g 2.5wt%RuCl 3/Ac was added to 40mL of water and stirred. Then 0.014g of sodium borohydride was mixed with 20mL of water. An aqueous sodium borohydride solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac suspension over 10 min. And carrying out suction filtration on the obtained liquid, and drying the obtained solid to obtain the Ru/Ac catalyst with the concentration of 2.5wt%.
Reaction part we used a two-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added and placed in a reaction vessel and reacted at 100℃under 0.5MPa of nitrogen for 2 hours.
After cooling, 0.1g of 2.5wt% Ru/Ac catalyst is added, and the mixture is put into a reaction kettle again to react for 2 hours under the hydrogen condition of 3.0MPa at the temperature of 250 ℃ to obtain the organic amine.
Example 6
Four steps are required to prepare 2.5wt% Ru/Ac-HNO 3 catalyst:
In the first step, ac-HNO 3 is first prepared. 33.38mL of concentrated nitric acid was first mixed with 66mL of water to give an 8mol/L nitric acid solution. Then, 100mL of 8mol/L nitric acid solution was mixed with 10g of 400 mesh activated carbon, and stirred at 300rpm at 80℃for 8 hours. And (3) carrying out suction filtration on the liquid after stirring, and drying to obtain the Ac-HNO 3.
In the second step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And thirdly, mixing 0.78g of catalyst carrier Ac-HNO 3 with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac-HNO3.
Fourth, 2.5wt% RuCl 3/Ac-HNO3 was reduced by sodium borohydride to give 2.5wt% Ru/Ac-HNO 3. First 0.325g 2.5wt%RuCl 3/Ac-HNO3 was added to 40mL of water and stirred. Then 0.014g of sodium borohydride was mixed with 20mL of water. An aqueous solution of sodium borohydride was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-HNO3 -melamine suspension over 10 min. And carrying out suction filtration on the obtained liquid, and drying the obtained solid to obtain the Ru/Ac-HNO 3 catalyst with the weight percent of 2.5.
Reaction part we used a two-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added and placed in a reaction vessel and reacted at 100℃under 0.5MPa of nitrogen for 2 hours.
After cooling, 0.1g of 2.5wt% Ru/Ac-HNO 3 -melamine catalyst is added, and the mixture is put into a reaction kettle again to react for 2 hours under the condition of hydrogen at 250 ℃ and 3.0MPa to obtain the organic amine.
Example 7
The preparation of 2.5wt% Ru/Ac-melamine catalyst requires four steps:
firstly, 1.5g of Ac and 1.5g of melamine (melamine) are mixed and ground and then put into a porcelain boat, the porcelain boat with the mixture is put into a tube furnace, nitrogen is firstly introduced for 10 minutes, then the temperature is increased from 25 ℃ to 600 ℃ for 190 minutes, and then the temperature is kept at 600 ℃ for 120 minutes. The catalyst carrier Ac-melamine can be obtained after cooling.
In the second step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And thirdly, mixing 0.78g of catalyst carrier Ac-melamine with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac-melamine.
Fourth, 2.5wt% RuCl 3/Ac-melamine was reduced by sodium borohydride to give 2.5wt% Ru/Ac-melamine. First 0.325g 2.5wt%RuCl 3/Ac-melamine was added to 40mL of water and stirred. Then 0.014g of sodium borohydride was mixed with 20mL of water. An aqueous solution of sodium borohydride was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-melamine suspension over 10 min. The obtained liquid was suction filtered, and the obtained solid was dried to obtain 2.5wt% Ru/Ac-melamine catalyst.
Reaction part we used a two-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added and placed in a reaction vessel and reacted at 100℃under 0.5MPa of nitrogen for 2 hours.
After cooling, 0.1g of 2.5wt% Ru/Ac-melamine catalyst is added, and the mixture is put into a reaction kettle again to react for 2 hours under the hydrogen condition of 3.0MPa at the temperature of 250 ℃ to obtain the organic amine.
Example 8
Five steps are required to prepare 2.5wt% Ru/Ac-HNO 3 -melamine catalyst:
In the first step, ac-HNO 3 is first prepared. 33.38mL of concentrated nitric acid was first mixed with 66mL of water to give an 8mol/L nitric acid solution. Then, 100mL of 8mol/L nitric acid solution was mixed with 10g of 400 mesh activated carbon, and stirred at 300rpm at 80℃for 8 hours. And (3) carrying out suction filtration on the liquid after stirring, and drying to obtain the Ac-HNO 3.
Secondly, 1.5g of Ac-HNO 3 and 1.5g of melamine (melamine) are mixed and ground and then put into a porcelain boat, the porcelain boat with the mixture is put into a tube furnace, nitrogen is firstly introduced for 10 minutes, then the temperature is increased from 25 ℃ to 600 ℃ for 190 minutes, and then the temperature is continuously maintained at 600 ℃ for 120 minutes. The catalyst carrier Ac-HNO 3 -melamine can be obtained after cooling.
Third, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
Fourth, 0.78g of catalyst carrier Ac-HNO 3 -melamine is taken and mixed with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, stirring is continued in a fume hood until the liquid is stirred to dryness, and then 2.5wt% RuCl 3/Ac-HNO3 -melamine is obtained after drying.
Fifth, 2.5wt% RuCl 3/Ac-HNO3 -melamine was reduced by sodium borohydride to give 2.5wt% Ru/Ac-HNO 3 -melamine. First 0.325g 2.5wt%RuCl 3/Ac-HNO3 -melamine was added to 40mL of water and stirred. Then 0.014g NaOH was mixed with 20mL water. The aqueous sodium hydroxide solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-HNO3 -melamine suspension over 10 min. The obtained liquid is filtered, and the obtained solid is dried to obtain 2.5wt% Ru/Ac-HNO 3 -melamine catalyst.
Reaction part we used a two-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added and placed in a reaction vessel and reacted at 100℃under 0.5MPa of nitrogen for 2 hours.
After cooling, 0.1g of 2.5wt% Ru/Ac-HNO 3 -melamine catalyst is added, and the mixture is put into a reaction kettle again to react for 2 hours under the condition of hydrogen at 250 ℃ and 3.0MPa to obtain the organic amine.
The types of organic amines obtained in examples 1-8 and the corresponding yields are shown in FIG. 1.
Example 9
The preparation of 2.5wt% RuO x/Ac catalyst requires three steps:
In the first step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And secondly, mixing 0.78g of catalyst carrier Ac-HNO 3 with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac.
In a third step, 2.5wt% RuO x/Ac was obtained by hydrolyzing 2.5wt% RuCl 3/Ac with sodium hydroxide (NaOH). First 0.325g 2.5wt%RuCl 3/Ac was added to 40mL of water and stirred. Then 0.014g NaOH was mixed with 20mL water. The aqueous sodium hydroxide solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac suspension over 10 min. The obtained liquid was suction filtered, and the obtained solid was dried to obtain 2.5wt% ruo x/Ac catalyst.
Reaction part we used a one-step process:
15mL of water is firstly mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin is added, then 0.1g of 2.5 wt% RuO x/Ac catalyst is added, and the mixture is reacted for 2 hours under the condition of hydrogen at 250 ℃ and 3.0MPa to obtain the organic amine.
Example 10
Four steps are required to prepare 2.5wt% ruox/Ac-HNO 3 catalyst:
In the first step, ac-HNO 3 is first prepared. 33.38mL of concentrated nitric acid was first mixed with 66mL of water to give an 8mol/L nitric acid solution. Then, 100mL of 8mol/L nitric acid solution was mixed with 10g of 400 mesh activated carbon, and stirred at 300rpm at 80℃for 8 hours. And (3) carrying out suction filtration on the liquid after stirring, and drying to obtain Ac-HNO3.
In the second step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And thirdly, mixing 0.78g of catalyst carrier Ac-HNO 3 with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac-HNO3.
Fourth, 2.5wt% RuCl 3/Ac-HNO3 was hydrolyzed by sodium hydroxide (NaOH) to give 2.5wt% RuO x/Ac-HNO3. First 0.325g 2.5wt%RuCl 3/Ac-HNO3 was added to 40mL of water and stirred. Then 0.014g NaOH was mixed with 20mL water. The aqueous sodium hydroxide solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-HNO3 -melamine suspension over 10 min. The obtained liquid was suction-filtered, and the obtained solid was dried to obtain 2.5wt% ruo x/Ac-HNO3 catalyst.
Reaction part we used a one-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added, and then 0.1g of 2.5% wt RuO x/Ac-HNO3 catalyst was added to react for 2 hours under hydrogen at 250℃and 3.0MPa to obtain an organic amine.
Example 11
Four steps are required to prepare 2.5wt% RuO x/Ac-melamine catalyst:
firstly, 1.5g of Ac and 1.5g of melamine (melamine) are mixed and ground and then put into a porcelain boat, the porcelain boat with the mixture is put into a tube furnace, nitrogen is firstly introduced for 10 minutes, then the temperature is increased from 25 ℃ to 600 ℃ for 190 minutes, and then the temperature is kept at 600 ℃ for 120 minutes. The catalyst carrier Ac-melamine can be obtained after cooling.
In the second step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And thirdly, mixing 0.78g of catalyst carrier Ac-melamine with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac-melamine.
In the fourth step, 2.5wt% RuCl 3/Ac-melamine was hydrolyzed by sodium hydroxide (NaOH) to give 2.5wt% RuO x/Ac-melamine. First 0.325g 2.5wt%RuCl 3/Ac-melamine was added to 40mL of water and stirred. Then 0.014g NaOH was mixed with 20mL water. The aqueous sodium hydroxide solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-melamine suspension over 10 min. The resulting liquid was suction filtered and the resulting solid was dried to give 2.5wt% ruo x/Ac-melamine catalyst.
Reaction part we used a one-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added, and then 0.1g of 2.5 wt% RuO x/Ac-melamine catalyst was added to react for 2 hours under hydrogen conditions of 3.0MPa at 250℃to obtain an organic amine.
Example 12
Five steps are required to prepare 2.5wt% ruo x/Ac-HNO3 -melamine catalyst:
In the first step, ac-HNO 3 is first prepared. 33.38mL of concentrated nitric acid was first mixed with 66mL of water to give an 8mol/L nitric acid solution. Then, 100mL of 8mol/L nitric acid solution was mixed with 10g of 400 mesh activated carbon, and stirred at 300rpm at 80℃for 8 hours. And (3) carrying out suction filtration on the liquid after stirring, and drying to obtain the Ac-HNO 3.
Secondly, 1.5g of Ac-HNO 3 and 1.5g of melamine (melamine) are mixed and ground and then put into a porcelain boat, the porcelain boat with the mixture is put into a tube furnace, nitrogen is firstly introduced for 10 minutes, then the temperature is increased from 25 ℃ to 600 ℃ for 190 minutes, and then the temperature is continuously maintained at 600 ℃ for 120 minutes. The catalyst carrier Ac-HNO 3 -melamine can be obtained after cooling.
Third, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
Fourth, 0.78g of catalyst carrier Ac-HNO 3 -melamine is taken and mixed with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, stirring is continued in a fume hood until the liquid is stirred to dryness, and then 2.5wt% RuCl 3/Ac-HNO3 -melamine is obtained after drying.
Fifth, 2.5wt% RuCl 3/Ac-HNO3 -melamine was hydrolyzed by sodium hydroxide (NaOH) to give 2.5wt% RuO x/Ac-HNO3 -melamine. First 0.325g 2.5wt%RuCl 3/Ac-HNO3 -melamine was added to 40mL of water and stirred. Then 0.014g NaOH was mixed with 20mL water. The aqueous sodium hydroxide solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-HNO3 -melamine suspension over 10min. The obtained liquid was suction-filtered, and the obtained solid was dried to obtain 2.5wt% ruo x/Ac-HNO3 -melamine catalyst.
Reaction part we used a one-step process:
15mL of water is firstly mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin is added, then 0.1g of 2.5 wt% RuO x/Ac-HNO3 -melamine catalyst is added, and the mixture is reacted for 2 hours under the condition of hydrogen at 250 ℃ and 3.0MPa to obtain the organic amine.
Example 13
The preparation of 2.5wt% Ru/Ac catalyst requires three steps:
In the first step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And secondly, mixing 0.78g of catalyst carrier Ac-HNO 3 with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac.
In a third step, 2.5wt% RuO x/Ac was obtained by reducing 2.5wt% RuCl 3/Ac with sodium borohydride. First 0.325g 2.5wt%RuCl 3/Ac was added to 40mL of water and stirred. Then 0.014g of sodium borohydride was mixed with 20mL of water. An aqueous sodium borohydride solution was then slowly added dropwise to the 2.5wt% RuCl 3/Ac suspension over 10 min. And carrying out suction filtration on the obtained liquid, and drying the obtained solid to obtain the Ru/Ac catalyst with the concentration of 2.5wt%.
Reaction part we used a one-step process:
15mL of water was first mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin was added, and then 0.1g of 2.5% wt Ru/Ac catalyst was added to react for 2 hours at 250℃under 3.0MPa of hydrogen to obtain an organic amine.
Example 14
Four steps are required to prepare 2.5wt% Ru/Ac-HNO 3 catalyst:
In the first step, ac-HNO 3 is first prepared. 33.38mL of concentrated nitric acid was first mixed with 66mL of water to give an 8mol/L nitric acid solution. Then, 100mL of 8mol/L nitric acid solution was mixed with 10g of 400 mesh activated carbon, and stirred at 300rpm at 80℃for 8 hours. And (3) carrying out suction filtration on the liquid after stirring, and drying to obtain Ac-HNO3.
In the second step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And thirdly, mixing 0.78g of catalyst carrier Ac-HNO 3 with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac-HNO3.
Fourth, 2.5wt% RuCl 3/Ac-HNO3 was reduced by sodium borohydride to give 2.5wt% RuO x/Ac-HNO3. First 0.325g 2.5wt%RuCl 3/Ac-HNO3 was added to 40mL of water and stirred. Then 0.014g of sodium borohydride was mixed with 20mL of water. An aqueous solution of sodium borohydride was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-HNO3 -melamine suspension over 10 min. And carrying out suction filtration on the obtained liquid, and drying the obtained solid to obtain the Ru/Ac-HNO 3 catalyst with the weight percent of 2.5.
Reaction part we used a one-step process:
15mL of water is firstly mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin is added, then 0.1g of 2.5wt% Ru/Ac-HNO 3 catalyst is added, and the mixture is reacted for 2 hours under the condition of hydrogen at 250 ℃ and 3.0MPa to obtain the organic amine.
Example 15
The preparation of 2.5wt% Ru/Ac-melamine catalyst requires four steps:
firstly, 1.5g of Ac and 1.5g of melamine (melamine) are mixed and ground and then put into a porcelain boat, the porcelain boat with the mixture is put into a tube furnace, nitrogen is firstly introduced for 10 minutes, then the temperature is increased from 25 ℃ to 600 ℃ for 190 minutes, and then the temperature is kept at 600 ℃ for 120 minutes. The catalyst carrier Ac-melamine can be obtained after cooling.
In the second step, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
And thirdly, mixing 0.78g of catalyst carrier Ac-melamine with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, continuously stirring in a fume hood until the liquid is stirred to dryness, and drying to obtain 2.5wt% RuCl 3/Ac-melamine.
Fourth, 2.5wt% RuCl 3/Ac-melamine was reduced by sodium borohydride to give 2.5wt% Ru/Ac-melamine. First 0.325g 2.5wt%RuCl 3/Ac-melamine was added to 40mL of water and stirred. Then 0.014g of sodium borohydride was mixed with 20mL of water. An aqueous solution of sodium borohydride was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-melamine suspension over 10 min. The obtained liquid was suction filtered, and the obtained solid was dried to obtain 2.5wt% Ru/Ac-melamine catalyst.
Reaction part we used a one-step process:
15mL of water is firstly mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin is added, then 0.1g of 2.5 wt% Ru/Ac-melamine catalyst is added, and the mixture is reacted for 2 hours under the condition of hydrogen at 250 ℃ and 3.0MPa to obtain the organic amine.
Example 16
Five steps are required to prepare 2.5wt% Ru/Ac-HNO 3 -melamine catalyst:
In the first step, ac-HNO 3 is first prepared. 33.38mL of concentrated nitric acid was first mixed with 66mL of water to give an 8mol/L nitric acid solution. Then, 100mL of 8mol/L nitric acid solution was mixed with 10g of 400 mesh activated carbon, and stirred at 300rpm at 80℃for 8 hours. And (3) carrying out suction filtration on the liquid after stirring, and drying to obtain the Ac-HNO 3.
Secondly, 1.5g of Ac-HNO 3 and 1.5g of melamine (melamine) are mixed and ground and then put into a porcelain boat, the porcelain boat with the mixture is put into a tube furnace, nitrogen is firstly introduced for 10 minutes, then the temperature is increased from 25 ℃ to 600 ℃ for 190 minutes, and then the temperature is continuously maintained at 600 ℃ for 120 minutes. The catalyst carrier Ac-HNO 3 -melamine can be obtained after cooling.
Third, a ruthenium trichloride (RuCl 3) acetone solution was prepared. 0.041g of RuCl 3 was mixed with 15mL of acetone and stirred at 300rpm for 6h.
Fourth, 0.78g of catalyst carrier Ac-HNO 3 -melamine is taken and mixed with the ruthenium trichloride (RuCl 3) acetone solution obtained in the third step, stirring is continued in a fume hood until the liquid is stirred to dryness, and then 2.5wt% RuCl 3/Ac-HNO3 -melamine is obtained after drying.
Fifth, 2.5wt% RuCl 3/Ac-HNO3 -melamine was reduced by sodium borohydride to give 2.5wt% Ru/Ac-HNO 3 -melamine. First 0.325g 2.5wt%RuCl 3/Ac-HNO3 -melamine was added to 40mL of water and stirred. Then 0.014g of sodium borohydride was mixed with 20mL of water. An aqueous solution of sodium borohydride was then slowly added dropwise to the 2.5wt% RuCl 3/Ac-HNO3 -melamine suspension over 10 min. The obtained liquid is filtered, and the obtained solid is dried to obtain 2.5wt% Ru/Ac-HNO 3 -melamine catalyst.
Reaction part we used a one-step process:
15mL of water is firstly mixed with 0.86465g of phosphoric acid (H 3PO4), 0.3047g of chitin is added, then 0.1g of 2.5 wt% Ru/Ac-HNO 3 -melamine catalyst is added, and the mixture is reacted for 2 hours under the hydrogen condition of 3.0MPa at the temperature of 250 ℃ to obtain the organic amine.
The types of organic amine obtained in examples 9 to 16 and the corresponding yields are shown in FIG. 2.

Claims (4)

1.一种海洋生物质两步法转化制备生物基胺类化合物的方法，其特征在于，包括以下步骤：1. A method for preparing bio-based amine compounds by two-step conversion of marine biomass, characterized in that it comprises the following steps: 1)将30％～68％的硝酸水溶液与0.05～0.25质量当量的活性炭，即Ac，混合，在60～100℃下100～1000rpm搅拌1～24h即可得到Ac-HNO3；将Ac-HNO3与三聚氰胺按照1：1～1：5质量配比混合研磨后置于管式炉里，氮气流速0.1～200mL/min，然后温度从25℃升温到400～600℃，保持120～360分钟，降温后可获得催化剂载体Ac-HNO3-melamine；将Ac与三聚氰胺，即melamine，按照1：1～1：5质量配比混合研磨后置于管式炉里，氮气流速0.1～200mL/min，然后温度从25℃升温到400～800℃，保持0.5～10h，降温后可获得催化剂载体Ac-melamine；将RuCl3于丙酮中溶解，并分别与催化剂载体Ac、AC-HNO3、Ac-melamine、Ac-HNO3-melamine以0.5％～10％的Ru质量负载率进行混合，搅拌直至液体搅干后，即分别获得RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine；通过相当于Ru质量1～10倍的氢氧化钠水解RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine分别得到RuOx/Ac、RuOx/Ac-HNO3、RuOx/Ac-melamine、RuOx/Ac-HNO3-melamine；通过相当于Ru质量0.1～100倍的硼氢化钠还原RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine分别得到Ru/Ac、Ru/Ac-HNO3、Ru/Ac-melamine、Ru/Ac-HNO3-melamine；1) Mix 30% to 68% nitric acid aqueous solution with 0.05 to 0.25 mass equivalent of activated carbon, i.e., Ac, and stir at 60 to 100° C. and 100 to 1000 rpm for 1 to 24 hours to obtain Ac-HNO 3 ; grind Ac-HNO 3 and melamine in a mass ratio of 1:1 to 1:5, and place in a tube furnace, with a nitrogen flow rate of 0.1 to 200 mL/min, and then heat from 25° C. to 400 to 600° C., maintain for 120 to 360 minutes, and cool down to obtain the catalyst carrier Ac-HNO 3 -melamine; Ac and melamine, i.e., melamine, are mixed and ground in a mass ratio of 1:1 to 1:5, and then placed in a tube furnace with a nitrogen flow rate of 0.1 to 200 mL/min, and then the temperature is raised from 25°C to 400 to 800°C, maintained for 0.5 to 10 hours, and the catalyst carrier Ac-melamine is obtained after cooling; RuCl 3 is dissolved in acetone, and mixed with the catalyst carrier Ac, AC-HNO 3 , Ac-melamine, and Ac-HNO 3 -melamine at a Ru mass loading rate of 0.5% to 10%, and stirred until the liquid is dried to obtain RuCl 3 /Ac, RuCl 3 /Ac-HNO 3 , RuCl 3 /Ac-melamine, and RuCl 3 /Ac-HNO 3 -melamine, respectively; RuCl 3 /Ac, RuCl 3 /Ac-HNO 3 , RuCl 3 /Ac-melamine, and RuCl 3 /Ac-HNO 3 -melamine are hydrolyzed with sodium hydroxide equivalent to 1 to 10 times the mass of Ru /Ac-melamine, RuCl 3 /Ac-HNO 3 -melamine to obtain RuO x /Ac, RuO x /Ac-HNO 3 , RuO x /Ac-melamine, RuO x /Ac-HNO 3 -melamine respectively; RuCl 3 /Ac, RuCl 3 /Ac-HNO 3 , RuCl 3 /Ac-melamine, RuCl 3 /Ac-HNO 3 -melamine are reduced by sodium borohydride equivalent to 0.1 to 100 times the mass of Ru to obtain Ru/Ac, Ru/Ac-HNO 3 , Ru/Ac-melamine, Ru/Ac-HNO 3 -melamine respectively; 2)将75～95％水、1～30％磷酸、0.5～30％几丁质混合，置于反应釜里，在80～150℃，0.1～10MPa氮气条件下反应1～8小时；2) Mix 75-95% water, 1-30% phosphoric acid and 0.5-30% chitin, place in a reaction kettle, and react for 1-8 hours at 80-150° C. and 0.1-10 MPa nitrogen; 3)等反应液冷却后，加入相当于上述反应液0.1～10％的催化剂的一种或多种，再次放入反应釜中，在200～250℃，1.0～3.0MPa氢气条件下反应1～10小时，得到磷酸化的有机胺。3) After the reaction liquid is cooled, one or more catalysts equivalent to 0.1-10% of the above reaction liquid are added, and the mixture is put into the reactor again to react for 1-10 hours at 200-250° C. and 1.0-3.0 MPa of hydrogen to obtain a phosphorylated organic amine. 2.一种海洋生物质一步法转化制备生物基胺类化合物的方法，其特征在于，包括以下步骤：2. A method for preparing bio-based amine compounds by one-step conversion of marine biomass, characterized in that it comprises the following steps: 1)将30％～68％的硝酸水溶液与0.05～0.25质量当量的活性炭，即Ac，混合，在60～100℃下100～1000rpm搅拌1～24h即可得到Ac-HNO3；将Ac-HNO3与三聚氰胺按照1：1～1：5质量配比混合研磨后置于管式炉里，氮气流速0.1～200mL/min，然后温度从25℃升温到400～600℃，保持120～360分钟，降温后可获得催化剂载体Ac-HNO3-melamine；将Ac与三聚氰胺，即melamine，按照1：1～1：5质量配比混合研磨后置于管式炉里，氮气流速0.1～200mL/min，然后温度从25℃升温到400～800℃，保持0.5～10h，降温后可获得催化剂载体Ac-melamine；将RuCl3于丙酮中溶解，并分别与催化剂载体Ac、AC-HNO3、Ac-melamine、Ac-HNO3-melamine以0.5％～10％的Ru质量负载率进行混合，搅拌直至液体搅干后，即分别获得RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine；通过相当于Ru质量1～10倍的氢氧化钠水解RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine分别得到RuOx/Ac、RuOx/Ac-HNO3、RuOx/Ac-melamine、RuOx/Ac-HNO3-melamine；通过相当于Ru质量0.1～100倍的硼氢化钠还原RuCl3/Ac、RuCl3/Ac-HNO3、RuCl3/Ac-melamine、RuCl3/Ac-HNO3-melamine分别得到Ru/Ac、Ru/Ac-HNO3、Ru/Ac-melamine、Ru/Ac-HNO3-melamine；1) Mix 30% to 68% nitric acid aqueous solution with 0.05 to 0.25 mass equivalent of activated carbon, i.e., Ac, and stir at 60 to 100° C. and 100 to 1000 rpm for 1 to 24 hours to obtain Ac-HNO 3 ; grind Ac-HNO 3 and melamine in a mass ratio of 1:1 to 1:5, and place in a tube furnace, with a nitrogen flow rate of 0.1 to 200 mL/min, and then heat from 25° C. to 400 to 600° C., maintain for 120 to 360 minutes, and cool down to obtain the catalyst carrier Ac-HNO 3 -melamine; Ac and melamine, i.e., melamine, are mixed and ground in a mass ratio of 1:1 to 1:5, and then placed in a tube furnace with a nitrogen flow rate of 0.1 to 200 mL/min, and then the temperature is raised from 25°C to 400 to 800°C, maintained for 0.5 to 10 hours, and the catalyst carrier Ac-melamine is obtained after cooling; RuCl 3 is dissolved in acetone, and mixed with the catalyst carrier Ac, AC-HNO 3 , Ac-melamine, and Ac-HNO 3 -melamine at a Ru mass loading rate of 0.5% to 10%, and stirred until the liquid is dried to obtain RuCl 3 /Ac, RuCl 3 /Ac-HNO 3 , RuCl 3 /Ac-melamine, and RuCl 3 /Ac-HNO 3 -melamine, respectively; RuCl 3 /Ac, RuCl 3 /Ac-HNO 3 , RuCl 3 /Ac-melamine, and RuCl 3 /Ac-HNO 3 -melamine are hydrolyzed with sodium hydroxide equivalent to 1 to 10 times the mass of Ru /Ac-melamine, RuCl 3 /Ac-HNO 3 -melamine to obtain RuO x /Ac, RuO x /Ac-HNO 3 , RuO x /Ac-melamine, RuO x /Ac-HNO 3 -melamine respectively; RuCl 3 /Ac, RuCl 3 /Ac-HNO 3 , RuCl 3 /Ac-melamine, RuCl 3 /Ac-HNO 3 -melamine are reduced by sodium borohydride equivalent to 0.1 to 100 times the mass of Ru to obtain Ru/Ac, Ru/Ac-HNO 3 , Ru/Ac-melamine, Ru/Ac-HNO 3 -melamine respectively; 2)将75～95％水、1～30％磷酸、0.5～30％几丁质、0.1～10％的上述催化剂的一种或多种混合，置于反应釜里，在200～250℃，1.0～3.0MPa氢气条件下反应1～10小时，得到磷酸化的有机胺。2) 75-95% water, 1-30% phosphoric acid, 0.5-30% chitin, and 0.1-10% of one or more of the above catalysts are mixed, placed in a reaction kettle, and reacted for 1-10 hours at 200-250° C. and 1.0-3.0 MPa hydrogen to obtain a phosphorylated organic amine. 3.如权利要求1-2所述的方法，其特征在于，所述Ac-HNO3与三聚氰胺的质量比为1：5～5：1，管式炉温度从30℃升温到600℃，保持2h。3. The method according to claim 1-2, characterized in that the mass ratio of Ac- HNO3 to melamine is 1:5 to 5:1, and the temperature of the tube furnace is increased from 30°C to 600°C and maintained for 2 hours. 4.一种根据权利要求1-2所述的方法制得的有机胺，其特征在于，所述有机胺中包含线性胺和环状胺，所述线性胺为乙胺、丙胺、丁胺中的一种或多种，所述环状胺为吡咯烷、2-甲基吡咯烷、2，5-二甲基吡咯烷、哌啶、2-甲基哌啶中的一种或多种，所述有机胺的产率为5～99％。4. An organic amine prepared according to the method of claim 1-2, characterized in that the organic amine comprises linear amine and cyclic amine, the linear amine is one or more of ethylamine, propylamine, and butylamine, the cyclic amine is one or more of pyrrolidine, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, and 2-methylpiperidine, and the yield of the organic amine is 5 to 99%.
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Citations (2)

* Cited by examiner, † Cited by third party
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US4431836A (en) * 1981-02-23 1984-02-14 Uop Inc. Hydrogenation using chitin and chitosan based immobilized metal catalysts
CN1820843A (en) * 2006-03-03 2006-08-23 厦门大学 Mixed ruthenium-based ammonia synthesis catalyst and preparation method thereof

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US4431836A (en) * 1981-02-23 1984-02-14 Uop Inc. Hydrogenation using chitin and chitosan based immobilized metal catalysts
CN1820843A (en) * 2006-03-03 2006-08-23 厦门大学 Mixed ruthenium-based ammonia synthesis catalyst and preparation method thereof

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